JP2005060538A - Polyester resin composition for profile extrusion molding and molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition for profile extrusion molding, whereby the continuous productivity of the profile extrusion is improved through the formulation for reducing the adhesion of the polyester resin to the sizing die in the sizing die processing step of the profile extrusion, whereby the dimensional accuracy and surface smoothness (elimination of chatter marks) of a profile extrusion product are improved, whereby the warpage of the product during the continuous production is ameliorated, and whereby the profile accuracy in corner/edge portions of the product between the die and the sizing is improved through amelioration of resin sags at the time of the profile extrusion molding; and to provide a molded article using the same. <P>SOLUTION: The polyester resin composition for profile extrusion molding contains a polyester resin and a resin (I) having a melt flow rate (MFR) of ≤30 g/10min. Preferably, the composition further contains a reactive compound containing a glycidyl group and/or an isocyanate group by two or more per molecule. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyester resin composition suitable for profile extrusion molding. Specifically, profile extrusion processing, improvement of profile extrusion continuous productivity by reducing sizing mold adhesion of discharged resin, improvement of dimensional accuracy and surface smoothness (removal of chatter) of profile extrusion products, product warpage during continuous production The present invention relates to a polyester resin composition that improves the shape accuracy of product corners and edges between die and sizing by improvement and resin sag improvement during profile extrusion, and a molded product using the same.

  Conventionally, when manufacturing window frames, rain gutters and the like as building material products with plastics, profile extrusion molding has been adopted. The resin used for the profile extrusion molding is required to follow the complicated shape of the die and have a good dimensional accuracy. Until now, vinyl chloride resin and polyolefin resin have been generally used from the viewpoint of cost in addition to these two characteristics. In particular, in applications that require adhesion, polyolefins that do not have good adhesion to various adhesives are generally difficult to use, and vinyl chloride is the main resin material. However, for example, in recent years, there has been a movement to replace vinyl chloride resin with other materials due to environmental problems. Among a number of alternative materials, polyester is a powerful material in terms of its physical properties, environmental suitability, adhesive properties, and price. However, there is a big problem in replacing vinyl chloride used for profile extrusion with polyester.

  In general, the profile extrusion process starts with an extrusion process and proceeds in the order of a profile mold process, a sizing process, a cooling process, a cutting process, and a secondary processing process. In particular, when a polyester resin typified by PET (polyethylene terephthalate) resin is applied to those processes, the problem is that “the melt viscosity of the discharged resin that has undergone the extrusion process, that is, the deformed mold process, is very low. The problem is that it adheres to the sizing mold due to its properties and clogs the resin and stops continuous production. Furthermore, the problem is that the dimensional accuracy of the product shape deteriorates in the sizing process, and the resin melting in the sizing mold. Resin stickiness during sizing mold processing such as “problems that cause chattering on the surface of the molded product due to characteristics” (“problems in which product warpage occurs in the direction of profile extrusion”) There are a lot of problems with.

  In the profile extrusion process, unlike the normal extrusion process, the shape of the molding material is very complicated, the shape is relatively small, the dimensions are very precise, and the shape is hollow. It may be a product that combines all cases. Designs that require fine dimensional accuracy at the corners and edges of sizing molds in the case of sticky polyester resins, which often have edges at the edges of sharp corners or open parts of profile extrusion products. Since the resin clogging phenomenon tends to become apparent at the part, continuous production for a long time becomes difficult, and it becomes impossible to supply a profile-extruded product having substantially good dimensional accuracy.

  Usually, in order to solve this problem, attempts have been made to reduce the apparent tackiness and forcibly adjust the shape by using a multi-plate sizing method or a vacuum sizing method in the sizing process. However, in this case, since the polymer is forcedly deformed during cooling, there is a problem that residual stress remains in the product, and stress cracking occurs due to the solvent, solvent vapor, and rapid temperature change in the product. Therefore, in order to suppress this problem, it is required to improve the adhesiveness in the molten state of the polyester as compared with the normal extrusion process.

  The conventional literature in this application is that the polymer is branched, the viscosity of the resin is reduced in the high shear region in the die, and the melt strength is maintained by restoring the viscosity in the non-shear region after extrusion, thereby improving the profile extrudability. Although the method to improve is proposed, the problem in the above sizing processes is not mentioned (for example, refer patent document 1).

International Publication No. 00/77096 (Claims etc.)

