TW482798B - Crystal aromatic polyester resin pre-foamed particles - Google Patents

Abstract

Pre-foamed particles of crystalline aromatic polyester-based resin which is excellent in foaminess fusion bonding during foaminess molding, and an in-mold foamed product being improved particularly in fusion bonding ratio and mechanical strength and an foamed laminate using the pre-foamed particles. The pre-foamed particles have a bulk density of 0.01 to 1.0 g/cm<SP>3</SP> and a peak temperature of crystallization of 130 to 180 DEG C, and can be suitably used in in-mold foaming molding. The in-mold foamed product is formed by the in-mold foaming molding of the above pre-foamed particles, and the foamed laminate is prepared by laminating a film or sheet of an aromatic polyester-based resin directly on the above in-mold foamed product and forming them in one piece.

Description

482798

V. Description of the invention (1)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Technical Field of the Invention] The present invention relates to crystalline aromatic polyacetate resin pre-expanded particles having superior foaming fusion properties during foam molding in a model and the use of the pre-foam The body particles can be foamed molded bodies and foamed laminated bodies which can improve the fusion rate or mechanical strength. [Background of the Invention] Aromatic polyester resins have superior properties not found in polystyrene or polyolefins, which have high rigidity, good shape stability, and excellent heat resistance and chemical resistance. Through the foaming of aromatic polyester resins, it is expected to produce lightweight and in-mold foam moldings with excellent heat resistance, heat insulation, cushioning, and chemical resistance. 0 Aromatic polyester resins used in the past (general purpose) PET) is mainly synthesized by the polycondensation of terephthalic acid of diacid acid and glycol of glycol. One of the methods for manufacturing this general-purpose PET foamed molded body is considered to be the same as polystyrene or polyolefin. First, a particulate resin is impregnated into a foaming agent to produce foamable resin particles (impregnation process), and then heated, Pre-foaming, manufacturing pre-foamed particles (pre-foaming process), filling most of the pre-foamed particles in a mold cavity, heating, and foaming the pre-foamed particles while fusing between the particles. Method for in-mold foam molding (in-mold foam molding process). However, the aromatic polyester resin containing general-purpose PET generally has high gas barrier properties, and it takes a lot of time to impregnate the foaming agent. Therefore, the above method has problems of time, cost and labor. ------------- Installation -------- Order · (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specifications ( 210 X 297 public love) 1 311038 482798

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) If the crystallization peak temperature of the pre-expanded particles made of the above-mentioned general-purpose PET is lower than 130 ° C, the rapid crystallization speed will cause The heating during the impregnation of the foaming agent and the pre-foaming in the next process, the crystallization is easy to proceed, leading to an excessively high degree of crystallization. Especially for the pre-foamed particles with a degree of crystallization exceeding 25%, even if the in-mold foaming is performed in the mold cavity, there is a problem that the in-mold foamed molded body cannot be obtained because the particles are almost completely insoluble. . Japanese Unexamined Patent Publication No. 51-50365 discloses the potential foaming property of polyester based on impregnating unstretched fibers of general-purpose PET through a wet spinning method or a dry-spinning method with a low-boiling-point liquid that is non-solvent or difficult-to-solvent for the general-purpose pET. As a fiber, there is a report that a foamed body can be obtained by heating the latent foamable fiber above a plasticizing temperature. The above-mentioned publication discloses that even if a general-purpose PET is used, the longer it is impregnated with the low-boiling-point liquid, the better. In fact, under heating in the range of 90 ° C to 150 ° C, even if it is impregnated for 4 to 5 hours, the degree of crystallization can be easily estimated to exceed 25%, and the method is time-consuming, costly, and labor-intensive. The above-mentioned publication does not disclose the formation of the foamed molded body in the mold, nor does it disclose the pre-expanded particles that can be used in the molding. After the long-term heating as described above, the crystallization degree of general-purpose PET becomes too high. According to this method, even when the pre-expanded particles are made, when the foam is molded in the mold, the above-mentioned particles can hardly be expected. In this case, the foamed molded body in the mold cannot be obtained. Therefore, the above method has a problem that a good in-mold foam molding cannot be obtained.

X 297 mm) 311038 (Please read the notes on the back before filling this page)

482798 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) Mr. Hirai of the present inventor proposed that the general-purpose PET extruder be mixed with a blowing agent under high pressure and melted under atmospheric pressure After extruding and foaming, foam particles produced by cutting the foam to suppress the degree of crystallization to 25% or less are used as pre-foam particles, and the pre-foam particles are filled in a mold cavity. Method for foam molding in a model (Japanese Patent Application Laid-Open No. 8-174590). According to these methods, the degree of crystallization of the pre-expanded particles can be suppressed to less than 25%, so the pre-expanded particles can be subjected to in-mold foam molding, and light-weight and excellent heat-resistant in-mold foam can be obtained. Shaped body. However, in the above-mentioned in-mold foam molding method, since the general-purpose PET is used, the resin crystallizes very quickly. Therefore, although the fusion property can be improved to a certain degree (the fusion rate is about 30%), and an in-mold foamed molded body can be produced, it is not possible to produce mechanical strength that raises the fusion rate to 40% or more. Excellent in-mold foam molding. These reasons are due to the use of general-purpose PET. In the following two processes (1) and (2), crystallization is promoted by heating. In particular, it is clear from subsequent research that the promotion of crystallization during (2) has a great effect on the fusion between particles. (1) The process of extruding and foaming to produce pre-expanded particles &apos;, and manufacturing an extruded foam. (This foam is cut into pre-foam particles). (2) Fill the pre-foamed particles in the mold cavity, and perform the in-mold foaming process. Through the heating during the foam molding in the model, because of the ------ install ----- order · -------- line in the foam (please read the precautions on the back before filling in this page) ) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 3 311038 482798 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ~ ^ ---- ΜΙ _______ V. Description of Invention (4) Accelerating crystallization has a hindrance to the fusion between particles. As long as the in-mold molded product of aromatic polyester resin can solve the above-mentioned problems and activate the above-mentioned superior properties, it can be expected to be applied to, for example, construction materials, civil engineering, and other materials with higher performance than polystyrene or polyene. Materials, industrial materials, automotive parts, etc. The main object of the present invention is to provide a novel crystalline aromatic polyester that can improve the inter-particle fusion during foam molding in a mold, and can easily and efficiently produce a good foam expansion molded body with excellent mechanical strength and the like. System resin pre-foamed particles. Another object of the present invention is to use the above-mentioned crystalline aromatic polyester-based resin pre-expanded particles to provide an in-mold foamed molded article having excellent fusion or mechanical strength between the particles and a good appearance. Another object of the present invention is to provide a novel foamed laminated body in which a film or sheet of the above-mentioned foamed molded body and an aromatic polyester-based resin is laminated. [Disclosure of the invention] The crystalline aromatic polyester-based resin pre-expanded particles of the present invention are characterized in that they can be used for in-mold foam moldings with a bulk density of 0.01 to 10 g / cm3 and a crystallization peak temperature of 130 to 1 80 ° c crystalline aromatic polyester resin pre-expanded particles. The in-mold foamed molded body of the present invention is characterized by filling a mold groove having a shape corresponding to the shape of the in-mold foamed molded body formed by closing the male mold and the female mold for the in-mold foamed molding. After inventing the crystalline aromatic polyester-based resin pre-foamed particles, the above crystalline aromatic polyacetate-based resin pre-foamed particles are foamed by heating, and the particles are fused together. The paper size is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 311038 (Please read the precautions on the back before filling this page)

482798 A7 B7

i Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5). The foamed laminate of the present invention is characterized in that the foamed molded body of the model of the present invention and a film or sheet of an aromatic polyester resin are laminated and integrated. The crystalline aromatic polyester-based resin pre-foam particles of the present invention are pre-foamed bodies formed from a special reformed aromatic polyester-based resin whose crystallization rate is suppressed as compared with the conventional general-purpose PET. The crystallization peak temperature of the particles is also higher than that of the pre-expanded particles made of general-purpose PET, which is 130 to 180 ° C. Since the crystallization rate can be delayed, the production of the pre-expanded particles can be suppressed. The degree of crystallization caused by heating during the process, or the subsequent process of forming the foam in the mold, increases rapidly. When foaming in the mold, the fusion between particles can be significantly improved. Since the crystalline aromatic polyester-based resin pre-foamed particles according to the present invention can improve the fusion between the particles during foam molding in a mold, it is possible to easily manufacture a mold having a high fusion rate and improved mechanical strength and the like. Inner foam molding. In addition to the excellent fusion properties or mechanical strength between the particles, the foamed molded article in the present invention has no gaps between the particles and has a good appearance. The foamed laminated body of the present invention is obtained by laminating and integrating the above-mentioned foamed molded body in a mold with a film or sheet of a square family resin, and has a smooth surface, good printability, beautiful appearance, and excellent appearance. The foamed laminated body of the present invention is one of the most desirable forms of making the heat-bonded person through the process disclosed in item 14 of the scope of patent application by using the above-mentioned foamed molded body in the model and the film or sheet of the aromatic polyester resin. . — — — — — — — — — — — — — 11 (Please read the precautions on the back before filling out this page) --Line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 5 311038

Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. The reason can be cited as the need for adhesives and superior recycling. Foamed laminates using polyester adhesives as adhesives can also be recovered, which is also one of the ideal aspects. [Best Mode for Carrying Out the Invention] The present invention will be described below. &lt; Pre-foamed particles &gt; The crystalline aromatic polyester-based resin pre-foamed particles of the present invention must have a peak temperature of 130 to 18 (rc. The peak temperature of crystallization is the maximum crystallization by heating. The higher the crystallization peak temperature, the higher the crystallization speed can be delayed. The pre-expanded particles formed from the conventionally used general-purpose PET ', as mentioned above, have a crystallization peak temperature lower than 13 (rc, crystallization The crystallization speed is very fast. At this point, because the crystallization peak temperature of the present invention is higher than that of the pre-expanded particles of the PET and the general-purpose PET, the crystallization speed is slower, so its crystallization The degree can be limited to a lower range. 'The crystallization can be moderately suppressed during the foam molding in the model. That is, the fusion between the particles during the foam molding in the model can be improved, and a model with excellent appearance or strength can be manufactured. Internal foamed molded body. Pre-foamed particles whose crystallization peak temperature exceeds 1 80 ° C, because its crystallization rate is too slow, will hardly crystallize and cannot be given the heat resistance of the foamed molded body in the model. In-model foam The conditions for shaping are narrow, it is not easy to form, and it hardly crystallizes during foam molding in the mold, which causes problems such as shrinkage of the molded body, poor appearance, and failure to obtain a foamed laminated body with good appearance. And consider, judge to get a good model inward --------------------- Order --------- (Please read the precautions on the back first (Fill in this page again) -h. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 6 311038 482798

A7 B7 V. Description of the invention (7) The crystallization peak temperature of the foamed body and the manufacture of the foamed laminated body, the crystalline aromatic polyester resin pre-foamed particles is about 13 2 to 17 0 ° C. Ideally, it is more preferably in the range of about 135 to 160 ° C. The crystallization peak temperature was measured using a differential scanning calorimeter (DSC: Differential Scanning Calorimetry) in accordance with a measurement method disclosed in Japanese Industrial Standard JIS K7 121. Specifically, a predetermined amount of pre-expanded pellets as a measurement sample is first placed in a DSC measurement container, and the amount is set at 10. (: The temperature rise rate was increased to 280 C / min. Maintain the temperature (28 ° C) for 10 minutes, and then cooled to room temperature (23. (3), and the above crystallization was measured while increasing the temperature at a temperature rise rate of 10 C / min. Peak temperature. In order to make the crystallization south peak temperature of the pre-foamed particles within the above range, the composition of the diweilic acid component and the monoalcohol component of the aromatic polyester resin forming the pre-foamed particles can be changed. The molecular structure can be modified. Specifically, for example, a dicarboxylic acid is represented by formula (1) ------------- installation -------- order -------- --- line (Please read the precautions on the back before filling this page) The Ministry of Economic Affairs-The Intellectual Property Office of the Intellectual Property Bureau has printed the isophthalic acid shown in HOOC ^^ / COOH or the diol using formula (2) ⑴ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 7 311038 482798

V. Description of the invention (8 hoch2- &lt; ^ H: h2oh (2) M-cyclohexanedimethanol as shown in (2) or a combination of the two, the unit derived from the above isophthalic acid (hereinafter referred to as IPA unit) and The content ratio of the unit derived from 14 cyclohexanedimethanol (hereinafter referred to as the CHDM unit) in the aromatic polyester resin (the content ratio of the individual units when one type is used alone, and the total of the two when used together) The content ratio) is adjusted in the range of 0.5 to 1 (% by weight). If the content ratio of the IPA unit and / or CHDM unit is less than 0.05% by weight, there is no effect of suppressing crystallization. On the contrary, if the content of the two units is contained When the ratio exceeds 10% by weight, the crystallization rate becomes extremely slow. In any case, the foamed molded body and foamed laminated body having excellent appearance, strength, and heat resistance as described above cannot be produced. The content of the foamed molded body and the foamed laminated body in a good model, the IPA unit and / or the CHDM unit is even within the above range, and is preferably about 0.6 to 9.0% by weight, and about 0.7 to 8.0% by weight. More ideal. In addition to isobenzene Formic acid and 1,4 · cyclohexanedimethanol, among other components constituting the aromatic polyester resin, examples of dicarboxylic acids include terephthalic acid or phthalic acid. Examples of glycols include ethylene glycol and α -Butanediol (1,2-butanediol), butanediol (1,3-butanediol), tetramethylene glycol (1,4-butanediol), 2,3-butanediol This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- tr --------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 311038 482798 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description (9) Alcohol, neopentyl glycol, etc. Raw materials of aromatic polyester resins, except the above In addition to each component, as long as it does not exceed the crystallization peak temperature j 30 to 180 ° C of the above-mentioned aromatic polyester resin, a small amount of dicarboxylic acid such as trimellitic acid and cumene as acid components may be contained. Trivalent or higher polyvalent carboxylic acid or its anhydride of tetracarboxylic acid such as tetracarboxylic acid, triol such as glycerol as the alcohol component, and tetraol such as pentaerythritol Polyvalent alcohols, etc. above. The above-mentioned aromatic polyester resin used in the present invention can be specified by the above-mentioned respective components, that is, isopolyphthalic acid and / or U4_cyclohexanedimethanol after polycondensation. The raw material in which the content ratio of the IPA unit and / or € 111)] ^ unit in the resin ranges from 0.5 to 10% by weight of the total amount is produced through the same polycondensation reaction as before. The above-mentioned aromatic polyester-based resin may also be obtained by (1) crystallization peak temperature lower than 13 (TC aromatic crystalline polyester-based resin (for example, the content ratio of IPA unit and / or CHDM unit is less than 0.05% by weight) Resin) and (2) crystalline aromatic polyester resins with a crystallization peak temperature of 130 ° C or more and at least one selected from non-crystalline aromatic polyester resins (for example, the content ratio of ιρΑ units and / or CHDM units) Resin at a weight of 0.5 y 重量 or more) so that the content ratio of IPA units and / or CHDM units in the whole resin is within a range of 0.5 to 10% by weight of the total resin, and melted under heating using an extruder or the like, According to this method, during the manufacturing stage of the pre-foamed particles, 2 paper sizes can be applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------- --- install -------- order --------- line (please read the precautions on the back before filling this page) 482798 A7

The blending ratio of aromatic polyester resins containing more than one IPA unit and / or CHDM unit ratio can be changed to adjust the content ratio of the above-mentioned two monomers in the pre-foam particles, thereby adjusting the crystallization peak of the pre-foam particles The temperature makes it easier to adjust the crystallization peak temperature of the pre-foamed particles, and has the advantage of being able to respond flexibly, such as changing the specifications. For example, as one of the aromatic polyacetate resins to be blended, it is also possible to use recycled raw materials from Baote bottles, which has the advantage of effectively reusing resources. In the method described above, each resin is aromaticized by transesterification reaction between two or more aromatic polyester resins, and becomes a homogeneous aromatic polyester resin, which is preferably sufficiently melted and kneaded under heating. When using an extruder or the like to mix an aromatic polyester resin and a foaming agent under high-pressure melting, the extruded foamed body is cut to produce pre-foamed particles. Melting, mixing, making uniform aromatic

