JP7049971B2 - Molding method for polyarylene ether ketone resin sheet - Google Patents

Description

The present invention relates to mechanical properties, heat resistance, electrical insulation, chemical resistance, radiation resistance, hydrolysis resistance, low water absorption, gas barrier property, recyclability, light weight, slidability, molding processability, etc. It relates to a molding method for a polyary ether ketone resin sheet having excellent properties.

Polyarylene etherketone (PAEK, also called aromatic polyetherketone) resin has mechanical properties, heat resistance, electrical insulation, chemical resistance, radiation resistance, hydrolysis resistance, low water absorption, recyclability, etc. It is an excellent thermoplastic crystalline resin. In view of this excellent property, the polyarylene ether ketone resin has been proposed and used in a wide range of fields such as an automobile field, an energy field, a semiconductor field, a medical field, and an aerospace field.

Most of the molded products made of polyarylene ether ketone resin are injection molded. However, in order to mold a wide variety of molded products in large quantities and at a low cost, extrusion molding using a polyarylene ether ketone resin is used for thermoforming by vacuum molding, pneumatic molding, vacuum pneumatic molding, press molding, etc. Therefore, it is common to once mold a polyarylene ether ketone resin sheet and then thermoform using a polyarylene ether ketone resin sheet.

However, when the polyarylene ether ketone resin sheet is thermoformed, a crystalline resin such as the polyarylene ether ketone resin has a small melt tension, so that it is easy to draw down (hanging phenomenon), and vacuum forming, pressure forming, and vacuum forming are performed. Thermoforming such as molding and press molding is difficult.

In order to prevent the occurrence of such drawdown, conventionally, (1) a method of adding an acrylic polymer to, for example, a thermoplastic engineering resin (see Patent Document 1), and (2) a poly of meta-xylylene diamine and dicarboxylic acid. A method for preparing a composition containing at least one kind of polyamide obtained by condensation and at least one kind of a copolymer of methyl methacrylate and acrylic acid and / or methacrylic acid (see Patent Document 2), (3) polyamide-based resin. (A) Acrylic copolymer (B) 0.1 to 15 containing 85 to 99.9 parts by mass and an unsaturated acid unit of 0.5 to 5% by mass and having a mass average molecular weight of 100,000 to 1.4 million. A method for preparing a polyamide-based resin composition containing a mass portion (the total of the polyamide-based resin (A) and the acrylic copolymer (B) is 100 parts by mass) has been proposed (see Patent Document 3).

Japanese Unexamined Patent Publication No. 1-2686761 Japanese Unexamined Patent Publication No. 8-67815 Japanese Unexamined Patent Publication No. 2008-255215

However, when the methods (1), (2) and (3) are adopted, drawdown can be suppressed to some extent and thermoforming can be performed, but poly by adding an acrylic polymer or a predetermined copolymer. A new major problem arises, which leads to the loss of the excellent properties of the arylene ether ketone resin. Further, since the acrylic polymer is inferior in heat resistance, when it is added to the polyarylene ether ketone resin, there arises a problem that it is decomposed at the time of preparing the molding material. Further, the production of the polyarylene ether ketone resin sheet becomes complicated, which leads to an increase in cost.

The present invention has been made in view of the above, and it is unlikely that the excellent properties of the polyarylene ether ketone resin will be lost, and it is possible to prevent the production of the polyarylene ether ketone resin sheet from becoming complicated and reduce the cost. It is an object of the present invention to provide a molding method for an arylene ether ketone resin.