  The object of the present invention is to improve the continuous extrusion productivity of the profile resin by reducing the sizing mold adhesion of the polyester resin during the profile extrusion sizing mold processing process, improve the dimensional accuracy of the profile extrusion product, and improve the surface smoothness (removal of chatter). , Polyester resin composition for profile extrusion processing that improves the shape accuracy of product corners and edges between dies and sizing by improving product warpage during continuous production and improving resin sag during profile extrusion It is to provide a molded product.

  As a result of intensive studies to achieve the above problems, the present inventors have found that the above problems can be solved by combining a polyester resin and a resin (I) having a melt flow rate (MFR) of 20 g / 10 min or less. Was completed. That is, the present invention is the following polyester resin composition for profile extrusion molding and a molded article using the same.

(1) A polyester resin composition for profile extrusion processing, comprising a polyester resin and a resin (I) having a melt flow rate (MFR) of 30 g / 10 min or less.

(2) Resin (I) is polyethylene, polypropylene, α-olefin copolymer, ethylene polymer (ethylene vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylate copolymer, ethylene-methacrylic acid) The polyester resin composition for profile extrusion processing according to (1), comprising at least one selected from the group consisting of a copolymer), a styrene elastomer, and an ethylene ionomer copolymer.

(3) The polyester resin composition for profile extrusion processing according to (1), wherein the resin (I) contains glycidyl methacrylate.

(4) The polyester resin for profile extrusion processing according to any one of (1) to (3), further comprising a reactive compound containing two or more glycidyl groups and / or isocyanate groups per molecule. Composition.

(5) The polyester resin composition for profile extrusion processing according to (4), wherein the reactive compound has a weight average molecular weight of 200 to 500,000.

(6) The reactive compound is (X) 20 to 99% by weight of vinyl aromatic monomer, (Y) 1 to 80% by weight of hydroxyalkyl (meth) acrylate or glycidylalkyl (meth) acrylate, and (Z) The polyester resin composition for profile extrusion processing according to (5), comprising 0 to 40% by weight of alkyl (meth) acrylate.

(7) The polyester resin composition for profile extrusion processing according to any one of (1) to (6), wherein the polyester resin is amorphous.

(8) The amorphous polyester contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms in an amount of 50 mol% or more of each of the acid component and the glycol component. The polyester resin composition for profile extrusion processing according to (7).

(9) The polyester resin composition for profile extrusion processing according to (8), wherein the aromatic dicarboxylic acid having 8 to 14 carbon atoms is terephthalic acid and / or isophthalic acid.

(10) The group in which the aliphatic or alicyclic glycol having 2 to 10 carbon atoms is composed of ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol and 2-methyl-1,3-propanediol. The polyester resin composition for profile extrusion processing according to (8), wherein the polyester resin composition is at least one selected from the group consisting of more than one.

(11) The total number of moles of polyfunctional compound units derived from at least one of polyfunctional compounds having 3 or more carboxyl groups, hydroxyl groups and / or ester-forming groups thereof as the total structural units of the polyester. The polyester resin composition for profile extrusion processing according to any one of (1) to (10), wherein 0.001 to 5 mol% is contained.

(12) A molded product obtained by profile-extrusion molding of the resin composition according to any one of (1) to (11).

  The present invention improves profile extrusion continuous productivity by sizing the profile extrusion process / discharge resin, improves the dimensional accuracy / surface smoothness (removal of chatter) of profile extrusion products, improves product warpage during continuous production, and profile extrusion. Improve shape accuracy of product corners and edges between die and sizing by improving resin sag during processing, further improve impact resistance of molded products, and exhibit sufficient mechanical properties It is.

  The polyester resin composition for profile extrusion processing of the present invention preferably contains a polyester resin and a resin (I) having a melt flow rate (MFR) of 30 g / 10 min or less, and further contains 1 glycidyl group and / or isocyanate group. It is desirable to contain two or more reactive compounds per molecule. Here, the melt flow rate (MFR) is a measurement method defined as Method A in JIS K7210. However, it is necessary to measure the sample in a dried state with a moisture content of 0.02 wt% or less. The measurement temperature is usually measured at 190 ° C, but in the case of a resin that does not soften at 190 ° C, it is measured at 230 ° C. The load is 2160 g. The unit is g / 10 minutes.