Is said that the operation of the tree is more efficient and ideal in the above-mentioned extruder. However, the above-mentioned operation may be carried out by first melting or mixing two or more resins with another device. Japanese Unexamined Patent Publication No. Hei 6-505452 discloses an extruded and foamed foam obtained by extruding an aromatic polyester-based resin containing only 20% or less of isophthalic acid. Japanese Unexamined Patent Publication No. 5-507761 and Japanese Unexamined Patent Publication No. 5-507762 respectively disclose the melting, kneading, and granulation of a low-molecular-weight aromatic polyester resin containing up to 25% of an IPA unit and a reforming additive. After modification, high-molecular-weight polyester resins used for blow molding and the like are manufactured. In Japanese Patent Application Laid-Open No. 4_278346, it is disclosed that the dicarboxylic acid component contains 1 to 80 mole% isobenzene (please read the precautions on the back before filling this page) -------- tT ---- ----- · The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 10 311038

5. Description of the invention (u

An aromatic polyester-based resin layer of monoformic acid and a non-foamed laminated film in which a diol component contains 1 to mol% of an aromatic polyester-based resin layer containing M-cyclohexanedimethanol is melted, extruded, and laminated. . However, in these publications, none of the pre-expanded particles used for the foamed molded body of a model for producing an aromatic polyester resin was mentioned. It is also not mentioned that the content ratio of the two components is specified to be 0.5 to 5% by weight in order to ensure good foaming fusion properties of the pre-expanded particles. One of the characteristics of the present invention is that the content ratio of the above components is specified to be 10% by weight or less, and an in-mold foamed shape having excellent heat resistance and appearance can be obtained. The aromatic polyester resin used in the present invention takes into consideration the melting and kneading properties during the production of pre-expanded foam particles and the moldability when using the pre-expanded particle molding model foamed molded body produced. The inherent viscosity (measurement temperature · 35 ° C, solvent: o-phenol) is preferably about 0 to 15. In the present invention, the following additives may be added to the aromatic polyester resin. Examples of the additives include, in addition to the foaming agent, a melt tension modifier, a flame retardant, an antistatic agent, a colorant, a bubble regulator, and an oxidizing agent. P foaming agents can use any of chemical foaming agents and physical foaming agents. Among them, chemical foaming agents that perform eight decomposition at a temperature above the softening point of the daddy polyester resin and generate gas can be exemplified by azo. Formamidine, mono-schizylpentamethylenetetramine, hydrazinedimethylformamide, sodium bicarbonate, etc. Examples of physical blowing agents include propylene, n-butyl, iso-butyl, _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 11 3 Π038 I -------- ^ --------- ^ (Please read the phonetic on the back? Matters before filling out this page} Printed by the Ministry of Economic Affairs, Consumer Property Cooperative of the Bureau of Intellectual Property, 482798 A7 V. Description of Invention (l2) Saturated hydrocarbons such as Wuyuan and Jiyuan, i-generation hydrocarbons such as digasmethane, gas-leon (trademark registration), ether compounds such as methyl ether and methyl tert-butyl ether, etc. Inert gases such as carbon dioxide and nitrogen are also used. It can be used as a foaming agent. Among them, saturated hydrocarbon, carbon dioxide and nitrogen are particularly suitable as the foaming agent. The bubble regulator is preferably polytetrafluoroethylene resin. Polytetrafluoroethylene resin has the advantage of only a small amount to play The effect of miniaturizing air bubbles hardly promotes the crystallization of aromatic polyester resins, and has the effect of producing foamed molded articles with fine air bubbles and excellent appearance. The above-mentioned polytetrafluoroethylene resin is the hafnium atom of polyethylene. A thermoplastic resin completely substituted with fluorine atoms. Among the polytetrafluoroethylene resins, commercially available polytetrafluoroethylene resins have an effect as foaming regulators when the aromatic polyester resin is extruded and foamed. The reason is that the polytetrafluoroethylene resins have the same properties as the polytetrafluoroethylene resins for molding. The following characteristics are different. 'One of its characteristics is melt viscosity. That is, even if a PTFE resin heated from a hole with an inner diameter of 2 lmm and a length of 8.0mm to a temperature of 340t is at a gauge pressure of 2.0MPa, The melt index test was performed for 10 minutes under pressure, and the polytetrafluoroethylene for molding did not flow out of the holes at all, and the melt index was 0. At this point, the polytetrafluoroethylene resin used for lubrication was extruded under the above conditions. , It will flow out from the pores, and the flow rate is more than 10g. That is, it is most desirable to have a melting index of 1 · 0 or more. ^ ^ ^ ^ The amount of resin added is 100% for aromatic polyester resin 100 ί Paper size National Standards for Financially Suitable Countries (CNSM4 Specification (21 () x 297 12 311038 t --------- rtt First read the note on the back? Matters before filling out this page} 482798

Printed by the Ministry of Economic Affairs and Consumer Affairs Co., Ltd. of the Smart Property Bureau 311038 A7 V. Description of the invention (13) It is preferable that the weight part is about 0.005 to 0.1 weight part. Within this range, as described above, polytetrafluoroethylene resin, as a bubble regulator for an aromatic polyester resin, has the property of effectively acting without affecting the crystallization of the aromatic polyester resin. When the polytetrafluoroethylene resin is added to the aromatic polyester resin in an amount within the above-mentioned addition amount range, when extruding and foaming to produce an extruded foam, it can not only exert an increase in the melt tension of the aromatic polyester resin. The effect is to improve the stability of extrusion foaming. It can also prevent bubbles from bursting due to too thin bubble film when the bubbles are miniaturized, and can form fine and good bubbles. This is the best type of cancer. The polytetrafluoroethylene resin is preferably added in an amount of 0.0007 to 0.08 parts by weight with respect to the aromatic polyester-based resin, and particularly preferably added in an amount of 009 to 2006 parts by weight. The method of adding polytetrafluoroethylene resin can use aromatic polyester resin and dry blended product as raw materials for extrusion foaming. In order to improve the dispersibility, the state of the master batch used for the aromatic polyester resin is also ideal. The master batch can be extruded from an aromatic polyester resin that is the main body of the pre-expanded particles, the same resin, and / or other aromatic polyester resins compatible with the resin, and polytetrafluoroethylene resin. After being melted and kneaded by a machine, it is granulated by a granulator. The aromatic polyacetate-based resin of the present invention may be added with thermoplastic elastomers such as polyolefin-based resins such as polypropylene-based resins and polyester-based elastomer resins within a range that does not significantly affect its crystallinity and crystallization rate. Resin, polycarbonate This paper is sized for China National Standard (CNS) A4 (21〇 297 公 II) ----- -------------------- --1 --------- ^ (Please read the phonetic on the back? Matters before filling out this page: &gt; Printed by A7 of the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs -----__ V. Description of the Invention (U) 's resin, ionomer polymer resin, etc. Pre-foamed particles can be manufactured by ## foaming a square family polyester resin and cutting the pile foam into particles. According to the above method, Omit the process of impregnating the foaming agent with the aromatic polymer grease. In addition to saving time, cost and labor, it can also make the crystallinity of the pre-foamed particles lower, which can improve the particle-to-particle foaming during molding. The fusion property of the present invention is to mix special aromatic polyfluorene resin with a foaming agent under high-pressure melting to cut off the extruded foamed body and manufacture Foam particles. The above-mentioned extruder is not particularly limited, and is generally a uniaxial extruder or a biaxial extruder used in this type of extrusion foaming. Connected tandem extruder. An extruder with sufficient melting and mixing capabilities is ideal. There are many types of extruder die, such as: ring die, flat die, nozzle die Head and multi-nozzle die with multiple nozzles, etc. Using these die, you can produce extruded foam in various shapes such as sheet, plate, and monofilament. In order to make the extruded foam into the specified shape For example, the following methods can be used: For example, extruding a cylindrical foam from a ring-shaped die, and cooling it on a mold core that has been cooled or adjusted in temperature. After cooling, it is cut and expanded to produce a sheet foam. In order to manufacture a monofilament foam extruded from a nozzle die or a multi-nozzle die. Except for the air cooling or water cooling of the monofilament foam, please read the precautions on the back before filling in this page)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 14 311038 482798

Printed by the Consumer Affairs Co., Ltd. of the Intellectual Property Office of the Ministry of Economic Affairs A7 B7 5. In addition to the description of the invention (I5), it is ideal to use a cooling device whose temperature has been adjusted for cooling. Regardless of which method is used, cooling as soon as possible after extrusion of the foam can avoid accidental crystallization. The particles cut from the sheet-shaped extruded foam produced by these methods are present in the shape of a square shape or a pellet. The monofilament-shaped extruded foam was cut into pre-foam particles having a substantially cylindrical shape. The above-mentioned foam can be cooled and cut at an appropriate timing. For example, the foam extruded through the die can be cut into a specified shape and size with a granulator or the like at any time during the foaming to the completion of foaming. In addition, the foam extruded from the die may be completed immediately after the foaming is completed, or the foamed body immediately before the cooling may be cut off and then cooled. The foam extruded into a sheet shape may be rolled into a roll shape by a winder and then cut with a pulverizer or a cutter. The size of the pre-expanded particles produced by these methods is preferably an average particle diameter of about 0.5 to 5 mm. The shape of the pre-foamed particles is preferably a substantially cylindrical shape among the above-mentioned slightly cylindrical shape, square shape, and pellet shape. The reason is that during the foam molding in the mold, the pre-foam particles can be filled more uniformly in the mold groove formed by closing the male mold and the female mold described below. Further, the foamed molded body produced in the mold produced by uniformly filling the pre-foamed particles was found to have excellent mechanical strength. It has been described in detail that the substantially cylindrical pre-foamed particles are mainly produced by cutting an extruded and foamed monofilament-like foam into any size. When extruded and foamed into a monofilament, it was found through experiments that the melt tension of the aromatic polyester resin is about the size of this paper. The Chinese National Standard (CNS) A4 specification (210 X 297 public love) is applicable. ------- ------ install -------- order --------- line (please read the precautions on the back before filling this page) 311038 482798 A7 --- -B7 ____ V. Invention It shows that (I6) 0.7 to 3g is ideal. In the past, when an aromatic polyester resin was extruded and foamed into a sheet or plate shape, its melt tension must be increased to about 18 2 lg. [Page 1257] 'This item is also one of the novel technologies discovered by the inventors. The melt tension of the 'aromatic polyester-based resin is preferably about 0.9 to 2.5 g, and more preferably about 1.0 to 2.0 g. The melt tension modifier can be added to adjust the melt tension of the aromatic polyester resin | within the above range. The melt tension modifier can be used alone or in combination of two or more epoxidized compounds such as glycidyl phthalate, acid anhydrides such as pyromellitic dianhydride, sodium carbonate such as la, and Π a as metal compounds. . The addition amount of the melt tension modifier varies depending on the type of the modifier used, and is generally about 0.05 to 1.0 part by weight, preferably about 0.06 to 100 parts by weight for the aromatic polyester resin. 0.5 parts by weight, more preferably from about 0.81 to 0.3 weight. By adding a melt tension modifier in this range, the melt tension of the aromatic polyester resin can be adjusted within the above range. I It is also possible to melt and knead the aromatic polyester resin and the melt tension modifier at a specified ratio | rate, and adjust the melt tension within the above-specified range. The compound of I is used as the raw material for production and is put into the extruder. . In addition, by confirming the manufacturing state of the pre-foamed particles, the melting tension can be finely adjusted. The above two can also be separately put into the extruder without melting and kneading in advance. I The average cell diameter of the above-mentioned approximately cylindrical pre-foamed particles is preferably about 0.05 to 0.8 mm. f I 丨 ㈣ If the bubble diameter is lower than the above range, the bubble wall becomes too thin.

This paper size applies to the national standard (CNS) A4 specification (210 X 297 public love) --------J

(Please read the precautions on the back before filling out this page)-^ 9 -------- Order --------- 482798 40 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention It shows that (η) has a bad influence on the moldability of the foam in the model. On the other hand, if the average foaming diameter exceeds the above-mentioned range, the cell diameter becomes too large, and there is a concern that the appearance thereof will be adversely affected. Even if the average cell diameter of the pre-foamed particles is within the above range, it is preferably about 0.1 to 0-7 mm, and more preferably about 0.15 to 0.6 mm. The degree of crystallinity of the pre-foamed particles is the foamed molded body in the mold in order to obtain the high-strength high-intensity foamed body with excellent fusion between the foamed particles and the foamed molded body in the mold and the film or The appearance or superior strength of the foamed laminates with excellent fusion properties between the sheets is preferably about 8% or less. Even if the degree of crystallization of the pre-foamed particles is within the above range, it is preferably about j to 7%, and more preferably about 1 to 6%. The degree of crystallization (%) is the same as the above-mentioned measurement of the crystallization peak temperature. Using a differential scanning calorimeter (DSC), the cold crystallization heat and melting heat measured according to the measurement method disclosed in Japanese Industrial Standard JISK7121 are based on the following. Find the formula. Melting heat per mole-Cold crystallization heat per mole Crystallization degree (%) = ------- X100 Fully crystalline PET melting heat per mole In the formula, the melting heat per mole of fully crystalline PET is The polymer data book [issued by Peifeng Pavilion] contains 26.9KJ. Specifically, a predetermined amount of pre-foamed particles as a measurement sample is charged into a DCS measurement container, and the cold crystallization heat and melting heat are measured at a temperature increase rate of 10 ×: / min, and the measurement results are based on the above. Formula (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 17 311038 482798 Printed by A7, B7, Employee Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (M) Calculate the crystallinity of the pre-foamed particles. In order to obtain the bulk density of the pre-foamed particles, in order to obtain lightweight and excellent in-mold foamed molded bodies having excellent mechanical strength, heat resistance, heat insulation, cushioning, and chemical resistance, in the present invention, it is from 0. 01 to丨 〇g / cm3 range. If the bulk density of the pre-foamed particles is lower than the above range, the apparent density of the foamed molded body in the produced mold becomes small, resulting in insufficient mechanical strength, heat resistance, or cushioning properties. Conversely, if the bulk density exceeds the above range, a lightweight molded foam body cannot be obtained, resulting in insufficient thermal insulation or cushioning properties. Even if the bulk density of the pre-foamed particles is within the above range, it is more preferable to be about 0.003 to 0.8 g / Cm3, and more preferable to be about 0.004 to 0.6 g / cm3. In order to produce a more lightweight in-mold foamed molded body, the bulk density of the pre-foamed particles is preferably less than 0.1 g / cm3 even if it is in the range of 0.001 to 1.0 gkm3. Pre-expanded particles having a relatively low bulk density of less than 0.1 g / cm3 are produced, and the pre-expanded particles manufactured according to the method described above are immersed in a gas under pressure and heated, and then re- In the foaming process, it is ideal to adjust the bulk density to a smaller value. The refoaming process can also be repeated two or more times. In this case, a crystallinity of more than 8% is preferable. In the re-foaming process, various gases such as nitrogen, carbon dioxide, helium, neon, rat, oxygen, air, or a mixture of these can be used at normal temperature and pressure. The impregnation pressure of the pre-expanded rhenium particles impregnated in the gas phase I immersion of the gas described above is about 0.1 to 10 MPa, and the gauge pressure is about 0.2 to 7 MPa.: The paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 Male 18 311038 (Please read the notes on the back before filling this page) ------- Order --------- 482798