The present inventor is a molding method for a polyarylene ether ketone resin sheet for molding a predetermined molded product using a polyarylene ether ketone resin sheet as a result of diligent research in order to solve the above problems.
The polyarylene ether ketone resin sheet has a storage elastic modulus (E') of [glass transition point (Tg) -10 ° C] or higher of the polyarylene ether ketone resin sheet [glass transition point (Tg) +50] of the polyarylene ether ketone resin sheet. In the temperature range of [° C.] or less, it has a recessed portion when it is drawn in a graph by temporarily decreasing to 2.0 × ¹⁰⁸ Pa or less and then increasing, and the relative crystallinity is less than 80%. The thickness of the polyarylene ether ketone resin sheet melt-extruded is 1 μm or more and 1000 μm or less.
This polyarylene ether ketone resin sheet is used in a temperature range of [glass transition point (Tg) -10 ° C] or higher of the polyarylene ether ketone resin sheet or lower [glass transition point (Tg) + 50 ° C] of the polyarylene ether ketone resin sheet. Preheat and then preheat the polyarylene ether ketone resin sheet into the female mold of the mold in the temperature range above the glass transition point (Tg) of the polyarylene ether ketone resin sheet and below the melting point of the polyarylene ether ketone resin sheet. It is characterized in that a predetermined molded product is thermoformed by inserting it into a hollow male mold and pumping a gas into the male mold to reduce the pressure inside the female mold .

A molding material containing a polyarylene ether ketone resin is melt-kneaded in a temperature range equal to or higher than the melting point of the polyarylene ether ketone resin and lower than the thermal decomposition temperature of the polyarylene ether ketone resin, and the molding material is melted and kneaded in a temperature range equal to or higher than the melting point of the polyarylene ether ketone resin. A polyarylene ether ketone resin sheet is formed by continuously extruding it from a die set in a temperature range lower than the thermal decomposition temperature of the polyarylene ether ketone resin, and this polyarylene ether ketone resin sheet is used as a polyarylene ether ketone resin sheet. It is preferable to cool to a glass transition point (Tg) + 20 ° C.] or lower.

Further, the polyarylene ether ketone resin sheet formed by continuously extruding from the die can be sandwiched between a cooling roll and a crimping roll having a [glass transition point (Tg) + 20 ° C.] or less of the polyarylene ether ketone resin sheet. ..

Here, the polyarylene ether ketone resin sheet within the scope of the claims includes a polyarylene ether ketone resin film as well as a polyarylene ether ketone resin sheet. The polyarylene ether ketone resin sheet is subjected to surface treatment such as corona treatment, plasma treatment, acid treatment, flame treatment, itro treatment, and coating treatment, if necessary. Further, the molding material of the polyarylene ether ketone resin sheet can be melt-kneaded while supplying an inert gas.

For thermoforming, the space between this mold and the polyarylene ether ketone resin sheet is evacuated through at least the holes of the mold, and the polyarylene ether ketone resin sheet is adsorbed and molded. Includes compressed air forming, vacuum forming, press forming, etc., in which a resin sheet is crimped onto a mold to form. Further, a winder for a polyarylene ether ketone resin sheet can be installed downstream of the cooling roll and the crimping roll. Between the cooling roll and the crimping roll and the winder, a blade for forming a slit in the polyarylene ether ketone resin sheet and a rotatable tension roll for applying tension to the polyarylene ether ketone resin sheet are arranged. It is possible.

According to the present invention, when a predetermined molded product is molded using a polyarylene ether ketone resin sheet, first, the prepared polyarylene ether ketone resin sheet is preheated. At this time, the temperature of the polyarylene ether ketone resin sheet is equal to or higher than [glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet and lower than [glass transition point (Tg) + 50 ° C] of the polyarylene ether ketone resin sheet. Preheat in the range to soften.

After the polyarylene ether ketone resin sheet is preheated in this way, a predetermined molded product can be obtained by thermoforming the polyarylene ether ketone resin sheet with a mold. At the time of this thermoforming, if the temperature of the mold is set in the range of the glass transition point (Tg) of the polyarylene ether ketone resin sheet or more and less than the melting point of the polyarylene ether ketone resin sheet, the crystallinity during thermoforming can be determined. Can be advanced.