  According to this formulation, the problem is that the discharged resin that has passed through the extrusion process and the profile mold process adheres to the sizing mold, causing clogging of the resin and stopping continuous production, and the problem that the sizing process deteriorates the dimensional accuracy of the product shape. , "Problems that cause chatter on the surface of the molded product due to the resin melting characteristics in the sizing mold", "Problems in which product warpage occurs in the direction of profile extrusion molding", etc. It can be improved.

  In other words, the polyester resin and the resin (I) having a melt flow rate (MFR) of 30 g / 10 min or less are contained, so that the sizing mold can be smoothly maintained while maintaining the resin fluidity necessary for determining fine dimensions. It is possible to pass through. As a result, adhesion to the sizing mold can be reduced, enabling continuous production, and excellent resin flowability in the sizing mold, resulting in fine dimensional accuracy and a resin adhesive reduction effect. The product surface smoothness was realized by the excellent sizing mold lubricity, and the product warpage problem was solved by the effects of uniform and reduced resin wettability and adhesiveness on the sizing mold wall surface.

  The resin (I) having a melt flow rate (MFR) of 30 g / 10 min or less used in the present invention has a polyester resin-based tackiness present in a sizing mold at a high temperature in a profile extrusion sizing mold processing process. This reduces the processability and lubricity within the mold. Such a resin preferably has a melt flow rate (MFR) of 30 g / 10 min or less, more preferably 25 g / 10 min, and most preferably 20 g / 10 min or less. If the MFR exceeds 30 g / 10 min, the adhesiveness of the resin to be added will increase when it is melted, and it will adhere to the sizing mold in the middle of the profile extrusion process and will not pass smoothly through the mold. Inferior.

  The resin having a melt flow rate (MFR) of 30 g / 10 min or less is not particularly limited. For example, polyethylene, polypropylene, α-olefin copolymer, ethylene-ethyl acrylate copolymer (EEA), ethylene vinyl acetate copolymer (EVA), styrene-based elastomer, ethylene-based ionomer copolymer, and the like may be used, and these may be used alone or in combination of two or more. Of these, those containing glycidyl methacrylate are particularly preferred from the viewpoint of improving the compatibility with the polyester resin and preventing the deterioration of the mechanical properties of the polyester resin composition by micro-dispersing in the polyester matrix.

  The polyester resin composition for profile extrusion processing according to the present invention preferably contains 0.1 part by mass or more of the resin (I) with respect to 100 parts by mass of the polyester resin. If the resin (I) is less than 0.1 parts by mass, the adhesiveness of the resin composition will increase when it is melted, and it will adhere to the sizing mold in the middle of the profile extrusion molding process and will not pass smoothly through the mold. Continuous productivity may be inferior. Preferably it is 1 mass part or more, More preferably, it is 3 mass parts or more. The upper limit is not particularly limited, but it is 40 parts by mass or less, preferably 20 parts by mass or less in consideration of transparency, mechanical properties, and the like.

  Any polyester resin may be used as long as it is composed of a dicarboxylic acid component and a glycol component.

  The polyester resin used in the present invention is preferably amorphous. If the polyester resin is amorphous, crystallization shrinkage hardly occurs in the sizing mold, so that it is possible to exhibit performance with excellent dimensional stability. Note that the term “amorphous” as used herein means that the temperature was raised from −100 ° C. to 300 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and then was lowered to −100 ° C. at 50 ° C./min. Subsequently, in the two temperature rising processes in which the temperature is raised from −100 ° C. to 300 ° C. at 20 ° C./min, neither indicates a melting peak. On the other hand, crystallinity refers to those showing a clear melting peak in either temperature rising process.

  The polyester resin used in the present invention preferably contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms as 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%. If both components are less than 50 mol%, the elongation and mechanical properties of the profile extrusion-molded product may be lowered.

  Furthermore, among the polyester resins, the aromatic dicarboxylic acid having 8 to 14 carbon atoms is preferably terephthalic acid and / or isophthalic acid. When these dicarboxylic acids are used, the elongation and mechanical properties of the profile extrusion-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 polyester resin 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 glycol having 2 to 10 carbon atoms is ethylene glycol or diethylene glycol. , Neopentyl glycol, cyclohexane dimethanol, 1,3-propanediol, and at least one selected from the group consisting of 2-methyl-1,3-propanediol in terms of versatility of obtaining raw materials and cost preferable. Moreover, what contains 50 mol% or more of ethylene glycol, and also 60 mol% or more is preferable in the tendency which improves the impact resistance of a molded article.