Printed by the Consumer Affairs Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs 311038 A7 B7 5. The description of the invention (I9) is particularly preferably about 0.3 to 5 MPa. The impregnation time is about 15 minutes to 48 hours, preferably about 30 minutes to 24 hours, and particularly about 1 to 12 hours depending on the type of gas used. In order to prevent the degree of crystallization of the pre-foamed particles from increasing, the impregnation temperature is preferably 60 ° C or lower. When the gas for impregnating the pre-foamed particles is refoamed, hot air, warm water, steam, heating oil, heating gas, or the like can be used as a heating medium. If the operability of the pre-expanded particles after re-foaming or the efficiency of re-foaming are considered, hot air, warm water or steam is more suitable. The re-foaming process is particularly suitable for making pre-expanded particles ("secondary pre-expanded particles") having a bulk density of less than 0 lg / cm3. Therefore, even if the bulk density of the pre-foamed particles before re-foaming ("primary pre-foamed particles") is greater than 0.1 g / cm3, the bulk density can be reduced by implementing the re-foaming process. Finally, the continuous cell ratio of the pre-expanded particles (primary pre-expanded particles and secondary pre-expanded particles) used for the foam molding in the model is preferably 5 to 3 5%. If the continuous cell ratio of the pre-expanded particles exceeds 35/0, it will have an adverse effect on the foam molding in the mold, and there is a concern that a good foam molded body cannot be produced. On the other hand, if the continuous bubble ratio is 5% or less, the shrinkage of the foamed molded body in the mold when the mold is taken out may increase. In this regard, when using pre-expanded particles having a continuous bubble ratio in the range of 5 to 35/0, the shrinkage of the foamed molded body in the model when taken out of the mold can be suppressed, and there is no surface of the foamed molded body in the model. It may be wrinkled or have a poor appearance, so it is especially suitable for industrial materials that require dimensional accuracy. ^ ， The Zhang scale is applicable to the Chinese national standard (cns) A4 specification (2ig χ tear public love) ------------- ^ --------------- -^ (Please read the notes on the back before filling out this page) 482798 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs, V. Invention Description (20) Even if the continuous bubble rate is within the above range, it is 30%. The following is ideal: The Ping Shao bubble diameter of the pre-foamed particles can be adjusted by the method of adding a bubble adjusting agent such as polytetrafluoroethylene resin to the aromatic poly§ | series resin as mentioned above and adjusting the melt tension of the resin during extrusion foaming Or control the shear rate when extruding from the die, etc. In addition, according to the latter method, it is also possible to adjust the continuous cell ratio of the pre-expanded particles. Among them, the latter method adjusts the average of the pre-expanded particles. For the bubble diameter, the faster the shear rate is, the smaller the bubbles are. However, if the shear rate is too fast, a molten cross section will be generated in the molten resin, which is not ideal. Specifically, as described above, the melt tension is adjusted to About 07 to 3§, the average cell diameter of the pre-foam particles having a substantially cylindrical shape, The cell opening rate is in the above-mentioned ideal range, and the shear rate is set to about 3000 to 30000 seconds4, preferably about 4000 to 25,000 seconds ", more preferably about 5,000 to 20000 seconds". &lt; In-mold foam molding &gt; The above-mentioned pre-foamed particles are used to manufacture the in-mold foam molding of the present invention so that the male mold and the female mold for molding the foam in the mold are closed and cannot be sealed. The mold tank is filled with pre-foamed particles, and then steam is used as the heating medium. The molding method is ideal. In this case, the heating medium can use hot air in addition to steam, but for efficient molding, The most effective is steam. When using steam to perform in-mold foam molding, use a widely used in-mold foam molding machine for in-mold foam molding. That is, the paper size of the pre-expanded pellets is subject to Chinese national standards. (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page)

A7 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs --------. &Quot; 1 —___ 15. Description of Invention (21) After filling the mold groove, the mold from one side is under low pressure For example, at a gauge pressure of about 0.01 to 0.05 MPa), steam is blown into the mold tank at a certain time to exhaust the air between the particles (at this time, it can also be extracted from the other side of the mold). Then the pressure of the steam is increased (for example, the gauge pressure is about 0 to 0.1 MPa), and the steam is blown in from the molds on both sides, that is, the pre-foam particles are subjected to in-mold foam molding to manufacture the in-mold foam molded body. . In addition, the expansion force of the pre-expanded particles when foamed and molded in the mold is maintained in a sealed container in which an inert gas such as carbon dioxide, nitrogen, and helium is pressed, and the pre-expanded particles are maintained in the mold while maintaining the atmosphere of the infused gas. When it is large, it is one of the more desirable forms because a good in-mold foamed molded body can be obtained. The obtained in-mold foamed molded body can have a fusion rate between particles of more than 40%. In particular, the foamed molded article having a mold appearance of 50% or more and 60% or more has particularly excellent appearance and mechanical strength. The degree of crystallinity of the foamed molded body in the mold is 15% or more, and the foamed molded body that has been raised to 20 to 40% is a molded body having excellent heat resistance. The foamed molded body in the mold of the present invention is also excellent in dimensional stability. The in-mold foamed molded article of the present invention can be reused after being used in the above-mentioned various applications. Because the in-mold foam molded body can be reused, in addition to the resources that can be effectively reused and the contribution of waste reduction, the cost of the in-mold foam molded body can be reduced. &lt; Foamed laminated body &gt; The foamed laminated body of the present invention is one in which the above-mentioned molded foam body is laminated with an aromatic polyester resin film or sheet. IIIIII i ί IIII t! 1! (Please read the precautions on the back before filling this page) This paper size _ towel _ mound standard (CNS) A4 size (210 X 297 male f) 21 311038 482798

V. Description of the invention (22) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Melting, lamination and integration forming is one of the most ideal forms. In detail, the crystallization peak temperature is 130 to 180. (; The crystalline aromatic polyester resin pre-foam particles not only show excellent fusion between the particles during foam molding in the mold, but also for the film or sheet of the aromatic polyester resin, foam in the mold. It also shows excellent adhesion during molding. That is, the male and female molds used for foam molding are equipped with a film or sheet of aromatic polyester resin on either or both sides of the mold, and the male and female molds are closed. The formed mold cavity is filled with the crystalline aromatic polyester-based pre-foam particles of the present invention, and then a heating medium such as steam is introduced to perform in-mold foam molding. The film or sheet is laminated and integrated by thermal bonding (in-mold foam molding lamination method). Alternatively, the in-mold foam molded body can also be formed by pre-foaming particles through in-mold foam molding in advance. , The method for forming the foamed molded body in the model and the film or sheet above 130 ° C, preferably above 140 ° C, while pressing or laminating, integrating, and the like while hot pressing or heating with a heat roller. However, This method is not suitable The mold-in-foam molding provided with heat resistance is preferably the above-mentioned mold-in-foam molding and lamination method. The manufacturing conditions of the mold-in-foam molding using steam as a heating medium will be described. During foam molding, pre-foam particles are filled in the mold tank with a film or sheet of an aromatic polymer-based resin installed in the mold tank. After that, the mold from one side is under low pressure (such as gauge pressure). (Approximately 0.001 to 0.05 MPa) to blow steam into the mold cavity at a certain time to make the space between the particles (please read the precautions on the back before filling this page)

Γ. Emm§ 11 ϋ I tmmK tMmmmm I «y Mt§ n i IM§ ammmm n ammmm I This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 22 311038 482798 A7

The printed gas of employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs is discharged outward. Then, the pressure of the blown steam is increased (for example, the gauge pressure is about 0.04 to 0.1 MPa), and the steam is blown from the molds on both sides of the male mold and the female mold, so that the pre-foam particles are foamed and the foam is also foamed. The body particles and the foam particles are fused to the film or sheet. Then, at 90. (: Above, it is preferred to maintain the temperature from about 90 ° to less than the above-mentioned foaming molding temperature in the mold to maintain about 60 to shift, promote crystallization, and improve the heat resistance of the foamed laminate. The degree of crystallization of the foamed body and the film or sheet is maintained at more than 20%, and the foamed laminated body can be given excellent heat resistance. Finally, it is cooled and taken out from the mold to obtain the foamed laminated body. The crystalline aromatic polyester-based resin pre-foam particles used have a temperature of 130 to 180 ° C, preferably 13 2 to 170 ° C, and more preferably 135 to 160 t, and the pre-expanded particles having a degree of crystallinity of i to 8% can exhibit excellent in-mold foaming moldability and adhesion. Among the aromatic polyester resins laminated in the present invention, The film or sheet is preferably non-crystalline or has a degree of crystallinity of 15% or less. The reason is to obtain a practically superior delamination resistance, specifically, a foam having a delamination resistance of 5N / 25mm or more. Laminated body. Specifically, the film or sheet of an aromatic polyester resin is considered for its mechanical strength. Heat resistance, chemical resistance, printing suitability, etc. are preferred. Films or sheets with PET as the main component synthesized by polycondensation of terephthalic acid as a diacid and ethylene glycol as a diol are preferred. The film or sheet can also be the resin used in the pre-expanded particles of the present invention. The degree of crystallinity of the film or sheet is preferably below 15%. The reason I -------- ^ ---- ----- Line (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 23 311038 482798 A7 Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing 5. Description of the invention (24) As mentioned above, X, it is also possible to use a film or sheet formed from an aromatic polyester resin having a crystallinity of 0% or non-crystalline. However, ^ obtained The thermally foamed laminate is preferably a crystalline aromatic polyacetate-based tree film or sheet. The thickness of the above film or sheet is preferably about 50 // 111 to 1 mm, and the film is manufactured by extrusion molding. Or thin sheet is more suitable. The thickness of the foamed sheet is preferably about 0.5 to 3 mm, and the degree of crystallinity is preferably 15% or less. [Industrial Application Possibility] As described above, according to the present invention, it is possible to obtain in-mold foam molding. A model of a novel crystalline aromatic polyacetate resin pre-expanded particle having excellent compatibility between particles and a particle having excellent solubility or mechanical strength between the particles formed by the pre-expanded particle and a good appearance The special effect of the inner foamed molded body and the good foamed laminated body in which the molded inner foamed molded body and the film or sheet are firmly adhered and laminated. [Examples] The following examples and comparative examples are given to the advantages of the present invention. Specific instructions. In addition, each of the following measurements was performed under a measurement environment with a temperature of 23 ± 2 C and a humidity of 50 ± 5% RH based on Japanese Industrial Standard jlSK7 [Standard Condition of Plastic Condition Adjustment and Test Site]. The peak crystallization temperature of the pre-foamed particles and the degree of crystallization of the pre-foamed particles, films, flakes, and foam moldings in the model are also subject to the Chinese National Standard (CNS) A4 specification according to the above paper size ( 210 X 297)) -------- 24 311038 (Please read the notes on the back before filling out this page) -------- ti ------- -tt ϋ I LI. 482798 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Obtained from the results of the measurement method disclosed in Japanese Industrial Standard JISK7 121 described in the description of the invention (25). The content ratio of the IPA unit and the CHDM unit in the aromatic polyester resin and the melt tension of the resin were measured by the following methods, respectively. The content of the IPA unit is determined. About 100 mg of the sample is weighed in a pressure-resistant Teflon cup, and then added to 10 ml of dimethylarsine for light absorption analysis manufactured by Wako Pure Chemical Industries and 6 ml of 5N sodium hydroxide-methanol solution. The pressure-resistant Teflon cup is placed in a pressure-resistant heating cup made by SUS, and it is surely sealed and heated at 10 ° C for 15 hours. Then, 'the heated pressure-resistant heating cup is cooled at room temperature and in a completely cooled state Take out the pressure-resistant Teflon cup, move the contents to a 200ml beaker, and add distilled water to about 150ml. Next, after confirming that the contents are completely dissolved, neutralize with hydrochloric acid to a pII value of 6.5 to 7.5 '. The turbidity was diluted by a factor of 10 to 200 ml with distilled water as a sample solution. The sample solution and the isophthalic acid standard solution were measured in a high-speed liquid chromatography (HPLC) apparatus under the following conditions. Iso-benzyl dicarboxylic acid manufactured by Tokyo Chemical Industry Co., Ltd. is used as a standard solution of isophthalic acid in distilled water. Device: Waters HPLC LC-module 1 Column: inertsil 〇DS_2 5 β m (4.6 X 250) )

Column temperature: 23 soil 2 ° C 唧 Cylinder temperature: 23 ± 2 ° C ^ -------- ^ --------- ^ (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 25 311038 482798 A7 _____ B7 V. Description of the invention (26) Mobile phase: 0.1% phosphoric acid / B = 80/20 Flow rate: 〇. 5ml / min analysis time · 50 minutes injection volume: 5 0 // 1 detection ·· UV-210nm Use the maximum area of isophthalic acid obtained from the standard solution as the Y axis and the concentration as the Y axis to make a calibration curve. Using the obtained calibration curve, the isophthalic acid concentration (V g / ml) in the sample solution was calculated. From the above concentration, the content ratio (% by weight) of the IPA unit in the aromatic polyester resin was calculated using the following formula. Concentration of isophthalic acid (Vg / ml) Content of IPA unit-X 159.05 ratio (wt%) Sample weight (mg) Measurement of CHDM unit content ratio Approximately 100mg of sample is weighed in a pressure-resistant Teflon cup Then, add 10 ml of dimethyl acerite for light absorption analysis manufactured by Wako Pure Chemical Industries, Ltd. and 6 ml of 5N sodium hydroxide monomethanol solution, and then put the pressure-resistant Teflon cup into a pressure-resistant heating cup made by SUS. Heat at 100 ° C for 15 hours. Next ', the heated pressure-resistant heating cup is cooled at room temperature, and the pressure-resistant Teflon cup is taken out under complete cooling. The content is transferred to a 100 ml beaker, and the special reagent methanol is added to about 70 ml. Next, after confirming that the content is completely dissolved, neutralize it with hydrochloric acid to a pH of 6.5 to 7.5. After neutralization, dilute the turbidity by 10 times with the special reagent acetone (please read the note on the back? Matters before filling this page) ) ------- Order --------- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 26 311038 482798 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (27) 100ml as the sample solution. Take 10 ml of this sample solution and 1,4-cyclohexyldimethanol standard solution into a centrifugal sedimentation tube, evaporate the solvent to dryness after centrifugation, add 0.2 ml of TMS chemical agent manufactured by Tokyo Chemical Industry Co., Ltd. in Heat at 60 ° C for 1 hour. The heated liquid was measured using a gas chromatography (GC) device under the following conditions. Device: Perkin Elmer GC AutoSystem Column: DB_5 (0.25mm (p X30mx0.25 / zm) Oven temperature: 100 ° C (2 minutes) to ri to 2000 ° c to R2 to 320 ° C (5 minutes) Speed: Rl = 10 ° C / min, R2 = 40 ° C / min. Analysis time: 20 minutes injection temperature · 300. Detector: FID (300 ° C) Gas pressure: 18psi will be obtained from b quasi solution The peak area of the TMS compound of 1,4-cyclohexanedimethanol was taken as the X-axis, and the concentration was used as the Y-axis to prepare a calibration curve. The obtained calibration curve was used to calculate the concentration of 4,4-cyclohexanedimethanol (// g / ml). From the above concentration, use the following formula to calculate the content ratio (wt%) of the CHDM unit in the aromatic polyester resin. ---- I--11 ---- pack --- -II order · -------- line (please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 27 311038

V. Description of the invention (28) The content of CHDM unit = ratio (% by weight) 1,4-cyclohexanedimethanol concentration sample weight (mg) 'X98.62 Sign _ measurement of melting tension t measurement of melting tension is The non-foamed particles produced in accordance with the following conditions were performed under the following measurement apparatus and conditions. The non-foamed particles were placed in a vacuum dryer at 110 C, and dried under reduced pressure for 24 hours. The water contained therein was removed for measurement. Measuring device: capillary chart PMD-C (Toyo Seiki Seisakusho Co., Ltd.) Temperature: 270 ° C Preheating time: 5 minutes Capillary shape • (Direct control) 1.0mm, (length) 20mm, (inflow angle) 9 ° Degree extrusion speed: 30mm / minute (shear speed 364.8 seconds-1) Pull speed: 100m / minute The density of the pre-foam particles printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, The apparent density and the apparent density of the foamed sheet were measured by the following methods. The degree and appearance of the Tang Dynasty are determined based on the method disclosed in the Japanese industrial standard JIS K6767, and the bulk density (g / cm3) of the pre-expanded particles and the foam in the model are determined by the following formula Apparent density (g / cm3) of molded body and density (g / cm3) of foamed sheet 〇 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 7 &quot;-28 311038 (Please (Read the notes on the back before filling out this page)

482798 A7 B7 29 V. Description of the invention (Weight of pre-foam particles (g) Pre-foam particles = __ Bulk density (g / cm3) Volume of pre-foam particles (cm3) Weight of foamed sheet ( g) Appearance of foamed sheet = —____ Stiffness (g / cm) Volume of foamed sheet (cm3) Weight of foamed molded body in model (g) foamed molded body in model = ___; _ Density (g / cm3) The volume of the foamed molded body in the model (cm3) The continuous foaming rate and average bubble diameter of the pre-foamed particles are measured by the following method. Calculate the continuous cell ratio (%) of the pre-foamed particles in each of the tests described in (1) to (3). (1) Measure the weight and volume of the pre-foamed particles in an air-comparison hydrometer (made by Tokyo Science Co., Ltd. 1) 〇〇〇 type) into the sample cup about 80% of the pre-foamed particles in advance to determine its weight [pre-foamed particle weight A (g)]. Put the pre-foamed particles into the cup, The cup was mounted on the above-mentioned hydrometer, and the volume was measured by the 1-1 / 2-1 air pressure method [volume B (cm3) of the pre-foamed particles]. (2) The volume of the pre-foamed particles was measured. Observe the volume of the electronic weighing scale (HB3 000 manufactured by Yamato System Co., Ltd.) to take the measuring paper of this paper to fit the national standard of the country (CNS) A4 specifications (〇x 297 public love) ------------ -Install -------- Order --------- line (Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 482798 A7 ------- B7______ V. Description of the invention (30) The container made of barbed wire in the installation accessory is in a suspended state. The container was immersed in water and the Container weight [container weight in water C (g)]. Put the entire amount of the pre-expanded particles measured in (1) above in the same container, and perform the same operation, and measure the total weight of the container and the pre-expanded particles in the state of being immersed in water [total weight in water D (g)]. The apparent volume E (cin3) of the pre-foamed particles was calculated according to the following formula. The water lg is converted to a volume of 1 cm3. E = A + (C- D) (3) Succession bubble rate The result (1) (2) above is used to calculate the succession bubble rate [%] according to the following formula.