According to the present invention, it is unlikely that the excellent properties of the polyarylene ether ketone resin will be lost, and molding by the melt extrusion molding method will prevent the production of the polyarylene ether ketone resin sheet from becoming complicated and reduce the cost. It has the effect of being able to. Further, since the polyarylene ether ketone resin sheet has a thickness of 1 μm or more and 1000 μm or less, it is possible to prevent the mechanical strength of the polyarylene ether ketone resin sheet from deteriorating. Further, the storage elastic modulus (E') is in the temperature range of [glass transition point (Tg) -10 ° C.] or more of the polyarylene ether ketone resin sheet [glass transition point (Tg) + 50 ° C. or less] of the polyarylene ether ketone resin sheet. Among them, since it is a resin sheet that forms recesses when graphed by temporarily decreasing to 2 × ¹⁰⁸ Pa or less and increasing, softening of the polyarylene ether ketone resin sheet can be expected. Therefore, thermoforming after using the polyarylene ether ketone resin sheet becomes easy. Further, the deformed polyarylene ether ketone resin sheet is brought into close contact with the cavity in the mold, and a high-precision molded product or the like can be thermoformed. In addition, since thermoforming is performed, it becomes easier to handle from design to production in a shorter number of manufacturing days as compared with injection molding.

According to the second aspect of the present invention, since the polyarylene ether ketone resin sheet is molded by the melt extrusion molding method, the handleability can be improved and the equipment can be simplified. Further, since the temperature at the time of melt-kneading and the temperature at the time of extruding the die are in the range of the melting point of the polyarylene ether ketone resin or more and lower than the thermal decomposition temperature of the polyarylene ether ketone resin, smooth melt extrusion molding can be expected. There is little risk of the polyarylene ether ketone resin in the molding material decomposing.

Further, since the polyarylene ether ketone resin sheet is cooled at a temperature equal to or lower than the [glass transition point (Tg) + 20 ° C.] of the polyarylene ether ketone resin sheet, crystallization of the polyarylene ether ketone resin sheet is suppressed and the polyarylene ether is suppressed. It is possible to prevent thermoforming using the ketone resin sheet from becoming difficult.

According to the invention of claim 3, the cooling roll and the crimping roll are adjusted to a temperature of [glass transition point (Tg) + 20 ° C.] or less of the polyarylene ether ketone resin sheet and brought into contact with the polyarylene ether ketone resin sheet. Therefore, it is possible to suppress the progress of crystallization of the polyarylene ether ketone resin sheet and prevent thermoforming by the polyarylene ether ketone resin sheet from becoming difficult.

Further, since the polyarylene ether ketone resin sheet can be pressed against the cooling roll by the crimping roll to be brought into close contact with the cooling roll, the thickness of the polyarylene ether ketone resin sheet can be controlled with high accuracy in the range of 1 μm or more and 1000 μm or more. Moreover, it is possible to improve the handleability and simplify the equipment.

It is an overall explanatory view schematically showing the manufacturing apparatus of the polyarylene ether ketone resin sheet in embodiment of the molding method for a polyarylene ether ketone resin sheet which concerns on this invention. It is a graph which shows typically the storage elastic modulus (E') of the polyetheretherketone resin sheet which the relative crystallinity is 27% in embodiment of the molding method for a polyarylene ether ketone resin sheet which concerns on this invention. It is a graph which shows typically the storage elastic modulus (E') of the polyetheretherketone resin sheet which the relative crystallinity is 100% in embodiment of the molding method for a polyarylene ether ketone resin sheet which concerns on this invention. It is sectional drawing which shows typically the state of preheating the polyarylene ether ketone resin sheet in embodiment of the molding method for a polyarylene ether ketone resin sheet which concerns on this invention. FIG. 3 is a cross-sectional explanatory view schematically showing a state in which the polyarylene ether ketone resin sheet of FIG. 4 is inserted into a female mold of a molding die by a male mold. FIG. 5 is a cross-sectional explanatory view schematically showing a state in which the polyarylene ether ketone resin sheet of FIG. 5 is compressed by a male plug. It is sectional drawing which shows typically the state which presses the male type plug of FIG. 6 and depressurizes the inside of a female type.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIGS. 1 to 7, the molding method for a polyarylene ether ketone resin sheet in the present embodiment is a polyarylene ether ketone resin sheet 1. Is melt-extruded, and the polyarylene ether ketone resin sheet 1 is subjected to [glass transition point (Tg) -10 ° C.] or higher of the polyarylene ether ketone resin sheet 1 [glass transition point (Tg)] of the polyarylene ether ketone resin sheet 1. ) + 50 ° C.] or less, and then the preheated polyarylene ether ketone resin sheet 1 is subjected to the glass transition point (Tg) of the polyarylene ether ketone resin sheet 1 or more and the melting point of the polyarylene ether ketone resin sheet 1. It is thermoformed with a molding mold 72 having a temperature lower than that.