  Suitable amorphous polyester combinations are specifically terephthalic acid / isophthalic acid // ethylene glycol = 90-70 / 10-30 // 100 mol%, terephthalic acid // ethylene glycol / 1,2-propylene Glycol = 100 // 80 to 50/20 to 50 mol%, terephthalic acid / isophthalic acid // ethylene glycol / 1,3-propylene glycol = 95 to 80/5 to 20 // 90 to 70/10 to 30 mol% Terephthalic acid / isophthalic acid // ethylene glycol / 1,4-butanediol = 95 to 70/5 to 30 // 90 to 50/10 to 50 mol%, terephthalic acid // ethylene glycol / 2-methyl-1, 3-propanediol = 100 // 60 to 80/40 to 20 mol%, terephthalic acid / isophthalic acid // ethylene glycol Alcohol / 2-methyl-1,3-propanediol = 95-80 / 5-5 / 70-90 / 30-10 mol%, terephthalic acid / ethylene glycol / neopentyl glycol = 100 // 85-60 / 15-40 mol%, terephthalic acid / isophthalic acid // ethylene glycol / neopentyl glycol = 95-80 / 5-20 // 90-70 / 10-30 mol%, terephthalic acid // ethylene glycol / diethylene glycol = 100 // 75 to 50/25 to 50 mol%, terephthalic acid / isophthalic acid // ethylene glycol / diethylene glycol = 95 to 80/5 to 20 // 90 to 75/10 to 25 mol%, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol = 100 // 80 to 60/20 to 40 mol% It is.

  Furthermore, terephthalic acid // ethylene glycol / neopentyl glycol = 100 // 85-60 / 15-40 mol%, terephthalic acid / isophthalic acid // ethylene glycol / neopentyl glycol = 95-80 / 5-20 // 90-70 / 10-30 mol%, terephthalic acid // ethylene glycol / diethylene glycol = 100 // 75-50 / 25-50 mol%, terephthalic acid / isophthalic acid // ethylene glycol / diethylene glycol = 95-80 / 5 More preferably, the ratio is 20 // 90 to 75/10 to 25 mol%, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol = 100 // 80 to 60/20 to 40 mol%.

  Among these, combinations of 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)) are irregularly shaped. It is easy to achieve both extrudability and transparency of the molded product, and the combination of ethylene glycol and neopentyl glycol is most preferable.

  The polyester resin is copolymerized with other polyhydric alcohol components other than the above-mentioned ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol, and 2-methyl-1,3-propanediol. For example, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, nonanediol, dimer Diol, bisphenol A ethylene oxide adduct and propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecane dimethanol, neo Emissions chill hydroxypivalic acid ester, 2,2,4-trimethyl-1,5-pentanediol, trimethylolpropane and the like can be used.

  For the polyester resin used in the present invention, a polyfunctional compound having 3 or more carboxyl groups, hydroxyl groups or ester-forming groups thereof (for example, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, etc.) is added to the polyester acid. It is preferable to contain 0.001 to 5 mol% of each of the component and glycol component in order to improve the profile extrusion moldability.

  The number average molecular weight of the polyester resin used for this invention becomes like this. Preferably it is 15000-40000, More preferably, it is 18000-35000, More preferably, it is 20000-35000. If the number average molecular weight is less than 15000, the strength of the molded article is insufficient due to insufficient resin cohesive strength, and it may become brittle and cannot be used. On the other hand, if it exceeds 40,000, the melt viscosity will increase too much, so that the optimum temperature for profile extrusion will also increase, and as a result, profile extrusion may be deteriorated.

The acid value of the polyester resin used in the present invention is preferably 100 equivalents / 10 ⁶ g or less, more preferably 50 equivalents / 10 ⁶ g or less, and still more preferably 40 equivalents / 10 ⁶ g or less. On the other hand, the lower the lower limit, the better. If the acid value exceeds 100 equivalents / 10 ⁶ g, hydrolysis of the resin is further promoted when the resin is heated during profile extrusion, and the mechanical strength of the finished molded product is lowered. Further, as the decomposition of the resin proceeds, there is a possibility that the resin adhesiveness in the sizing mold will also progress and deteriorate.