Consecutive bubble ratio (%) = (E— B) X 100 / E Pan of average bubble diameter 丨 The average bubble diameter is determined from the resin flow direction (MD) and width direction (based on ASTM D2842-69) TD) and thickness direction (VD) are added together and averaged. While measuring the bending strength, buckling amount, and fusion rate of the foamed molded article in the model by the following method, the dimensional stability, heat resistance, and appearance were evaluated by the following method. Measurement of flexural strength and deflection amount The foamed molded body in the model was cut into a size of 50 mm x 10,000 mm &gt; &lt; 13 mm. As a test piece, a bending test was performed under the following conditions to calculate the maximum bending strength (MPa) and the time at which Curvature (mm). This paper size applies to China National Standard (CNS) A4 specifications (210 X 297) (Please read the precautions on the back before filling this page) ------- Order --------- 482798 A7 V. Description of the invention (31) Device: Tianshilong universal testing machine Bending speed: 50mm / min Tip drill die: Pressurized wedge 3.2R Support: 3.2R Tightening distance: 50mm Measurement of fusion rate The foamed body is bent and fractured in the thickness direction, and the number of all the pre-foam particles existing on the fracture surface and the number of the pre-foam particles in which the particle body material is broken are calculated. The fusion rate (%), which is the basis for the inter-particle fusion property, was calculated according to the following formula. Number of pre-foam particles destroyed by material. Fusion rate (%) == Number of all pre-foam particles existing on the fracture surface. X100 Evaluation of the stability of the size of the printed body by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The interval h corresponding to the maximum length of the foamed molded body in the mold and the maximum length of the foamed molded body in the mold when it is removed from the model is calculated according to the following formula (%). At a shrinkage rate of 2 /. The following are evaluated as 0 (good dimensional stability) and X (except for poor dimensional stability) for evaluation. Shrinkage (%) of the molded body = (Li _ Ljx 100 / Li The evaluation of the heat resistance is based on the Japanese industrial standard JIS K6767 to evaluate the heat resistance of the foamed molded body and foamed laminate in the model. That is, , The molded foam body 31 311038 ^ -------- ^ --------- ^ (Please read the precautions on the back before filling out this page) 482798 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by consumer cooperatives tr --------- (Please read the notes on the back before filling out this page) A7 ---------- B7___ V. Description of the Invention (32) or Foam Stack The body is placed in a high temperature tank of 150t: and heated for 22 hours. The absolute value of the difference between the dimension h before heating and the dimension I after heating in the model of the foamed molded body or foamed laminate is calculated according to the following formula: Rate (%). Dimensional change rate below 2¾ is 0 (good heat resistance), and the excess is X (bad heat resistance) for evaluation. ”Dimensional change rate (%) = 丨 T3-T4 I X100 / Τ3 Evaluation of the appearance The appearance of the foamed molded body in the model was visually observed. The appearance of melting or cracking on the surface was χ (outer beetle), and the appearance of melting or cracking on the surface was 0 (appearance). (Good), no melting or cracks on the surface, and fine lines on the surface are evaluated as ◎ (especially good appearance).… In a foamed laminate, the following methods are used to measure and evaluate the foam molding from the film or sheet model. The falling ball impact value is indicated by the delamination resistance of the body, the surface smoothness of the foamed laminate, and the overall impact strength. The measurement of the delamination strength is cut out of the foamed laminate to make a film or sheet on the cover. The size of the pressing surface is 160mm in length and 25mm in width (thickness of the laminated body = 20mm). From this sample, a film or sheet with a length of 100mm is peeled off from the sample before measurement, and then a Tianshilong universal testing machine is used. UCT] 0T)] manufactured by Gram Co., Ltd. The delamination resistance (N / 25mm) when the front end of the foamed molded body and the front end of the film or sheet in the mold were peeled from each other was measured in 180 directions. The test conditions are as follows: Stretching speed: 200mm / min

This paper is a Chinese national standard (CNS) A4 specification (210 X 297 publicly loved 32 311038 called 2798. Printed on sample A7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. V. Description of the invention (33 Stretching distance: 50mm) A rubber roller uniformly coated with black ink for printing on the surface rotates the film or sheet of the foamed laminate on the laminated surface. The black ink for printing on the surface of the drum copies and prints the film or sheet onto the laminated surface. Surface 〇 Visually observe the printing result. The surface smoothness is good if the surface is not peeled off (0), and the surface smoothness is not good because of unevenness on the surface (x). The appearance is evaluated. Gold cut the foamed laminate to make a sample of a film or sheet on the surface to be laminated with a length of 215 mm and a width of 40 mm (the thickness is the thickness of the laminate = 20 mm). The sample was arranged at a distance of 155 mm. On one pair of retaining materials, after placing the film or sheet on the laminated surface, it will weigh 32i from the specified height in the middle position of the two retaining materials and the center position of the sample width direction. Check the surface of the sample to see if there is damage on the surface of the ball. This test is to repeat the test after the steel ball is dropped from different heights. The lowest value of the damaged height is calculated as the falling ball impact value to evaluate the laminate. The strength is shown by the aromatics used in each of the following examples and comparative examples. ^ The purpose of the tree is to indicate that the paper size of the table applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 311038 — — — — — — — — — II I --— It ·! — —---- (Please read the notes on the back before filling this page) 33 482798 A7 B7 V. Description of the invention (34) Table 1 Content ratio of resin number (% By weight) IV value IPA unit CHDM unit 1 Ring pellet resin obtained from recycling of polytetra bottles 0 0 0.67 2 Aromatic polyester based on polycondensation reaction of ethylene glycol, isophthalic acid and terephthalic acid Resin (MA-1344 manufactured by Unica) 5.8 0 0.72 3 Aromatic polyester resin synthesized by polycondensation of ethylene glycol, cyclohexanedimethanol, and terephthalic acid 0 17.2 0.75 4 ethylene glycol , Isophthalic acid and terephthalic acid Aromatic polyester resin synthesized by polycondensation reaction 1.4 0 0.80 5 Aromatic polyester resin synthesized by polycondensation reaction of ethylene glycol, cyclohexanedimethanol and terephthalic acid 0 0.9 0.80 6 ethylene glycol Aromatic polyester resin synthesized by polycondensation with terephthalic acid 0 0 0.88 7 Aromatic polyester resin synthesized by polycondensation with ethylene glycol, isophthalic acid and terephthalic acid 1.40 0.82 (Please read the precautions on the back before filling this page) Order --------- · Example 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as the above table 1 75 parts by weight of No. 1 resin and 25 parts by weight of No. 2 resin, 0.30 parts by weight of pyromellitic dianhydride as a modifier, and 0.03 parts by weight of sodium carbonate as a modifier, were placed in an extruder [calibre: 65mm, L / D ratio: 35], melting and kneading under the conditions of a spiral revolution of 50 rpm and a barrel temperature of 270 to 290 ° C, butane (n-butane) used as a blowing agent from the barrel / Isobutane = 7/3) Press in at a ratio of 1.0 part by weight to 100 parts by weight of the mixture. Pass the molten mixture through the circular mold connected to the front end of the barrel. The paper size is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 34 311038 482798 40 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 Five Explanation of the invention (35) [Die opening gap · 0.4mm, 掇 口 · · η Ί &gt; production town diameter · 60mm], extruded into a cylindrical foam molding in the atmosphere, its inner surface and the mold core (internal use 2 ．。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。） 。。。。。。。 . This extruded foam was cut into a columnar shape with an angle of about 5 mm x 3 mm x 1 mm by a cutter to obtain pre-foamed particles. The pre-expanded particles have a bulk density of 012 g / cm3, a degree of crystallization of 3 · ", and a south peak temperature of crystallization of 135 rc. X. The content ratio of the pre-expanded particles IPA single το is 4% by weight The content ratio of the cjjdm unit is 0% by weight. Then, 'the above-mentioned pre-foamed particles are put into a closed container, carbon dioxide is pressed, and it is maintained for about 4 hours at a gauge pressure of 098 MPa. From the closed container The taken out pre-foamed particles were filled in a mold groove with an internal size of 300 min X 400 mm X 20 mm opened by closing the male mold and the female mold, and then the gauge pressure was 0.07 MPa from the female mold. Introduce into the mold tank for 45 seconds', and then introduce the steam with a gauge pressure of 0 · 10MPA from the two molds of the male mold and the female mold into the mold tank for 45 seconds. After performing the foam molding in the mold, maintain the state of stopping the vapor introduction for 120 seconds, and finally use water Cool and take out the foamed molded body in the model. The apparent density of the foamed molded body in the model is 0.12g / cm3. The fusion rate is 62%, showing good fusibility, bending strength is ί5Mpa, deflection amount is 2.73mm Is high strength. Example 2 In addition to using the above Table 1 Except that 100 parts by weight of No. 2 resin was used as the aromatic polyester resin, the same operation as in Example 1 was used to make a pre-foamed body (please read the precautions on the back before filling this page). Standard (CNS) A4 specification (210 X 297 mm) 35 311038 482798 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (36) Particles to obtain the foamed molded body in the model. Pre-foamed particles The bulk density is 0.12 g / cm3, the degree of crystallization is 2.6%, and the peak temperature of crystallization is 154 3t. In addition, the content ratio of the IPA unit of the pre-foamed particles is 58% by weight, and the content ratio of the CHDM unit is 0. % By weight. The foamed molded body in the model is a good molded body with no voids between the particles. It has an apparent density of 0.12 g / cm3 and a fusion rate of 92%. It shows good fusion properties, bending strength is 1.19 MPa, and deflection. It is 10.6 mm, which is high strength. Example 3 The same operation as in Example except that 85 parts by weight of No. 1 resin and 15 parts by weight of No. 3 resin are used as the aromatic polyester resin described in Table 1 above, Manufacture of pre-foamed particles and obtain models Foamed molded body. The pre-foamed particles have a bulk density of 0.12 g / cm3, a degree of crystallization of 4.0%, and a peak temperature of crystallization of i36 7 ° c. Also, the content ratio of the IPA unit of the pre-foamed particles described above It is 0% by weight, and the content ratio of the CHDM unit is 2.6% by weight. The apparent density of the foamed molded body in the model is 012 g / cm3, and the fusion rate is 68%. 'It shows good fusion properties, and its bending strength is 〇2MPa, The deflection amount is 3.42 mm, which is high strength. In the bending test of the foamed molded body obtained in the above-mentioned implementations 1 to 3, 'When observing the fractured surface of the fractured molded body, each melting rate is strong', so it will not be separated from the particle surface, and it is confirmed as the particle body. fracture. Example 4 Extrude the thin sheet before cutting, which is manufactured in the same operation as in Example 2. C Please read the phonetic on the back? Matters refill this page}