The polyarylene ether ketone resin sheet 1 can be manufactured by a known manufacturing method such as a melt extrusion molding method, a calendar molding method, or a casting method, but from the viewpoint of handleability and simplification of equipment, the melt extrusion molding method is used. It is preferable to continuously extrude thinly. Here, the melt extrusion method is a T-die of the melt extrusion molding machine 10 in which the molding material 2 is melt-kneaded using the melt extrusion molding machine 10 of the manufacturing apparatus for the polyarylene ether ketone resin sheet 1 shown in FIG. 20 is a method for continuously extruding a polyarylene ether ketone resin sheet 1 from 20 to produce a polyarylene ether ketone resin sheet 1.

The apparatus for producing the polyarylene ether ketone resin sheet 1 is not particularly limited, but as shown in FIG. 1, for example, the polyarylene ether ketone resin-containing molding material 2 is used and the thickness is 1 μm or more and 1000 μm or less. A melt extrusion molding machine 10 for melt-kneading the molding material 2 and a T-die mounted on the melt extrusion molding machine 10 to extrude the polyarylene ether ketone resin sheet 1. The 20 and the cooling roll 30 for cooling the polyarylene ether ketone resin sheet 1 extruded from the T die 20 and the polyarylene ether ketone resin sheet 1 extruded from the T die 20 are in contact with each other and pressed against the cooling roll 30. It includes a pair of crimping rolls 40 and a winder 60 for winding the polyarylene ether ketone resin sheet 1 cooled by the cooling roll 30.

The storage elastic modulus (E') of the polyarylene ether ketone resin sheet 1 is important, and the storage elastic modulus (E') is equal to or higher than the [glass transition point (Tg) -10 ° C.] of the polyarylene ether ketone resin sheet 1. The ether ketone resin sheet 1 needs to be a resin sheet having a recessed portion that once drops to 2 × 10 ⁸ Pa or less in the temperature range of [glass transition point (Tg) + 50 ° C. or less] (see FIG. 2). ..

This is because, for example, the polyarylene ether ketone resin sheet 1 does not soften when it does not have a concave portion (see FIG. 3) that once drops to 2.0 × 10 ⁸ Pa or less in the relevant temperature range. This is because thermoforming such as vacuum forming, vacuum forming, vacuum forming, and press forming after using the arylene ether ketone resin sheet 1 becomes very difficult.
Although FIGS. 2 and 3 show the storage elastic modulus (E') in the extrusion direction, the storage elastic modulus (E') in the width direction (direction perpendicular to the extrusion direction) is also substantially the same.

The relative crystallinity of the polypolyarylene ether ketone resin sheet 1 is preferably less than 80%, preferably 50% or less, more preferably 40% or less, still more preferably 30%. This is because when the relative crystallinity of the polyarylene ether ketone resin sheet 1 is 80% or more, the polyarylene ether ketone resin sheet 1 does not soften, so that the subsequent thermoforming property deteriorates. The lower limit of the relative crystallinity of the polyarylene ether ketone resin sheet 1 is not particularly limited, but is preferably 5% or more. The crystallization of the polyarylene ether ketone resin sheet 1 can be represented by the relative crystallinity.

The relative crystallinity of the polyarylene ether ketone resin sheet 1 is calculated by the following formula based on the thermal analysis results measured at a heating rate of 10 ° C./min using a differential scanning calorimeter.
Relative crystallinity (%) = {1- (ΔHc / ΔHm)} × 100
ΔHc: calorific value of recrystallization peak (J / g)
ΔHm: Calorific value of crystal melting peak (J / g)

In view of the above points, in the production of the polyarylene ether ketone resin sheet 1 to be softened by the subsequent thermoforming, among the melt extrusion molding machine 10, the T die 20, the cooling roll 30, and the pair of crimping rolls 40 of the manufacturing apparatus, At least the temperature of the cooling roll 30 is important, and the temperature of the cooling roll 30 needs to be adjusted to a predetermined temperature.