  In such a resin composition, the processing condition control range for expressing the “melt strength enhancement effect” that depends on the increase in molecular weight due to the reaction with the polyester resin is expanded, and the melt strength can be adjusted. In order to satisfy the bending whitening resistance of the product and the suppression of bleed-out of the unreacted product to the product surface layer, the weight average molecular weight is 200 to 500,000, the preferred lower limit is 500 or more, more preferably 700 or more, most preferably Is 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, voids are likely to occur due to poor compatibility between the melt strength improver and the amorphous polyester, and the possibility of whitening will increase.

  The reactive compound used in the present invention preferably has at least two functional groups capable of reacting with the hydroxyl group or carboxyl group of the polyester per molecule in terms of partially introducing crosslinking into the entire resin. 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 produced during the melt extrusion, an effect of improving the melt strength can be obtained by partially forming a crosslinked product. It is.

  Specific examples of functional groups possessed by the reactive compound include, for example, isocyanate groups, glycidyl groups, carboxyl groups, carboxylic acid metal salts, ester groups, hydroxyl groups, amino groups, carbodiimide groups, glycidyl groups, and the like, and Examples of the lactone, lactide, and lactam include functional groups that undergo ring-opening addition with a polyester terminal, and any functional group that reacts with a hydroxyl group or a carboxyl group during melt extrusion may be used. In addition, different types of functional groups may be present in one molecule. Among these, a preferable functional group includes a glycidyl group or an isocyanate group depending on the speed of the reaction.

Any form of the functional group 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 described above includes (X) 20 to 99% by weight of vinyl aromatic monomer, (Y) 1.0 to 80% by weight of hydroxyalkyl (meth) acrylate and / or glycidylalkyl (meth) acrylate. And (Z) a copolymer comprising 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, the reactivity with the polyester resin is lowered, and there is a risk of causing a resin sag during molding.

  The addition amount of the reactive compound can be individually selected depending on the molecular weight and the number of functional groups introduced, but is preferably 0.1% by weight or more and 20% by weight or less when the total composition is 100 parts by weight, and the lower limit is 0.5 More preferably, the upper limit is 15% by weight or less. If the content is less than 0.1% by weight, the targeted resin sag suppressing effect may not be exhibited, and if it exceeds 20% by weight, the mechanical properties of the product may be affected.

  Regarding the method of adding the reactive compound, there are a method of press-fitting into a polyester resin at the time of melt extrusion, a method of adding and blending the polyester resin pellets before extrusion, a method of once adding and kneading the polyester resin, and a method of extruding again. Though possible, it can be implemented in any way.

The melt viscosity of the polyester resin composition of the present invention at 220 ° C. and a shear rate of 100 sec ⁻¹ is preferably 6,000 to 600,000 dPa · sec, more preferably 7,000 to 100,000 dPa · sec, and further preferably 8,000 to 50,000 dPa · sec. is there. If the melt viscosity is less than 6000 dPa · sec, resin sag during processing may deteriorate. On the other hand, if it exceeds 600,000 dPa · sec, the melt viscosity is too high and the productivity is lowered, which may be impractical.

  The polyester resin composition of the present invention is used by blending an antioxidant in order to suppress thermal deterioration of the polyester resin during processing (to prevent the resin from being colored or sag due to thermal deterioration). desirable. 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 upper limit of the amount of the phenolic antioxidant is preferably 1.0 part by weight or less, particularly preferably 0.8 part by weight or less, while the preferable lower limit is 0.01 part by weight or more, particularly preferably 0.02 part by weight. That's it. 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 compounding amount of the organic phosphite compound is preferably 3.0 parts by weight or less, particularly preferably 2.0 parts by weight or less, and the preferred lower limit is 0.01 parts by weight or more, particularly preferably 0.02. It is more than part by weight. 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 polyester resin composition, polybutadiene, polyisoprene, butadiene-polyisoprene copolymer are used. Conjugated diene polymers such as acrylonitrile-isoprene copolymer, acrylate ester-butadiene copolymer, acrylate ester-butadiene-styrene copolymer, acrylate ester-isoprene copolymer; Hydrogenated product of: olefin rubber such as ethylene-propylene copolymer; acrylic acid rubber such as polyacrylate ester; polyorganosiloxane; thermoplastic elastomer; thermoplastic elastomer having epoxy group, carboxyl group, isocyanate group, etc .; Ethylene ionomer Body and the like, which one or are used in two or more. 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.