This paper size is in accordance with China National Standard (CNS) A4 (21〇X 297 public love) 36 311038 482798 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs and A7 printed by Consumer Cooperatives V. Description of the invention (37 Foam [Apparent density ·· 〇2g / em3, thickness ... K〇nim] is formed on a food container through a hot plate forming machine. At this time, the forming conditions are a heating plate temperature of 120 C, a heating time of 4 seconds, and a forming mold temperature of 25 ° c. The molding time was 6 seconds. The shape of the container was 120 mm in width, 50 mm in length, and 25 mm in height. The container was cut into a sheet shape of about 5 x 3 mm by a cutting machine, and used as a pre-foam particle. The foam particles were treated in the same manner as in Example 2 to obtain a molded foam body. The pre-foam particles had a bulk density of 0 08 g / em3, a degree of crystallization of 2.9%, and a peak crystallization temperature of 1545 ° F. The content ratio of the IPA unit of the pre-expanded particles is 58% by weight, and the content ratio of the chdm unit is 0% by weight. The foamed molded body in the model is a good molded body without voids between particles, and its apparent density is 0.08g / cm3, the fusion rate is 90%, showing good fusion properties The flexural strength is 1,000 MPa and the deflection amount is 8.6 mm, which is high strength. Comparative Example 1 Except using 100 parts by weight of No. 1 resin described in Table 1 above as an aromatic non-polyester-based resin, it is the same as the example. 1 In the same operation, pre-foamed particles were produced to obtain a foamed molded body in the model. The pre-foamed particles had a bulk density of 0.12 g / cm3, a degree of crystallization of 9.6%, and a peak crystallization temperature of 126.8 ° C. The content ratio of the IPA unit of the pre-foamed particles is 0% by weight, and the content ratio of the CHDM unit is 0% by weight. Although it is possible to produce in-mold foam molding with an apparent density of 0.12g / cm3 — I — — I — III — — III Order — — — — — I! · (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 * 297 mm) 37 311038 482798 A7 B7_______ V. Description of the invention (38), but its fusion rate is 33%, and the fusion rate is low. Moreover, the flexural strength is 0 61 MPa, and the deflection amount is 1.37 mm, which is more foam than in the models of Examples 1 to 4. Poor formed body. (Please read the precautions on the back before filling this page) II I I --- Order ----— II--, the results above are shown in Table 2 to Table 4. Table 2 Aromatic polyester resin IPA content ratio (wt%) CHDM content ratio (wt%) Actual 1 1.4 0 Application 2 5.8 0 Example 3 0 2.8 4 5.8 0 Comparative Example 1 0 0 Table 3 Crystallization degree of pre-foamed particles (%) South peak temperature of crystallization (° C) Bulk density (g / cm3) Solid 1 3.6 135.2 0.12 Application 2 2.6 154.3 0.12 Example 3 Γ 4.6 136.7 0.12 4 2.9 154.5 Γ 0.08 Comparative Example 1 9.6 126.8 0.12 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 4 _ The fusion rate (%) of the molded foam in the model Flexural strength (Mpa) Deflection scale Apparent density (s / cm3) Real 1 62 1.15 0.12 Application 2 92 1.19 _10j5 0.12 Example 3 '68 [1.02 ΓΤ42 0.12 4 90 1.00 8.60 0.08 Comparative Example 1 33 0.61 1.37 0.12 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 38 311038 Qi 2798 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 &quot; —-—-- 2Z______ One or five, description of the invention (39) Example 5 will be used as the aromatic polyester resin The above table! 100 parts by weight of the No. 4 resin, parts by weight of pyromellitic dianhydride as a modifier, and 0.03 parts by weight of sodium carbonate as a modifier, were placed in an extruder [caliber · 65mm, L / D ratio : 35], melting and kneading under the conditions of a spiral revolution of 50 rpm and a barrel temperature of 270 to 290 ° C, butane (n-butane / isobutane as a foaming agent) = 7/3) Press in at a ratio of 10 parts by weight to 100 parts by weight of the mixture. Next, extrude through the nozzles of a multi-nozzle die [15 nozzles with a diameter of 0.8mm are arranged on the line] connected to the front end of the extruder barrel, and extrude and cool in the cooling water tank immediately after foaming. After the cooled monofilament extruded foam was sufficiently removed from the water, it was cut into a substantially cylindrical shape with a pellet machine to obtain pre-expanded foam particles. The pre-expanded particles have a bulk density of 014 g / cm3, a particle size of 14 to 2.5 mm, a degree of crystallinity of 4 · 8%, a peak crystallization temperature of 13 5 · 0 ° C, and an average cell diameter of 0.4. mm, continuous bubble rate is 10 5%. The melt tension of the resin forming the pre-foamed particles was le81 g. Next, the pre-foamed particles described above were placed in a closed container, carbon dioxide was pressed thereinto, and the pressure was maintained at a pressure of 0.49 MPa for about 4 hours. The pre-expanded granules taken out of the closed container were filled into a mold groove having an internal size of 300 mm x 400 mm x 20 mm formed by closing the male mold and the female mold, and then the gauge pressure was set from the female mold to 0. 2 MPa of steam is introduced into the mold tank for 10 seconds, and then the two molds of the female mold and the negative pressure are introduced into the mold tank with a pressure of 0,06 MPa for 20 seconds. After the foam molding in the model is performed, it will remain stopped ------- ------i! --- til! —-- ^ (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 39 311038 482798 A7 B7 V. Description of the invention (40) Stop the introduction of steam for 120 seconds, and finally cool with water to take out the foamed molded body in the model. (Please read the notes on the back before filling this page) The apparent density of the foamed molded body in the model is 0.14g / cm3. The shrinkage ratio of this molded body was 0.2%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 70%, which showed good fusion properties, and the bending strength was 1.28Mpa and the deflection amount was 7.77 mm, which was high strength. The appearance is also good. Example 6 The same procedure as in Example 5 was performed except that 100 parts by weight of the No. 2 resin described in Table 1 was used as an aromatic polyester resin and 0.25 parts by weight of pyromellitic dianhydride as a modifier. In the same operation, pre-foamed particles are produced to obtain a foamed molded body in the model ^ The pre-foamed particles have a bulk density of 0.14 g / cm3, a particle diameter of 1.4 to 2.5 mm, a degree of crystallization of 3.0%, and crystals The peak chemical temperature was 153.9 ° C, the average cell diameter was 0.47 mm, and the continuous cell ratio was 20.2%. The melt tension of the resin forming the pre-expanded particles was 12 ig. The apparent density of the foamed molded body in the model printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 014 g / cm3. The fineness of the formed body was 0.3% ', and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 93%, showing good fusibility, and the bending strength was 1.38 MPa and the deflection amount was 12.5 mm, which was high strength. The appearance is also good. Example 7 Except that the resin No. 2 and No. 1 described in the above Table 1 as the aromatic polyester-based resin were mixed at a weight ratio of 25:75, a transesterified product [IPA Unit content ratio: 丨 4% by weight, CHDM unit content ratio: 0% by weight] In addition to 100 parts by weight, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to this paper size 40 311038 482798 Economy A7 B7 printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau V. Description of Invention (M) Example 5 The same operation was performed to produce pre-expanded particles and obtain the foamed molded body in the model. In addition, in order to melt and knead the transesterification, in the barrel of the above-mentioned extruder for extruding and foaming, firstly, as a foaming agent, Ding Yu; The pre-expanded particles have a bulk density of 0.14 g / cm3, a particle size of ι · 4 to 2.5 mm, a degree of crystallization of 4.8%, a peak crystallization temperature of 135.5 ° C, an average cell diameter of 0.47 mm, and continuous cells. The rate is 19.8%. The melt tension of the resin forming the pre-expanded particles was 1.22 g. The apparent density of the foamed molded body in the mold was 0.014 g / cm3. The shrinkage ratio of this molded body was 0.3%, and it was confirmed that the dimensional stability was good. The fusion rate was 65%, showing good fusion properties. The bending strength was 24 MPa, and the deflection amount was 6.54 mm, which was high strength. The appearance is also good. Example 8 The same operation as in Example 5 was performed except that 100 parts by weight of the No. 5 resin described in Table 1 was used as the aromatic polyester-based resin, to produce pre-expanded particles and obtain an in-mold foam molding. body. The pre-expanded particles had a bulk density of 0.14 g / cm3, a particle size of 14 to 2.5 mm, a degree of crystallization of 2.5%, and a peak crystallization temperature of 1367. 〇. The average bubble diameter is 0.42mm and the continuous bubble ratio is 13.6%. The melt tension of the resin forming the pre-foamed particles was 153 g. The apparent density of the foamed molded body in the mold was 0.14 g / cm 3. This molded article had a shrinkage of 0.2%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 64%, showing good fusibility, the bending strength was 22 Mpa, and the deflection amount was 7.00 mm, which was high strength. The appearance is also good. ------------- Installation -------- Order --------- Line (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 Specification (210 X 297 mm) 41 311038 482798 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 --------- £ L _____ V. Description of the Invention (42) ~~~ Example 9 Except that the resin No. 3 and No. 1 described in the above-mentioned table 丨 which is an aromatic polyester resin were used in a weight ratio of 50 ·· 50, a 3 melting and kneading transesterification was performed. [IPA unit content ratio · 〇 weight unit content: 8.6% by weight] 100 parts by weight and 0.35 parts by weight of pyromellitic dianhydride as a modifier, the same operation as in Example 5, = Manufacture of pre-expanded particles and obtain a foamed molded body in the mold. In order to melt and knead the transesterification, butane as a foaming agent was first introduced into the barrel of the extruder for extrusion foaming. The pre-expanded particles have a bulk density of 4 g / cm3, a particle size of 14 to 2.5 mm, a degree of crystallization of i 0%, a peak crystallization temperature of 15 i 2, an average cell diameter of 0.43 mm, and a continuous cell ratio It was 16.4%. The melt tension of the resin forming the pre-expanded particles was 144 g. The apparent density of the foamed molded body in the mold was 0 14 g / cm 3. This molded article had a shrinkage of 0.2%, and it was confirmed that the dimensional stability was good. In addition, the melting rate was 93%, showing good fusibility, the bending strength was 32 Mpa, and the deflection amount was 11.2 mm, which was high strength. The appearance is also good. Example 10 Except that the No. 2 resin, No. 3 resin, and No. 1 resin described in Table 1 above as the aromatic polyester resin were used in a weight ratio of 1: 5: 8 5 and then melted and mixed. Except for the refined transesterified product [IPA unit content ratio: 0.6% by weight, CHDM unit content ratio: 0.9% by weight], the pre-foamed particles were produced in the same manner as in Example 5 An in-mold foamed molded body was obtained. fRead the notes on the back before filling in this page}

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 42 311038 # ·, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 482798 A7 --------- B7 ____ V. Description of the invention (43) In order to melt and knead the transesterification, in the barrel of the extruder for extruding and foaming described above, the tincture as the foaming agent is first pressed. The pre-expanded particles have a bulk density of 014 g / cm3, a particle size of 14 to 2.5 mm, a degree of crystallization of 4 5%, a peak crystallization temperature of i36 ye, an average cell diameter of 0.55 mm, and successive bubbles. The rate is 25.6%. The melt tension of the resin forming the pre-expanded particles was 102 g. The apparent density of the foamed molded body in the model was 0.014 g / em3. The shrinkage ratio of this molded article was 0.4%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 70%, showing good fusion properties, bending strength of 12 readings, and deflection amount of 7.65 mm, which was high strength. The appearance is also good. Example 11 Except that the No. 2 resin, No. 3 resin, and No. 树脂 resin described in the above Table 丨 which are aromatic polyester-based resins were used at a weight ratio of 50:25:25, and then melted and kneaded. The transesterified product [IpA unit content ratio: 2.9% by weight, CHDM unit content ratio: 43% by weight] 100 parts by weight and 305 parts by weight of pyromellitic dianhydride as a modifier, and In the same manner as in Example 5, pre-foamed particles were produced, and an in-mold foamed molded body was obtained. For melting and kneading of the transesterification, the barrel of the above-mentioned extruder for extruding and foaming was first pressed into the sintered sintering agent as a foaming agent. The bulk density of the pre-initiated / inclusive particles is 0.14 g / cm3, the particle size is 14 to 2.5 mm, the degree of crystallization is 3.2%, the peak temperature of crystallization is 148 8 &lt; t, and the average bubble diameter is 0.46 mm The continuous bubble rate is 198%. The melt tension of the resin forming the pre-expanded particles was 121 g. ------------- Install .------- Order --------- Line (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 Regulations (210 X 297 Public Love) 43 311038 482798 A7 B7 V. Invention Description (44) (Please read the precautions on the back before filling this page} The appearance of the foamed molded body in the model The density was 〇14g / 〇n3. The shrinkage of the formed article was 0.3%, and it was confirmed that the dimensional stability was good. Moreover, the fusion rate was 90%, showing good fusion properties, the bending strength was 丨 30Mpa, flexure The amount is 10.5mm, which is high strength. The appearance is also good. Comparative Example 2 The same operation as in Example 5 was carried out except that 100 parts by weight of No. 1 resin described in Table 1 was used as the aromatic polyvine resin. Pre-foamed particles to obtain a molded foam in the model. The pre-foamed particles have a bulk density of 0.14 g / cm3, a particle size of 14 to 2.5 mm, a degree of crystallization of 9.4%, and a peak crystallization temperature of 126. It has an average bubble diameter of 0.52 mm and a continuous bubble ratio of 24.3%. The melt tension of the resin forming the pre-expanded particles is 112 g. The apparent density is 0.14 g / cm 3. The shrinkage of the formed article was 0.3%, and it was confirmed that the dimensional stability was good. However, the fusion rate was low at 34%, and the bending strength was 072 MPa and the amount of deflection. It is 1.40mm, and the strength is insufficient. Also, the appearance is not good. Comparative Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in addition to using 100 parts by weight of No. 6 resin described in Table 1 above as the aromatic polyester resin Except for 5 parts by weight of pyromellitic dianhydride, which is a modifier, the same operation as in Example 5 was performed to produce pre-expanded particles to obtain a foamed molded body in the mold. Looseness of the pre-expanded particles It is 0.14 g / cm3, the particle size is I # to 2.5mm, the degree of crystallization is 9.1%, and the peak temperature of crystallization is i28. (TC, the average bubble diameter is 0.43mm, and the continuous bubble rate is 14.7%. , Form this paper standard applicable to China National Standard (CNS) A4 (210 X 297 mm) 44 311038 482798

V. Description of the invention (45)

00 The melt tension of the resin of the pre-foamed particles printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 1 54g. The apparent density of the foamed molded body in the model was 014 g / cm3. This molded article had a shrinkage of 0.2%, and it was confirmed that the dimensional stability was good. However, the fusion rate was low at 30%, the bending strength was 0.58 MPa, and the deflection amount was 1.23 mm ', which was insufficient in strength. Also, the appearance was not good. Comparative Example 4 Except that the resin No. 2 and No. 3 described in the above-mentioned Table 1 which are ^ • family polyester resins were used in a weight ratio of 50:50, a transesterified product was melted and kneaded. IPA unit content ratio: 29% by weight, CHDM unit content ratio: 8.6% by weight, non-crystalline] 100 parts by weight and trimellitic dianhydride as a modifier in addition to 0.40 parts by weight In the same manner as in Example 5, pre-foamed particles were produced, and an in-mold foamed molded body was obtained. In order to melt and knead the transesterification, butyl sintering as a foaming agent is first pressed into the barrel of the above-mentioned extruder for extrusion foaming. The pre-expanded particles have a bulk density of 4 g / cm3, a pinch of 14 to 2.5 mm, a degree of crystallization of 0%, a peak temperature without crystallization 'average bubble diameter of 0.45 mm, and a continuous bubble ratio of 18 9% . The melt tension of the resin forming the pre-expanded particles was 1.27 g. The apparent density of the foamed molded body in the mold was 0 14 g / cm 3. The shrinkage ratio of this molded body was 2.5%, and it was confirmed that the dimensional stability was not good. In addition, the fusion rate was 89%, showing good fusion properties, bending strength of 29 Mpa, too large 'deflection amount of 1.88 mm, and too small, it was confirmed to be brittle. The appearance is also not good 0 -------------- install -------- order --------- line Γ% first read the &gt; it matter on the back then Fill out this page &gt; This paper size is applicable to China National Tomb Standard (CNS) A4 specification ⑵Q χ 297 public issue 45 311038 482798 A7 V. Description of invention (46) The results of the above are shown in Table 5 to Table 7 Bureau of Intellectual Property, Ministry of Economic Affairs Printed by Employee Consumer Cooperatives Table 5 Aromatic polyester resin IPA content ratio CHDM! Contains melt tension (wt%) ratio (WtQ / o) — (g) 5 Τα 0 &quot; 1.81 solid 6 5.8 0 1.21 7 1.4 0 1.22 Application 8 0 0.9 1.53 Example 9 0 8.6 1.44 10 0.6 0.9 1.02 11 2.9 4.3 1.21 than 2 0 0 '1.12 to 3 0 0 1.54 Example 4 2.9 8.6 1.27 Table Crystallinity (%) Apparent density ( g / cm3) Maximum crystallization temperature (° C) Average cell diameter (mm) Continuous cell ratio (%) 5 4.8 0.14 135.0 0.40 10.5 Solid 6 3.0 0.14 153.9 0.47 20.2 7 4.8 0.14 135.5 0.47 19.8 Application 8 2.5 0.14 136.7 0.42 13.6 9 1.0 0.14 151.2 0.43 16.4 Example 10 4.5 0.14 136.9 0.5 5 25.6 11 3.2 0.14 148.8 0.46 19.8 to 2 9.4 0.14 126.3 0.52 24.3 to 3 9.1 0.14 128.0 0.43 14.7 Example 4 0 0.14 No 0.45 18.9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 46 311038 (Please read the precautions on the back before filling this page)% 1T-- ------- ^ 9 #. Flying Q 厶 丨 ％ A7

V. Invention Description (47)

Observation 〇

11 cases To &quot; 93 70 1.32 1.28 11.2 7.65 0.14 0.14

I 4 〇 〇 〇 90 34 30 89 1.30 0.72 0.58 1.29 10.5 1.40 1.23 1.88 0.14 0.14 0.14 0.14 〇 〇 〇 〇 〇

X ο 〇 〇

X

X

X (Please read the notes on the back before filling out this page): Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs f 1 2 1 will be used as the aromatic polyester resin in the above table 丨 No. 7 resin 100 weight injury, pyromellitic dianhydride as a melt tension modifier, 0 parts by weight and sodium carbonate as a modifier assistant, 03 parts by weight are put into the extruder [caliber · 65mm, L / D ratio: 35 ], The barrel temperature is 270 to 280. Melting and kneading were performed under the conditions, and butane (butane / isobutane = 7/3) as a foaming agent was pushed in from a barrel at a ratio of 100 weight parts to 1 weight weight of the mixture. Next, each nozzle of a multi-nozzle mold [15 nozzles with a diameter of 0 · 8ππη is arranged on a straight line] connected to the front end of the barrel of the extruder at a shear rate of 10,438 seconds and a molten resin density of 2 g / cm3 ) Cool immediately in the cooling water tank after extrusion foaming. After the cooled monofilament extruded foam was sufficiently removed from the water, it was cut into a substantially cylindrical shape by a trimmer to form primary pre-expanded foam particles. This paper size is applicable to the national standard (CNS) A4 size (210x297 mm) 311038 47 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 482798