The polyarylene ether ketone resin, which is the molding material 2 of the polypolyarylene ether ketone resin sheet 1, is a crystalline resin composed of an arylene group, an ether group, and a carbonyl group, and is described in, for example, Japanese Patent No. 5709878 and Japanese Patent No. 5847522. The resin that has been used can be mentioned. Specific examples of this polyarylene ether ketone resin include a polyether ether ketone (PEEK) resin having a chemical structural formula represented by the chemical formula (1) and a polyether having a chemical structure represented by the chemical formula (2). A ketone (PEK) resin, a polyether ketone ketone (PEKK) resin having a chemical structure represented by the chemical formula (3), a polyether ether ketone ketone (PEEK) resin having a chemical structure represented by the chemical formula (4), or Examples thereof include a polyether ketone ether ketone ketone (PEKEKK) resin having a chemical structure represented by the chemical formula (5).

The polyarylene ether ketone resin may be used alone or in combination of two or more. Further, the polyarylene ether ketone resin may be a copolymer having two or more chemical structures represented by the chemical formulas (1) to (5). The polyarylene ether ketone resin is usually used in a form suitable for molding such as powder, granule, and pellet.

Among these polyetherylene ether ketone resins, the polyetheretherketone resin and the polyetherketoneketone resin are preferable in terms of easy availability, cost, moldability of the resin sheet 1, and moldability of the foam. Specific examples of the polyetheretherketone resin include Victrex Powder series, Victrex Granules series, Daicel Evonik product name: Vestakeep series, and Solvay Specialty Polymers product name: Ketaspire. The PEEK series can be mentioned. Further, as a specific example of the polyetherketoneketone resin, the product name: KEPSTAN series manufactured by Arkema Co., Ltd. corresponds.

The molding material 2 contains at least a polyarylene ether ketone resin, but in addition to this polyarylene ether ketone resin, a polyimide (PI) resin, a polyamide imide (PAI) resin, and a poly, as long as the characteristics of the present invention are not impaired. Polymer resin such as etherimide (PEI) resin, polyamide 4T (PA4T) resin, polyamide 6T (PA6T) resin, modified polyamide 6T (modified PA6T) resin, polyamide 9T (PA9T) resin, polyamide 10T (PA10T) resin, polyamide 11T (PA11T) resin, polyamide 6 (PA6) resin, polyamide 66 (PA66) resin, polyamide resin such as polyamide 46 (PA46) resin, polysulphon (PSU) resin, polyether sulfide (PES) resin, polyphenylene sulfide (PPSU). ) Polyphenylene sulfide resin such as resin, polyphenylene sulfide (PPS) resin, polyphenylene sulfide ketone resin, polyphenylene sulfide sulfone resin, polyphenylene sulfide resin such as polyphenylene sulfide ketone sulfone resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin. , Polyester resin such as polyethylene naphthalate (PEN) resin, polytetrafluoroethylene (PTFE) resin, polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) resin, tetrafluoroethylene-hexafluoropropyl copolymer ( FEP) resin, tetrafluoroethylene-ethylene copolymer (ETFE) resin, polychlorotrifluoroethylene (PCTFE) resin, polyphenylene sulfide (PVdF) resin, vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer Fluororesin Polycarbonate (PC) resin such as resin, polyarylate (PAR) resin, liquid crystal polymer (LCP) and the like are added as necessary.

In addition to the above resins, the molding material 2 includes antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, lubricants, flame retardants, antistatic agents, heat resistance improvers, and inorganic substances, as long as the characteristics of the present invention are not impaired. Compounds, organic compounds and the like are selectively added.