  Other components can be appropriately added to the polyester resin composition used in the present invention 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.

  As a condition for extruding the resin composition of the present invention, it is necessary to mix the polyester resin and the multilayer structure polymer particles (I), and in some cases, it is necessary to mix the reactive compound in a molten state. We need something that works. Specifically, there are a single screw extruder, a twin screw extruder, and the like, but these resins may be mixed sufficiently. Furthermore, a means for adding and kneading the polyester resin and the multilayer structure polymer particles (I), and in some cases, a reactive compound, and then re-extrusion molding the kneaded polymer can be used without any problem. As the temperature condition, any temperature can be used as long as the polyester resin used for extrusion can be melt-flowed. However, due to the nature of the polyester resin, it is considered to be 100 ° C. or higher and 350 ° C. or lower, more preferably 150 ° C. or higher and 300 ° C. or lower. C. or lower is preferred. 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 discharge amount in the profile extrusion and other conditions can be set by appropriately adjusting to the appropriate conditions of the machine base.

  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.

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

  Number average molecular weight of polyester resin: Using polystyrene gel permeation chromatography with chloroform as an eluent, a polystyrene equivalent measurement value was obtained.

Resin composition: The composition of the amorphous copolyester resin is 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. did.

  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.

  Acid value: Obtained by dissolving 1 g of resin in 30 ml of chloroform and titrating with 0.1N potassium hydroxide ethanol solution. Phenolphthalein was used as the indicator.

<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 transesterification 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 of the polyester resin (A), the dicarboxylic acid component has a composition of 63 mol% terephthalic acid, 10 mol% isophthalic acid, 27 mol% adipic acid, and the diol component has a composition of 100 mol% 1,4-butanediol. It was. 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 polyester resins (B) and (C) were produced in the same manner as the 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 condenser. 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 carried out at 130 Pa or lower for 55 minutes to obtain amorphous polyester (D).

As a result of NMR analysis, the amorphous polyester (D) had a composition of a dicarboxylic acid component of 100 mol% terephthalic acid, a diol component of 80 mol% ethylene glycol, and 20 mol% neopentyl glycol. The glass transition temperature was 78 ° C., the number average molecular weight was 28000, and the acid value was 30 equivalents / 10 ⁶ g.

  Amorphous polyesters (E) to (K) 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)

<Resin (I)>
Commercially available materials listed in Table 2 were used as they were.

<Synthesis Example of Reactive Compound (L)>
In a reactor equipped with a stirrer, thermometer, reflux apparatus and quantitative dropping apparatus, 50 parts of methyl ethyl ketone was added and heated to 70 ° C., then 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 (L).

  As a result of NMR analysis, this reactive compound (L) 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.

<Example 1>
100 parts by weight of polyester (A), 10 parts by weight of resin (I)-(a), bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate 0 as a stabilizer .3 parts by weight and 0.1 part by weight of glycerin monostearate ester were mixed, and the mixture was set to an extruder (L / D = 30, screw diameter = 20 mm, full) at a rotation speed of 30 rpm and a total barrel temperature of 180 ° C. It knead | mixed by the flight and the compression ratio 2.0). Next, the kneaded resin composition is attached to a single screw extruder (L / D = 25, full flight screw, screw diameter 65 mm) with a die lip for producing the molded product shown in FIG. A sizing mold that determines the final dimensions of the extruded product is attached, and the molded product is molded by a special extrusion molding equipment equipped with a take-off machine via a water tank. The sizing mold processing status of the molded product, product dimensional accuracy, and surface smoothness The product was warped.

  In addition, the evaluation criteria of the sizing die processing situation, product accuracy, and surface smoothness were as follows.

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

Evaluation of product warpage: The presence or absence of warpage in the vertical and horizontal directions with respect to the extrusion direction of the profile extrusion product was evaluated as follows.
Existence: Existence of warpage in the vertical and horizontal directions with respect to the extrusion molding direction Existence: Table 3 shows the evaluation results of the resin-free melt strength of warpage in the vertical and horizontal directions with respect to the extrusion molding direction.

<Examples 2 to 12, Comparative Examples 1 to 13>
Using the raw materials described in Tables 2 and 3, molding was performed in the same manner as in Example 1 under the conditions described in the respective tables.