The pre-foamed particles (primary pre-foamed particles) had a bulk density of 0.14 g / cm3, a particle size of 20 to 30 mm, a degree of crystallization of 4, and a peak crystallization temperature of 136.9. (: The average bubble diameter is 043 mm. In addition, the melting tension of the resin forming the pre-expanded particles is 133 g. Next, the pre-expanded particles are placed in a closed container, carbon dioxide is pressed, and the gauge pressure is After maintaining at a pressure of 0.49 MPai for about 2 hours, it was taken out of the closed trough. After that, it was heated in a pre-foaming machine equipped with a feather-shaped device with hot air (the temperature of the hot air blowing is 68 ° C) to refoam The secondary pre-foamed particles were obtained. The continuous bubble rate of the secondary pre-foamed particles was 4%, the bulk density was 0 06 g / cm3, and the degree of crystallization was 4.8%. The secondary pre-foamed particles are then placed in a closed container, carbon monoxide is pressed in, and the pressure is maintained at a pressure of 0.49 MPa for 4 hours. After that, it is taken out of the container and filled into the interior formed by closing the male mold and the female mold. After the size of the mold slot is 300mm X 400mm X 20mm, the steam with a gauge pressure of 0.02MPa is introduced into the mould slot from the female mold for 10 seconds, and then the gauge pressure is 0.06MPa from the female mold. Introduce into the mold cavity for 20 seconds to perform foam molding in the inner mold. Maintain the state of stopping the introduction of steam 120 After that, it was finally cooled with water to take out the foamed molded body in the model. The apparent density of the foamed molded body in the model was 0.060 g / cm3, and the shrinkage of the molded body was 0.80 / 0, and the dimensional stability was confirmed. Good. The fusion rate of the foamed molded body in the model is 85%, showing good fusion properties. The appearance is also good. (Please read the note on the back? Matters before filling out this page)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 48 311038 482798

Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (49) Example 13 In addition to using 100 parts by weight of No. 5 resin described in Table 1 above as an aromatic polyester resin and as a modifier The same procedure as in Example 12 was carried out except that the average weight of benzyltetracarboxylic acid was 2 002 parts by weight, and primary pre-expanded particles and secondary pre-expanded particles were produced to obtain a foamed molded body in the mold. ^ The pre-foam particles have a looseness of 0.14 g / cm3, a particle size of 20 to 3.0 mm, a degree of crystallization of 2.7%, a peak crystallization temperature of i36 70 ° C, and an average cell diameter of 0.51. mm. The melt tension of the resin forming the pre-expanded particles was 1.15 g. The secondary pre-foamed particles had a continuous cell ratio of 20.9%, a bulk density of 0.067 g / cm3, and a degree of crystallization of 2.7%. The apparent density of the foamed molded body in the model was 0.067 g / cm3. The shrinkage ratio of this molded article was 0.9%, and it was confirmed that the dimensional stability was good. The fusion rate of the foamed molded body in this model was 80%, showing good fusion properties. It also looks good. Example 14 Except using 100 parts by weight of No. 2 resin described in Table 1 above as an aromatic polyester resin, the addition amount of pyromellitic dianhydride was 0.25 parts by weight, and butane (n Butane / isobutane = 7/3) was pressed in an amount of 1.4 parts by weight with respect to 100 parts by weight of the mixture. An in-mold foamed molded body was obtained. The primary pre-expanded particles have a bulk density of 0.11 g / cm3, a particle size of 2.2 to 3.0 mm, a degree of crystallization of 3.2%, and a peak crystallization temperature of 153.9 ° C. — — — — — —-- I — — — — — — Til —----- ^ (Please read the note on the back? Matters before filling out this page) The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 49 311038 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives 50 482798 A7 ~ -5Z _____ V. Description of the invention (50) The average bubble diameter is 0.47ππη. The melt tension of the resin forming the primary pre-foamed particles was 1.2 lg. The continuous pre-foam particles had a continuous bubble rate of 15.2%, a bulk density of 0.055 g / cm3, and a degree of crystallinity of 3.3%. The apparent density of the foamed molded body in the model was 0.05 5 g / cm3. The shrinkage ratio of this molded article was 0.9%, and it was confirmed that the dimensional stability was good. The fusion rate of the foamed molded body in this model was 94%, showing good fusion properties. It also looks good. The combined results are shown in Tables 8 to 11. Table 8 Aromatic polyester resin IPA content ratio (wt%) CHDM content ratio (M%) Melt tension (g) Example 12 1.4 0 1.33 13 0 0.9 1.15 14 5.8 0 1.21 Table 9 Primary prefoam particles Day-end daily chemical degree (%) Apparent density (g / cm3) Crystallization south peak temperature (° C) Average bubble diameter (mm) Solid 12 4.8 0.14 136.9 0.43 Application of Ar »13 2.7 0.14 136.7 0.51 Example 14 3.2 0:11 153.9 0.47 311038 (Please read the notes on the back before filling this page)

482798 A7 B7 I. Description of the invention (51) Table 10 Crystallinity (%) of secondary pre-expanded particles Apparent density (g / cm3) Continuous cell ratio (%) Actual 12 4.8 0.060 11.4 Application 13 2.7 0.067 20- 9 Example 14 3.3 0.055 15.2 Table 11 Melt ratio (%) of foamed molded body in the model Apparent density (g / cm3) Dimensional stability Appearance 12 85 0.060 〇 Apply 13 80 0.067 〇 Example 14 94 0.055 〇 (Please read the precautions on the back before filling in this page) Ding 15 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Example 15 (Manufacture of Teflon resin master batch) It will be used as the aromatic polyester resin. 98 parts by weight of No. 4 resin described in Table 1 above and polytetrafluoroethylene resin [Polytetrachloroethylene 1 69 J manufactured by Asahi Glass Co., Ltd.] 2 parts by weight are put into an extruder [calibre: 40mm, L / D Ratio: 35], melting and kneading were performed under the conditions of a spiral revolution of 40 rpm and a barrel temperature of 270 to 280 ° C. Next, 'from a multi-nozzle die [8 nozzles with a diameter of 3.0 mm arranged on a straight line] connected from the front end of the barrel of the extruder, it was cooled in a cooling water tank immediately after extrusion. The monofilament extrudate after cooling is sufficiently removed from the water and cut with a pellet machine. This paper is suitable for standard + (CNS) A4 ^ (210 X 297 ^) 51 311038 482798

V. Description of the invention (52) Manufacture into small granules to produce polytetrafluoroethylene resin master batch. (Production of pre-expanded particles and in-mold foamed molded bodies) 100 parts by weight of the same aromatic polyester resin used in the above-mentioned polytetrafluoroethylene resin base compound, and the above-mentioned polytetrafluoroethylene resin base 0 parts by weight of rubber, 0.29 parts by weight of pyromellitic dianhydride as a modifier, and 0.03 parts by weight of sodium carbonate as a modifier, were placed in an extruder [batch: 65mm, L / D ratio: 35 ], Melting and kneading under the conditions of barrel temperature of 270 to 2901 'from the barrel of butyl sintering (n-butyl sintering / isobutyl sintering = 7/3) as a foaming agent to 100 parts by weight of the mixture It is pressed in at a ratio of parts by weight. With respect to 100 parts by weight of the square IS resin, the compounding amount of the polytetrafluoroethylene resin was 0.010 parts by weight. Next, a multi-nozzle die [15 nozzles with a diameter of K0mm arranged on a straight line] connected from the front end of the barrel of the extruder was extruded and immediately cooled in a cooling water tank. The monofilament extruded foam after cooling was sufficiently removed from the water, and then cut into a substantially cylindrical shape by a pellet machine to produce pre-expanded foam particles. The pre-foamed particles have a bulk density of 0.14 g / cm3, a particle size of 15 to 2.4 mm, a degree of crystallization of 5.0%, and a peak crystallization temperature of 135 °. . The average bubble diameter is 0.20mm and the continuous bubble ratio is 6.7%. The melt tension of the resin forming the pre-foam particles was 1.82 g. Next, "place the pre-foamed particles in a closed container and press in carbon dioxide", and maintain the pre-foamed particles taken out of the valley-closing device for about 4 hours under a pressure of 0.49 MPa. In the mold groove with an internal size of 300mm X 400mm 乂 20mm formed by closing the male mold and the female mold (please read the precautions on the back before filling this page) -------- tr ----- ---- This paper is printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economics, and the paper size is applicable to the Chinese National Standard (CNS) A4 (210 x 297 mm) 52 311038 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics 482798 A7 _ B7 5 After the invention is described (53), the steam with a gauge pressure of 0.02 MPa is introduced into the mold groove from the female mold, and then the gauge pressure is G. G6 MPa from the two molds of the male mold and the steam is introduced into the mold groove for 20 seconds. To perform in-mold foam molding. Next, the steam was stopped from being introduced for 120 seconds, and finally, it was cooled with water, and the foamed molded body in the mold was taken out. The apparent density of the foamed molded body in the model was 0.014 g / cm3, and the shrinkage of the molded body was 0.2%. It was confirmed that the dimensional stability was good. A fusion rate of 69% 'shows good solubility. The appearance is also good. Example 16 The same operation as in Example 15 was performed except that 100 parts by weight of No. 5 resin described in Table 1 was used as the aromatic polyester resin and 4 parts by weight of the above-mentioned polytetrafluoroethylene resin base compound. Pre-foamed particles are produced, and an in-mold foamed molded body is obtained. Moreover, with respect to 100 weight part of aromatic polyester resins, the compounding quantity of polytetrafluoroethylene resin was 0.077 weight part. The pre-foamed particles have a bulk density of 014 g / cni3, a grain grip of 15 to 2.4 mm, a degree of crystallization of 4.2%, a peak crystallization temperature of 136.7 ° C, an average cell diameter of 0.20 mm, and a continuous cell ratio 8.5%. The melt tension of the resin forming the pre-expanded particles was 170 g. The apparent density of the foamed molded body in the model was 0.14 g / cm3. The shrinkage ratio of this molded body was 0.3%, and it was confirmed that the dimensional stability was good. The solubility is 65%, showing good solubility. The appearance is also good. Example 17 Except that 100 parts by weight of the No. 2 resin described in Table 1 above was used as the aromatic polyester-based resin, pre-expanded particles were produced in the same manner as in Example 15 to obtain a molded foam body. Also, for aromatic polyester trees -------------- install ------ order --------- line 2 first read the precautions on the back before clearing Fill out this page} This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 53 311038 482798 A7 B7 V. Description of the invention (54) 100 parts by weight of fat, the compounding amount of polytetrafluoroethylene resin is 0.010 Parts by weight. The pre-expanded particles have a bulk density of 0.14 g / cm3, a particle size of 1.5 to 2.4 mm, a degree of crystallization of 3.1%, a peak crystallization temperature of 153.9 ° C, an average bubble diameter of 0.28 mm, and a continuous bubble rate 8.3%. The melt tension of the resin forming the pre-expanded particles was 1.75 g. The apparent density of the foamed molded body in the mold was 0.14 g / cm3. The shrinkage ratio of this molded body was 0.3%, and it was confirmed that the dimensional stability was good. The fusion rate was 90%, showing good fusion properties. The appearance is also good.

Ik Comparative Example 5 The same operation as in Example 15 was performed except that 100 parts by weight of the No. 1 resin described in Table 1 was used as the aromatic polyester resin, and the above-mentioned polytetrafluoroethylene resin master batch was not blended at all. Foam particles, thereby obtaining a molded foam in a mold. The pre-expanded particles had a bulk density of 0.14 g / cm3, a particle size of 1.5 to 2.4 mm, a degree of crystallization of 9.2%, and a peak crystallization temperature of 127.2. (:, Average bubble diameter is 0.55mm, continuous bubble ratio is 8.1%. In addition, the melt tension of the resin forming the pre-expanded particles is 1.85 g. The apparent density of the foamed molded body in the model is 0.14 g / cm3. The shrinkage rate of this molded product was 0.3%, and it was confirmed that the dimensional stability was good. However, the fusion rate was 30%, the fusion property was insufficient, and the appearance was also not good. The results are shown in Tables 12 to 14 in combination. (Please read the precautions on the back before filling in this page) m 0-丨 丨 丨 丨 丨 丨 丨 Order --- — — — — —. Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies Chinese national standards (CNS) A4 size (210 X 297 mm) 54 311038 482798

V. Description of the invention (55) i 00 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 Table Fangya Polyacetate PTFE (parts by weight) IPA content ratio (wt%) CHDM content ratio (wt ° / 〇) Actual 15 1.4 0 0.010 'Application 16 0 0.9 0.077 Example 17 5.8 0 0.010 Comparative Example 5 0 0 0 Table 13 Crystallinity of pre-foamed particles (%) Bulk density (g / cm3) Two peak temperatures (° C) of crystallization Diameter (mm) Continuous cell ratio (〇 / 〇) Actual 15 5.0 0.14 135.0 0.20 6.7 Application 16 4.2 0.14 136.7 0.23 8.5 Example 17 3.1 0.14 153.9 0.28 8.3 Comparative Example 5 9.2 0.14 127.2 0.55 8.1

Table 14 Fusion rate of foamed molded body in the model (0 / 〇) Apparent density (g / cm3) Dimensional stability appearance (mm) Actual 15 69 0.14 ○ ◎ 16 65 0.14 ○ ◎ Example 17 90 0.14 ○ ◎ Comparative Example 5 30 0.14 〇X Example 1R The resin No. 7 and No. 2 described in Table 1 above as the aromatic polyester resin are mixed at a ratio of 75:25 by weight, and then melted and mixed. ---------- Installation -------- Order --------- Line (Please read the precautions on the back before filling this page} This paper size applies to Chinese national standards (CNS) A4 specification (21〇x 297 mm)% 311038 ίο 厶 / ίο 厶 / Printed by A7 of the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (56) Refined vinegar exchange [IPA unit content ratio: 25 wt% chdm unit content ratio: 0 wt%] 100 parts by weight of the same polytetrafluoroethylene resin base compound as used in Example 15 above! Parts by weight of pyromellitic dianhydride as a modifier. 17.,. ^^ • 0.03 parts by weight of sodium carbonate as a modifier, put in the extruder [caliber: 65_, l / d ratio: 35] ' The rotation speed of the screw is 50 rpm, and the barrel temperature is 27 to 29. (The simmering and mixing under the condition of rc will be used as the simmering bun by the rich man (Jingdingyuan / Isobutan = 7/3) It is pressed at a ratio of 100 parts by weight to u parts by weight of the mixture. For aromatic polys based resin ⑽ by weight, the blending amount of polytetraethylene resin is 002 parts by weight. For S purpose For exchange melting and mixing, butane as a foaming agent is first pressed into the barrel of the above-mentioned extruder-extractor. Then, a multi-nozzle mold connected to the front end of the barrel of the extruder [15 is arranged on a straight line] Each nozzle with a diameter of 0 mm] was extruded and foamed and cooled in a cooling water tank immediately after cooling. The early filamentary extruded foam after cooling was sufficiently removed from the water and cut into a substantially cylindrical shape by a pellet machine as a pre-foaming. Pre-expanded particles have a bulk density of 0.14 g / cm3, a particle size of K5 to 2.4 mm, a degree of crystallization of 40%, a peak crystallization temperature of i38 9 &lt; &c; and an average cell diameter of 0. .22mm, continuous bubble ratio was 7.4%. The melt tension of the resin forming the pre-foamed particles was 1.8 g. Then, the pre-expanded particles described above were placed in a closed container, and carbon dioxide was injected thereinto, and the pressure was maintained at a pressure of 0.49 MPa for about 4 hours. The pre-expanded particles taken out from the closed container were filled in the The male mold and the paper size are applicable to China National Standard (CNS) A4 (210 X 297 mm)

-------- tr ---------. (Please read the note on the back? Matters before filling out this page) 56 311038 ^ 798

V. Description of the invention (57) After the female mold is closed, the internal size is 300 mm &gt; &lt; 400 mm &gt; &lt; 20 mm, and then the gauge pressure is 0.02 MPa from the female mold. The steam was introduced into the mold tank for 10 seconds, and then the steam with a gauge pressure of 006 MPa was introduced from the two molds of the male mold and the female mold into the branch tank for 20 seconds to perform in-mold foaming. Then, maintain the state of stopping the introduction of steam for 120 seconds, and finally cool it with water to take out the foamed shape in the model.