The melt extruder 10 of the apparatus for producing the polyarylene ether ketone resin sheet 1 comprises, for example, a single-screw extruder, a twin-screw extruder, or the like, and functions to melt-knead the charged molding material 2. A raw material input port 11 for the molding material 2 is installed behind the upper part of the melt extrusion molding machine 10, and the raw material input port 11 has helium gas, neon gas, argon gas, krypton gas, nitrogen gas, and carbon dioxide gas. An inert gas supply pipe 12 for supplying an inert gas such as (see the arrow in FIG. 1) as needed is connected, and the inflow of the inert gas through the inert gas supply pipe 12 causes the molding material 2 to be connected. Oxidation deterioration and oxygen cross-linking are effectively prevented.

The temperature of the polyarylene ether ketone resin at the time of melt kneading of the melt extruder 10 is not particularly limited as long as it can be melted and the polyarylene ether ketone resin does not decompose, but the polyarylene ether ketone resin is not particularly limited. The range above the melting point of the above and below the thermal decomposition temperature of the polyarylene ether ketone resin is good. Specifically, the range is preferably 320 ° C. or higher and 450 ° C. or lower, preferably 360 ° C. or higher and 420 ° C. or lower, and more preferably 380 ° C. or higher and 400 ° C. or lower. This is because if the temperature is lower than the melting point of the polyarylene ether ketone resin, the molding material 2 containing the polyarylene ether ketone resin cannot be melt-extruded, and conversely, if the thermal decomposition temperature is exceeded, the polyarylene ether is obtained. This is because the ketone resin may be severely decomposed.

The T-die 20 is attached to the tip of the melt extrusion molding machine 10 via a connecting pipe 21, and the melted molding material 2 is molded into a thin strip-shaped polyarylene ether ketone resin sheet 1 and continuously extruded downward. Works like. A gear pump 22 mounted on the connecting pipe 21 is located upstream of the T-dice 20, and the gear pump 22 transfers the molding material 2 to the T-dice 20 at a constant speed and with high accuracy. A filter (not shown) is selectively installed between the T die 20 and the gear pump 22 for the purpose of separating the gel or foreign matter of the molten molding material 2.

The temperature at the time of extruding the T-die 20 is equal to or higher than the melting point of the polyarylene ether ketone resin and lower than the thermal decomposition temperature of the polyarylene ether ketone resin, specifically, 320 ° C or higher and 450 ° C or lower, preferably 360 ° C or higher and 420 ° C or lower. More preferably, it is adjusted in the range of 380 ° C. or higher and 400 ° C. or lower. This makes it difficult to melt-extrude the molding material 2 containing the polyarylene ether ketone resin when the temperature is lower than the melting point of the polyarylene ether ketone resin, and conversely, when the thermal decomposition temperature is exceeded, the polyarylene ether ketone resin is produced. Is based on the reason that it may be severely decomposed.

The cooling roll 30 is made of, for example, a metal roll having a diameter larger than that of the pair of crimping rolls 40, and the polyaryletherketone resin sheet 1 rotatably supported and extruded below the T die 20 is combined with the crimping roll 40. It is sandwiched between them, and the thickness of the polyaryletherketone resin sheet 1 is controlled within a predetermined range while being cooled in a short time together with the crimping roll 40.

Like the pair of crimping rolls 40, the cooling roll 30 is below the [glass transition point (Tg) + 20 ° C.] of the polyarylene ether ketone resin sheet 1, preferably below the glass transition point (Tg) of the polyarylene ether ketone resin sheet 1. , More preferably, the temperature is adjusted to 50 ° C. or higher and lower than the [glass transition point (Tg) −10 ° C.] of the polyarylene ether ketone resin sheet 1, and the polyarylene ether ketone resin sheet 1 is in sliding contact with the polyarylene ether ketone resin sheet 1.