The stabilizers and lubricants listed in Tables 3 and 4 mean the following compounds.
P: Bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate Q: Glycerin monostearate Further, the blending ratio in the table is {polyester resin + resin (I) + Reactive compound} was defined as 100 weight ratio, and stabilizers and additives were represented as addition amounts with respect to the 100 weight ratio.

  As can be seen from Tables 3 and 4, Examples 1 to 12 are profile extrusion processing / improving the profile extrusion continuous productivity by improving the sizing die adhesion effect of the discharged resin, improving the dimensional accuracy of the profile extrusion product, and improving the surface smoothness. (Removal of chatter), improvement of product warpage during continuous production, and improvement of the shape accuracy of product corners and edges between dies and sizing by improved resin sag during profile extrusion.

  On the other hand, since Comparative Examples 1-13 do not contain resin (I), it is outside the scope of the present invention. In Comparative Examples 8, 9, and 11, the addition of the reactive compound improves the prevention of resin sagging and the product dimensional accuracy slightly, but the sizing mold processing condition is poor and the continuous productivity is poor. In other comparative examples, the adhesiveness at the time of melting unique to the polyester-based resin was affected, so that the adhesion to the sizing mold was increased, and it was impossible to continuously produce the profile extrusion. In addition, since the resin flowability in the sizing mold is not stable, the dimensional accuracy and surface smoothness of the profile extrusion product deteriorated, and further, the problem of product warpage occurred, and the profile extrusion product became unsuitable. .

  As explained above, profile extrusion processing / improving profile extrusion continuous productivity by sizing resin, dimensional accuracy / surface smoothness improvement (removal of chatter), profile warpage improvement during continuous production, and Improve shape accuracy of product corners and edges between dies and sizing by improving resin sag during profile extrusion, and improve impact resistance of molded products, and exhibit sufficient mechanical properties It can be made and has a significant contribution to the industry.

It is sectional drawing of a profile extrusion molded product. A hollow molded product is shown.

Claims (12)

  A polyester resin composition for profile extrusion molding, comprising a polyester resin and a resin (I) having a melt flow rate (MFR) of 30 g / 10 min or less.   Resin (I) is polyethylene, polypropylene, α-olefin copolymer, ethylene polymer (ethylene vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylate copolymer, ethylene-methacrylic acid copolymer) 2) The polyester resin composition for profile extrusion processing according to claim 1, comprising at least one selected from the group consisting of styrene elastomers and ethylene ionomer copolymers.   The polyester resin composition for profile extrusion processing according to claim 1, wherein the resin (I) contains glycidyl methacrylate.   The polyester resin composition for profile extrusion processing according to any one of claims 1 to 3, further comprising a reactive compound containing two or more glycidyl groups and / or isocyanate groups per molecule.   The reactive compound has a weight average molecular weight of 200 to 500,000, and the polyester resin composition for profile extrusion processing according to claim 4.   The reactive compound is (X) 20-99 wt% vinyl aromatic monomer, (Y) 1-80 wt% hydroxyalkyl (meth) acrylate or glycidylalkyl (meth) acrylate, and (Z) 0-40 The polyester resin composition for profile extrusion processing according to claim 5, comprising an alkyl (meth) acrylate in weight percent.   The polyester resin composition for profile extrusion molding according to any one of claims 1 to 6, wherein the polyester resin is amorphous.   The amorphous polyester contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms in an amount of 50 mol% or more of each of the acid component and the glycol component. 8. A polyester resin composition for profile extrusion processing according to item 7.   The polyester resin composition for profile extrusion processing according to claim 8, wherein the aromatic dicarboxylic acid having 8 to 14 carbon atoms is terephthalic acid and / or isophthalic acid.   The aliphatic or alicyclic glycol having 2 to 10 carbon atoms is selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol and 2-methyl-1,3-propanediol. The polyester resin composition for profile extrusion processing according to claim 8, wherein the polyester resin composition is at least one or more.   In the total number of moles of all the structural units of the polyester, the polyester has a polyfunctional compound unit derived from at least one of the polyfunctional compounds having three or more carboxyl groups, hydroxyl groups and / or ester forming groups thereof. The polyester resin composition for profile extrusion processing according to any one of claims 1 to 10, which comprises 0.001 to 5 mol%.   A molded product obtained by profile extrusion molding of the resin composition according to claim 1.

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