40 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The apparent density of the foamed molded body in the model is 0 14g / cm3. This molded article had a shrinkage of 0.2%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 86%, showing good fusibility and good appearance. The dimensional change was 0.5 to 3%, and the heat resistance was also good. Implementation Q1 except that isobutane was used alone as a foaming agent, the same operation as in Example i 8 was performed to produce pre-expanded particles and obtain a foamed molded body in the mold. The pre-expanded particles have a bulk density of 4 g / cm3, a particle size of ι · 5 to 2.4 mm, a degree of crystallization of 3.9%, a peak crystallization temperature of 139.1 ° C, an average cell diameter of 0.20 μm, and even The bubble rate was 7.0%. The apparent density of the foamed molded body in the model was 0.14 g / cm3. This molded article had a shrinkage of 0.2%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 84%, showing good fusibility and good appearance. The dimensional change was 0.556%, and the heat resistance was also good. Example 20 The same operation as in Example 18 was performed except that n-butane was used alone as a foaming agent to produce pre-expanded particles, and a molded body was obtained. The pre-foamed particles have a bulk density of 0.14 g / cm3 and a particle size of 1.5 to this paper size. The Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) is applicable. 57 311038 -------- ---- ^ Install -------- Order --------- line (please read the precautions on the back before filling this page) Called 798 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 &quot; ^-^ --------- V. Description of the invention (58) 2.4mm, crystallization degree is 40%, peak crystallization temperature is 138 generations, average bubble diameter is 0.22mm, continuous bubble rate 7 5%. The apparent density of the foamed molded article in the mold was 0.014 g / cm ^ The shrinkage of the molded article was 0.2% ', and it was confirmed that the dimensional stability was good. In addition, the dissolution ratio was 87%, which showed good fusion properties and good appearance. The dimensional change was 0.53%, and the heat resistance was also good. Except that butane was used as the foaming agent, and the injecting amount was 0.9% by weight with respect to the resin mixture, the same operations as in Example 18 were performed to produce pre-foamed particles to obtain a molded foam body. The pre-foamed particles have a bulk density of 014 g / cm3, a particle size of i 5 to 2.4 mm, a degree of crystallization of 3.90 / 〇, a peak crystallization temperature of 139 2 0 c, and an average cell diameter of 0.19 mm. 2. The consecutive bubble rate was 6.2%. The apparent density of the foamed molded body in the mold was 0.014 g / cm3. The shrinkage ratio of this molded body was 0.1%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 85%, which showed good fusion properties and good appearance. The dimensional change was 0.54%, and the heat resistance was also good. Example 2 7 Except that cyclopentane was used as the foaming agent, and the injecting amount was 1.4% by weight based on the resin mixture, the same operations as in Example 18 were performed to produce pre-foamed particles to obtain in-mold foam molding. body. The pre-expanded particles have a bulk density of 0.14 g / cm3, a particle size of 15 to 2.4 mm, a degree of crystallization of 4 2/0, a peak crystallization temperature of 138 7C, and c, and an average cell diameter of 0. 25mm, continuous bubble rate is 8.9%. (Please read the notes on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (21 × 297 mm) 58 311038 482798

A7 5. Description of the invention (59) The apparent density of the foamed molded body in the model is 014 g / cm3. The shrinkage ratio of this molded body was 0.2%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 90%, which showed good fusion properties and also good appearance. The dimensional change was 0.51%, and the heat resistance was also good. tExample 23 Except that Freon 134a was used as the foaming agent, and the amount of the resin was 1.9% by weight based on the resin mixture, the same operation as in Example 18 was performed to produce pre-foamed particles to obtain a foamed molded body in the mold. The pre-foamed particles have a bulk density of 014 g / cm3, a granule size of 15 to 2.4 mm, a degree of crystallization of 4.0%, a peak crystallization temperature of 138 ye, an average cell diameter of 0.20 mm, and a continuous cell ratio. 7 7〇 / 〇. The apparent density of the foamed molded body in the mold was 0.014 g / cm3. The shrinkage ratio of this molded body was 0.3%, and it was confirmed that the dimensional stability was good. In addition, the fusion rate was 85%, which showed good fusion properties and good appearance. The dimensional change was 0.55%, and the heat resistance was also good. Example 24 Except using the aromatic polyester resin described above, No. 2 resin, No. 3 resin, and No. 1 resin were mixed at a weight ratio of 50:25:25, and then melted and mixed. Refined transesterified product [IPA unit content ratio: 2.9% by weight, CHDM unit content ratio: 4.3% by weight] 100 parts by weight, and pyromellitic dianhydride as a modifier in addition to 0.33 parts by weight In the same manner as in Example 18, pre-foamed particles were produced, and an in-mold foamed molded body was obtained. In addition, in order to melt and mix the ester exchange, the Chinese National Standard (CNS) A4 specification (210 X 297 issued) is applicable to the above-mentioned paper size for extrusion foaming. -------- Order --- ----- line (Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperative, 311038 59 482798 A7 ______B7 _ V. Description of Invention (6〇) Press in butane as a blowing agent. (Please read the precautions on the back before filling this page) The pre-foamed particles have a bulk density of 0.14 g / cm3, a particle size of 15 to 2.4 mm, a degree of crystallization of 3.2%, and a peak crystallization temperature of 148 It has an average cell diameter of 0.27 mm and a continuous cell ratio of 15 3%. The melt tension of the resin forming the pre-expanded particles was 120 g. The apparent density of the foamed molded body in the model was 014 g / cm3. This molded article had a shrinkage of 0.3 ° / 0, and it was confirmed that the dimensional stability was good. In addition, the melt s ratio was 95%, which was a poor solubility, and the appearance was also good. fExample 25 Except that the resin No. 3 and No. 1 resin described in the above Table 1 as the aromatic polyester resin were mixed at a weight ratio of 50:50, and a transesterified product [IPA Unit content ratio: 0% by weight, Chdm monofluorene content ratio: 8.6% by weight] 100% by weight, 0.32 parts by weight of pyromellitic dianhydride as a modifier, and n-butane alone as a foaming agent Except that, in the same manner as in Example 18, pre-foamed particles were produced, and an in-mold foamed molded body was obtained. Printed by the Consumer Affairs Bureau of the Intellectual Property Office of the Ministry of Economic Affairs. Also for the purpose of melting and kneading for the transesterification, butane as a foaming agent is first pressed into the barrel of the above-mentioned extrusion foaming extruder. The pre-foam particles have a bulk density of 0.14 g / cm3 and a particle size of! 5 to 2.4 mm, the degree of crystallization is 1.2%, the peak temperature of crystallization is 1507 ° C, the average bubble diameter is 0.25 mm, and the continuous bubble ratio is 15 9%. The melt tension of the resin forming the pre-expanded particles was 144 g. The apparent density of the foamed molded body in the model was 014 g / cm3. The shrinkage of this molded article was 0.3%, and it was confirmed that the dimensional stability was good. In addition, the paper size is in accordance with China National Standard (CNS) A4 (210 X 297), &quot; ----- 311038 60 482798

V. Description of the invention (61) The printed rate of employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs is 95%, showing good fusion and good appearance. Example 26 The same operation as in Example 18 was performed except that 100 weight of No. 7 resin described in Table 1 was used to produce prefoamed particles once. The primary pre-foamed particles have a bulk density of 0.14 g / cm3, a particle size of 1.5 to 2.4 mm, a degree of crystallization of (8%, a peak crystallization temperature of 135,4, an average cell diameter of 0.20 mm, and continuous The bubble ratio is 6.7%. The melt tension of the resin forming the pre-expanded particles is 188 g. Then, the primary pre-expanded particles are placed in a closed container, and carbon dioxide is pressed in. The gauge pressure is 0.78 MPa. After being maintained under pressure for about 2 hours, it was taken out of the closed container and heated in a pre-foaming machine equipped with a feather-shaped device with hot air (the temperature of the hot air blowing is 68 ° C) to re-foam to obtain a secondary pre-foaming. The secondary pre-expanded particles have a continuous cell ratio of 11%, a bulk density of 0.045 g / cm3, and a degree of crystallization of 5.0%. Next, the secondary pre-expanded particles described above are placed again. Into a closed container, 'press in carbon dioxide, hold it at a pressure of 0.49 MPa for 4 hours, remove it from the closed container, fill it in a mold groove with an internal dimension of 300 mm x 400 mm x 20 mm, and then remove it from the female mold. The steam with a gauge pressure of 0.02 MPa was introduced into the mold groove for 10 seconds, and then the two molds from the male mold and the female mold were introduced. The steam is introduced into the mold with a gauge pressure of 0.06 MPa for 20 seconds, and the foam is formed in the mold. Maintain the state of stopping the introduction of steam for 120 seconds, and finally cool with water to take out the foamed molded body in the mold. The apparent density is 0.048g / cm3, the forming ---------! Equipment --- order --------- line (please read the precautions on the back before filling (This page) The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 61 311038 482798 A7 __ _B7_____ V. Description of the invention (62) The shrinkage of the body is 0.9%, which can confirm its size stability Good performance. The fusion rate of the foamed molded body in the model is 71%, which shows good fusibility. The appearance is also good. Example 27 Except the same pre-expanded particles produced in Example 18 as primary pre-expanded particles Used, the pressure of carbon dioxide during secondary foaming was 1.96 MPa except the gauge pressure, and the same operation as in Example 26 was used to produce secondary pre-foamed particles to obtain the foamed molded body in the model. The continuous bubble rate was 15.9%, the bulk density was 0.031 g / cm3, and the degree of crystallization was 4.2%. The apparent density of the inner foamed molded product was 0.034 g / cm3, and the shrinkage ratio of the molded product was 0.9%. It was confirmed that the dimensional stability was good. The fusion rate was 84%, showing good solubility. Appearance It is also good. The results above are shown in Table 15 to Table 18. (Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 15 Aromatic polyester resin IPA content ratio (wt %) CHDM content ratio (wt%) Melt tension (g) Real 18 2.5 0 1.80 19 2.5 0 1.80 20 2.5 0 1.80 21 2.5 0 1.80, application 22 2.5 0 1.80 23 2.5 0 1.80 24 2.9 4.3 1.20 25 0 8.6 1.44 cases 26 1.4 0 1.88 27 2.5 0 1.80 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2) ^ Γϋmm) 62 311038 482798 A7 B7 V. Description of the invention (63)

ί Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 16-Degree of crystallinity of pre-expanded particles (%) Bulk density (g / cm3) Peak crystallization temperature (° C) Average bubble diameter (mm) Continuous bubble rate (%) 18 4.0 0.14 138.9 0.22 7.4 Solid 19 3.9 0.14 139.1 0.20 7.0 20 4.0 0.14 138.8 0.22 7.5 21 3.9 0.14 139.2 0.19 6.2 Application 22 4.2 0.14 138.7 0.25 8.9 23 4.0 0.14 138.5 0.20 7.7 24 3.2 0.14 148.3 0.27 15.3 25 1.2 0.14 150.7 0.25 15.9 Example 26 4.8 0.14 135.4 0.20 6.7 27 4.0 0.14 138.9 0.22 7.4 Table 17 Crystallinity of secondary pre-foamed particles (%) Bulk density (g / cm3) Continuous cell ratio (%) Example 26 5.0 0.045 11.3 27 4.2 0.031 15.9 The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 63 311038 -------------- install --- (Please read the note on the back first Please fill in this page for matters) Order: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Description of the invention (64 Table 18: Foamed into the body in the model _ ^ ------ Appearance of heat resistance Example 0.0000000 ◎ ◎ ◎ ◎ (Manufacture of pre-foamed particles) 100 parts by weight of the No. 4 resin described in the above Table 1 of the family polyester resin, 0.30 parts by weight of pyromellitic dianhydride as a modifier, and 003 parts by weight of sodium carbonate as a modifier Put into the extruder [caliber: 65mm, L / D ratio: 35], and perform melting and kneading under the conditions of a spiral revolution of 50 rpm and barrels / litres of 270 to 29 ° C. The butane (n-butane / isobutane = 7/3) as a foaming agent was pressed in at a ratio of 1 part by weight to 100 parts by weight of the mixture. Then, a plurality of nozzles connected from the front end of the barrel of the extruder The mold [15 nozzles with a diameter of 08mm is arranged on a straight line] is immediately extruded and cooled in a cooling water tank. 311038 (Please read the precautions on the back before filling this page)

482798 A7 B7 V. Description of the invention (65) The monofilament extruded foam after cooling is sufficiently removed from the water and cut into a substantially cylindrical shape by a pellet machine to produce pre-foamed particles. The pre-foamed particles have a bulk density of 0.14 g / cm3, a particle size of 14 to 2.5 mm, a degree of crystallization of 4.8%, and a peak crystallization temperature of 136.9 ° C. (Manufacturing of foamed laminated body)

A foaming mold for manufacturing an in-mold foamed molded body having a length of 300 mm, a width of 400 mm, and a thickness of 20 mm was used. After the non-foamed PET film of the same size is installed on the bottom surface of the female mold corresponding to the side of the foamed molded body of 300 mm in length and 400 mm in width [degree of crystallinity: 4.1%, thickness: 200 // m], The closed mold cavity was filled with the pre-foamed particles manufactured as described above. Next, the steam of 106 ° C. and a gauge pressure of 0.02 MPa was introduced into the mold cavity from the male mold for 15 seconds, and then 1] 6 from the two molds of the male mold and the negative mold. 〇 Steam with a gauge pressure of 0.07 MPa is introduced into the mold tank for 45 seconds, and the foam is formed in the mold, and the PET film is laminated and integrated. Maintain the state of stopping the introduction of steam for 120 seconds, and finally cool with water to take out the foamed molded body in the mold. The foam layer of printed foam laminates printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs has a high delamination resistance of the foam layer and PET film in the model, which is 26.0N / 25mm. The fusion rate between them is 70%, showing good fusion properties, and a high falling ball impact value of 43 cm3. In addition to high strength and superior impact resistance, its surface smoothness is also good, and its appearance is also superior. The degree of crystallization of the foamed molded body in the model is 28.6%, and the degree of crystallization of the PET film is 25 6%, both of which have a degree of crystallization. It can be seen that the foamed laminated body has not only superior strength and appearance, 311038 ( Please read the notes on the back before filling in this page) ^ Zhang scale is applicable to Zhongguanjia Standard (CNS) A4 specification (2ig χ Norwegian public love) ---- 65 482798 A7 __B7 _V. Description of the invention (66) Its financial and thermal properties are also superior. Example 29 (Production of pre-expanded foam particles) A pre-expanded foam particle was produced in the same manner as in Examples 2 to 8 except that 100 weight of No. 5 resin described in Table 1 was used as the aromatic polyester resin. The pre-expanded particles have a bulk density of 0.14 g / cm3, a particle size of 1.4 to 2.5 mm, a degree of crystallization of 2.5%, and a peak crystallization temperature of i36.7 ° C. (Manufacturing of foamed laminated body) The same PET film [degree of crystallinity: 4.1%, thickness: 200 // m] was used as in Example 28, and a pair of molds were closed, and then formed in the mold groove The pre-foamed particles manufactured as described above are filled therein. Next, the steam of 106 ° C and the gauge pressure of 0.02 MPa was introduced into the mold tank from the male mold for 15 seconds, and then the steam of 122 ° c and the gauge pressure of 0.09 MPa was introduced into the mold tank from the male and female molds. In 45 seconds, it is laminated with PET film and integrated while performing in-mold foam molding. Maintain the state of stopping the introduction of steam for 120 seconds, and finally cool with water to take out the foamed molded body in the mold. The foamed laminated body has a high delamination resistance of the foamed layer of the foamed molded body in the model and the PE butt film, which is 25 · ON / 2 5 mm. The particle ratio of the foamed molded body in the model is 64. %, Showing good solubility, and the falling ball impact value is 42cm, in addition to the south strength and superior impact resistance, its surface smoothness is also good, and its appearance is also superior. The degree of crystallinity of the foamed molded body in the model is 28.2%, and the degree of crystallinity of PET film is 28 3%. Both have the paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 66 311038 (please (Please read the notes on the back before filling out this page) dw -I nn «ϋ -_i-i n ϋ ϋ -ϋ I ϋ n ϋ.

482798

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Affairs Co., Ltd. 311038 A7 B7 V. Description of the invention (67) The high degree of crystallinity indicates that the foamed laminate is not only superior in strength and appearance, but also superior in heat resistance. Example 30 0 (Production of pre-expanded particles) Except for using 100 weight of No. 2 resin described in Table 1 above and 0.25 parts by weight of pyromellitic dianhydride as a modifier, the same as Example 28 In the same manner, pre-foamed particles were produced. The pre-foamed particles have a bulk density of 014 g / cm3, a particle size of 1.4 to 2.5 mm, a degree of crystallization of 3.0%, and a peak crystallization temperature of 153 ye. (Manufacturing of foamed laminated body) The same pet film [degree of crystallinity: 4.1%, thickness: 200 // m] as that used in Example 28 was sealed with a pair of molds, and The mold cavity is filled with the pre-foamed particles manufactured as described above. Then, the steam of 106 ° C and gauge pressure of 0.02 MPa was introduced into the mold tank from the% mold for 15 seconds, and then the steam of U20c and gauge pressure of 0.05 MPa was introduced into the mold tank from the two molds of the male mold and the female mold. Within 45 seconds, while carrying out the in-mold foam molding, it is laminated with the PET film for integration. Maintain the state of stopping the introduction of steam for 120 seconds, and finally cool with water to take out the foamed molded body in the mold. The foamed laminated body has a high delamination resistance of the foamed layer of the foamed molded body in the model and the PEE film, which is 28.0N / 25mm. The fusion rate between the particles of the foamed molded body in the model is 93%, which is good. Weldability and high drop ball impact value of 51cm. In addition to high strength and superior impact resistance, its surface smoothness is also good, and its appearance is also superior. China National Standard (CNS) A4 specification (210 X 297 mm) is used for the knot of the foamed molded body in the model ------------- installation -------- order --- ------ Line (Please read the precautions on the back before filling this page) 482798 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7_______ V. Description of the invention (68) Crystallinity is 25.4%, PET film The degree of crystallization is 25.2%, and both have a high degree of crystallization. From this, it can be seen that the foamed laminate is not only excellent in strength and appearance, but also excellent in financial properties. Example 31 A foamed laminate was produced in the same manner as in Example 28 except that a non-foamed PET film having a degree of crystallinity of 7.5% and a thickness of 500 m was used as the laminated film. The foamed laminated body has a high delamination resistance between the foamed layer of the foamed molded body in the model and the PET film, which is 22. ON / 2 5 mm. The fusion rate between the particles of the foamed molded body in the model is 70%. Shows good fusion properties, and has a high drop ball impact value of 75cm. In addition to high strength and superior impact resistance, it also has good surface smoothness and excellent appearance. The degree of crystallinity of the foamed molded body in the model is 28.6%. The degree of crystallinity of the PET film is 29.6%, all of which have a high degree of crystallinity. It can be seen that the foamed laminated body has not only excellent strength and appearance, but also heat resistance Also superior. Example 32 A foamed laminate was produced in the same manner as in Example 28, except that a non-foamed PET film having a non-crystalline (crystallinity: 0/0) and a thickness of 2000 was used as the laminated film. The foamed laminated body has a high delamination resistance between the foamed layer of the foamed molded body in the model and the amorphous PET film, which is 32 〇N / 25lnm. The fusion rate between the particles of the foamed molded body in the model is 70%. It shows good fusion properties, and has a high falling ball impact value of 44cm. In addition to high strength and superior impact resistance, its surface smoothness is also good, and its appearance is also superior. This paper size applies to China National Standard (CNS) A4 specification (21 × 297 mm) 1 1 — --- 68 311038 (Please read the precautions on the back before filling this page)

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482798

V. Description of the Invention (69) Example 33 Foaming of aromatic polyester resin printed by polycondensation reaction of ethylene glycol, isophthalic acid, and terephthalic acid printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Film [IPA cover; &gt; content ratio of human body dryness: 0.8% by weight, crystallinity: 700 / 〇, thickness: i 〇 melon, apparent density: 0.2 g / cm3] outside the device, It carried out similarly to Example 29, and produced the foamed laminated body. The foamed laminated body has a high delamination resistance of the foamed molded body and the foamed film in the model, which is 22.0N / 25mm. The fusion rate between the particles of the foamed molded body in the model is 64%, which shows good fusion properties. In addition, the falling ball balance weight is high at 41cm. In addition to high strength and excellent impact resistance, its surface smoothness is also good, and its appearance is also superior. The degree of crystallization of the foamed molded body in the model is 28.2%, and the degree of crystallization of the foamed film is 28 5%, both of which have a high degree of crystallization. It can be seen that the foamed laminate has not only excellent strength and appearance, but also heat resistance. Also superior. Example 34 Except for a PET resin foamed film synthesized by a polycondensation reaction of ethylene glycol and terephthalic acid [degree of crystallinity: 12 3/0, thickness · 1, thickness · 0.2 g / cm3 ] Except that it was a foamed film, it carried out similarly to Example 33, and produced the foamed laminated body. The foamed laminated body has a high delamination resistance of the foamed molded body and the foamed film in the model 'is 18.0N / 25mm, and the fusion rate between the particles of the foamed molded body in the model is 64%, showing good fusion properties. , And the falling ball impact value is high, is 39cm, in addition to high strength and superior impact resistance, its surface smoothness is also good 'excellent appearance. The degree of crystallization of the foamed molded body in the model is ------------------------- order --------- line (please read the back of the first Note: Please fill in this page again.) This paper uses the Chinese standard (CNS) A4 specification (210 X 297 mm). 69 311038 482798 A7

V. Description of the invention (70) 28.2 / ^, the degree of crystallization of the foamed film is 306%, all of which have a high degree of crystallization. It can be seen that the foamed laminate has not only excellent strength and appearance, but also its heat-resistant economic department The Intellectual Property Bureau employee consumer cooperatives are also superior in printability. Comparative Example 6 Pre-foamed particles were produced in the same manner as in Example 28 except that 100 parts by weight of No. 1 bark wax described in Table 1 was used as the aromatic polyester resin. The pre-foamed particles have a bulk density of 0.4 g / cm3, a particle size of 4 to 2.5 mm, a degree of crystallization of 9.4%, and a peak crystallization temperature of 126 3 ^. A foamed laminate was produced in the same manner as in Example 28 except that the above-mentioned pre-expanded particles were used. The foamed laminated body has a low delamination resistance of the foamed molded body and the PET film in the model, which is 3.0N / 25mm. The foamed molded body in the model has a fusion rate between particles of 34% and poor fusion properties. In addition, the falling ball impact value was low at 24 cm, the strength was insufficient, and the impact resistance was poor. Comparative Example 7 An attempt was made to produce a foamed laminate in the same manner as in the example except that a non-foamed PET film having a crystallinity of 25.0% and a thickness of 200 // Π1 was used as the laminated film. However, the foamed molded body and the pET film in the mold are hardly fused, and a foamed laminate cannot be produced. A single product in-mold foam obtained by subjecting the above results and the same pre-foam particles used in Example 1 to in-mold foam molding under the same conditions as in Example 1 (known example 1 ) The results are summarized in Table 19 to Table 22. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 70 311038 (Please read the note on the back? Matters before filling out this page) $ Order ---------

482798 A7 B7 V. Description of the invention (71)

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 19 Aromatic polyester resin IPA content ratio (wt%) CHDM content ratio (wt%) Real 28 1.4 0 29 0 0.9 30 5.8 0 Application 31 1.4 0 32 1.4 0 Example 33 0 0.9 34 0 0.9 Comparative Example 10 0 0 11 1.4 0 Conventional Example 1 1.4 0 Table Crystallinity (%) Bulk Density (g / cm3) Crystallization Peak Temperature (° C) Type Crystallinity (%) Solid 28 4.8 0.14 136.9 Film 4.1 29 2'5 0 · 14 136.7 Film 4.1 30 3.0 0.14 153.9 Film 4.1 Application 31 4.8 0.14 136.9 Film 7.5 32 4.8 0.14 136.9 Film 0 Example 33 2.5 0.14 136.7 Foam Sheet 7.0 34 2.5 0.14 136.7 Foamed sheet 12.3 Comparative Example 10 9.4 0.14 126.3 Film 4.1 11 4.8 0.14 136.9 Film 25.0 Conventional Example 1 4.8 0.14 136.9 None of the paper sizes are in accordance with China National Standard (CNS) A4 (210 X 297) 71) 311038 (please read the precautions on the back before filling this page). Threading. 482798 A7 B7 V. Description of the invention (72 Delamination resistance (N / 25mm) Falling butterfly scour value (cm, table ^ Smooth Sex 28 2 6.0 * —---— 43 examples 29 25.0 42 30 28.0 ~ 51 31 31 22.0 75 32 32.0 44-〇 — Example 33 22.0 — 34 18.0 39 than 6 3.0 24 dry example 7 — one by one example 1 1 20 (Please read the Zhuyin on the back? Matters before filling out this page}

Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, Printed Table 22 Foamed Laminated Body ^] Foam forming body film or fusion rate (%) Crystallinity (%) Crystallinity (%) in the model. 25.6 29 64 28.2 28.3 30 93 25.4 25.2 Application 31 70 28.6 29.6 32 70 28.6 0 Example 33 64 28.2 28.5 34 64 28.2 30.6 Comparative Example 6 34 28.6 1 7 70 28.6 A conventional example 1 70 28.6 A paper size is applicable to China Standard (CNS) A4 size (210 X 297 mm) 72 311038

Claims (1)

8 79 2 8 4 (November 1, 1990) 1 · A crystalline aromatic polyester resin pre-foamed particle, which is characterized in that: it can be used for in-mold foam moldings with a bulk density of 0 〇1 to i 0g / cm3 and The crystallization peak temperature is 130 to 180 ° C. 2 As the aromatic polyester-based resin pre-expanded particles of the first patent application range, wherein the aromatic polyester-based resin contains isophthalic acid At least one of the derived unit and the unit derived from 1,4-cyclohexanediol, and the total amount is in the range of 0.5 to 10% by weight. 3. The aromatic polyester-based resin pre-foamed particles according to item 1 of the scope of the patent application, wherein the aromatic polyester-based resin is mixed with 0.005 to 0.1 weight &gt; Tetrafluoroethylene resin. 4. The aromatic polyester-based resin pre-expanded granules according to the patent application No. ^^, wherein the aromatic polyester-based resin is a manufacturer cut from an extruded foam. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs 5. If the aromatic polyester-based resin pre-expanded particles "wherein" is applied for the scope of patent application No. 4 is cut into a specified length, Form a slightly cylindrical shape. 6. The aromatic polyester resin pre-expanded particles according to item 5 of the scope of the patent application, wherein the extruded foam is added with a melt tension modifier to adjust the melt tension of the aromatic polyacetate resin to 0. In a state of 7 to 30 g, those who perform extrusion foaming. 7. The aromatic polyester resin pre-expanded granules according to item 6 of the patent application, wherein the continuous cell ratio is 5 to 35%. This paper Guona HCNS5A4 specifications (210X 297 Gongchu) 1 311038 482798 ----- H3 8 · As for the aromatic polyester-based resin pre-expanded particles of item 4 of the patent application scope, wherein the pre-expanded The body particles are subjected to a re-foaming process at least once after being immersed in a gas under a pressurized state to adjust the bulk density. 9. The aromatic polyester-based resin pre-expanded granules according to item 1 of the patent application range, wherein the degree of crystallization is 1 to 80/0. 1〇 · —An in-mold foamed molded article, characterized in that: a mold groove formed by closing a male mold and a female mold for foam molding in the mold is filled with an aromatic polyester system of the first patent scope; Resin pre-foamed particles are heated and foamed in a mold. 11. The in-mold expanded molded article according to item 10 of the scope of patent application, wherein the apparent density is 0.01 to 1.0 g / cm3 and the fusion rate of the pre-expanded particles is 40% or more. 12 · —A foamed laminated body having the following characteristics: layering and integrating the foamed molded body and a film or sheet of an aromatic polyester resin in the model of the scope of application for patent No. 10; 13. The foamed laminated body according to item 12 of the scope of patent application, wherein the film or sheet has a delamination resistance of the foamed molded body from the model of 5N / 25mm or more. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China 14. If the foamed laminated body of item 12 of the scope of patent application is applied, the laminated system is manufactured through the following steps (1) to (3), where: ) · The step of pre-installing the thin polyester or thin sheet of aromatic polyester resin in the mold groove formed by closing the male mold and female mold for foam molding in the mold; Step (2): Put the above male mold and The female mold is closed, and then the mold cavity is filled with the aromatic polyester resin pre-expanded body under the scope of patent application No. 1. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) 2 311038 482798 ~- _ The step of H3 particles; and step (3): a step of laminating the foamed molded body in the mold and the film or sheet while heating and foaming the mold. 15. The aromatic polyester-based resin pre-expanded particles according to item 2 of the scope of the patent application, wherein the aromatic polyester-based resin is mixed with 0.005 to 0.1 parts by weight based on 100 parts by weight of the resin. Polytetrafluoroethylene resin, which has a monofilament-shaped extruded foam cut into a specified length to form a slightly cylindrical shape. 16. · As for the aromatic polyester resin pre-expanded particles of the item 15 in the scope of the patent application, wherein the extruded foam is added with a melt tension modifier to adjust the melt tension of the aromatic polyester resin to 0 · In the state of 7 to 3.0 g, foaming is performed, and the continuous bubble rate is $ 5 to 35%. % 1 # 7. For example, the aromatic polyester resin pre-expanded particles of item 16 of the scope of patent application, wherein the pre-expanded particles are further impregnated with gas at least once after being impregnated with gas. , Adjust the bulk density, the degree of crystallization is 1 to 8%. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs 18 · —In-mold foam moldings, in which the mold groove formed by closing the male mold and the female mold for foam molding in the mold is filled with the patent application No. 17 Xiangzhi aromatic polyester resin pre-foamed particles are heated and foamed in a mold. 19. The in-mold foamed molded article according to item 18 of the scope of patent application, wherein the apparent density is 0.01 to 1.0 g / cm 3 and the fusion rate of the pre-expanded particles is 40 ° /. The above. 2．If the foamed laminated body according to item 13 of the scope of the patent application, the laminated paper is in accordance with China National Standard (CNS) A4 specification (210X 297 public love) The system is manufactured through the following steps (1) to (3). Order: Step (1): Pre-install the aromatic polyester in the mold groove formed by closing the male mold and the female mold for foam molding in the mold. Steps of film or sheet of resin; Step (2): the step of closing the above male mold or female mold, and then filling the mold groove with the aromatic polyester resin pre-foam particles of the scope of patent application No. 1; And step (3): a step of laminating the foamed molded body in the mold with a film or sheet while heating and foaming the mold in the mold. Printed by the Staff Welfare Committee of the Central Bureau of Standards, Ministry of Economic Affairs, Jade Paper, New Zealand (CNS) A4 (210X 297 mm) 4 311038