The temperature of the cooling roll 30 is adjusted to a temperature equal to or lower than the [glass transition point (Tg) + 20 ° C.] of the polyarylene ether ketone resin sheet 1, because the temperature of the cooling roll 30 is adjusted to the temperature of the polyarylene ether ketone resin sheet 1 [glass. When the transition point (Tg) + 20 ° C.] is exceeded, the relative crystallinity of the polyarylene ether ketone resin sheet 1 becomes 80% or more, and the polyarylene ether ketone resin sheet 1 does not soften, so that the subsequent thermoformability is improved. Based on the reason that it declines. Further, in the temperature range of [glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet 1 or more and [glass transition point (Tg) + 50 ° C] or less of the polyarylene ether ketone resin sheet 1, polyarylene ether ketone. This is based on the reason that the storage elastic modulus (E') of the resin sheet 1 is not preferable because it does not have a recessed portion where the storage elastic modulus (E') once drops to 2 × 10 ⁸ Pa or less.

The storage elastic modulus (E') of the polyarylene ether ketone resin sheet 1 is equal to or higher than the [glass transition point (Tg) -10 ° C.] of the polyarylene ether ketone resin sheet 1 [glass transition point (glass transition point (E') of the polyarylene ether ketone resin sheet 1. Polyarylene ether in the temperature range of Tg) + 50 ° C.] or less When the polyarylene ether ketone resin sheet 1 does not have a concave portion where the storage elastic modulus (E') once drops to 2 × 10 ⁸ Pa or less, the polyarylene ether It should be noted that the ketone resin sheet 1 does not soften, and as a result, thermoforming such as vacuum forming, pneumatic forming, vacuum pneumatic forming, and press forming using the polyarylene ether ketone resin sheet 1 becomes very difficult. be.

Further, during the production of the polyarylene ether ketone resin sheet 1, the polyarylene ether ketone resin sheet 1 may stick to the cooling roll 30 and break. On the contrary, when the cooling roll 30 is lower than 50 ° C., dew condensation is caused on the cooling roll 30, which is not preferable.
The temperature adjustment and cooling method of the cooling roll 30 are not particularly limited, but for example, a method using a heat medium such as air, water, or oil, or a method such as an electric heater or dielectric heating is applicable.

The pair of crimp rolls 40 are rotatably supported below the T-die 20 so as to sandwich the cooling roll 30. A slit blade 50 forming a slit on the side of the polyarylene ether ketone resin sheet 1 can be raised and lowered at least between the pair of crimp rolls 40 and the take-up pipe 61 of the take-up machine 60 located downstream thereof. A tension roll 51 is rotatably supported between the slit blade 50 and the take-up tube 61 so that tension is applied to the polyarylene ether ketone resin sheet 1 to smoothly take up the polyarylene ether ketone resin sheet 1. ..

From the viewpoint of improving the adhesion between the polyarylene ether ketone resin sheet 1 and the cooling roll 30, at least natural rubber, isoprene rubber, butadiene rubber, norbornene rubber, acrylonitrile butadiene rubber, and nitrile rubber are placed on the peripheral surface of each crimping roll 40. , Urethane rubber, silicone rubber, fluororubber and the like are covered and formed as needed, and inorganic compounds such as silica and alumina are selectively added to the rubber layer. Among these, it is preferable to use silicone rubber or fluororubber, which has excellent heat resistance.

As the crimping roll 40, a metal elastic roll having a metal surface is used as needed, and when this metal elastic roll is used, it is possible to form a polyarylene ether ketone resin sheet 1 having an excellent surface smoothness. Become. Specific examples of this metal elastic roll include a metal sleeve roll, an air roll (product name manufactured by Dimco Corporation), and a UF roll (product name manufactured by Hitachi Zosen Corporation).

Similar to the cooling roll 30, such a pair of crimping rolls 40 is equal to or less than the [glass transition point (Tg) + 20 ° C.] of the polyarylene ether ketone resin sheet 1, preferably the glass transition point of the polyarylene ether ketone resin sheet 1. The temperature is adjusted to Tg) or less, more preferably 50 ° C. or higher, and [glass transition point (Tg) -10 ° C.] or lower of the polyarylene ether ketone resin sheet 1, and the temperature is adjusted by sliding against the polyarylene ether ketone resin sheet 1 to cool it. Press contact with the roll 30.

The temperature range of the crimping roll 40 is the crystal of the polyarylene ether ketone resin sheet 1 when the temperature of the crimping roll 40 exceeds the [glass transition point (Tg) + 20 ° C.] of the polyarylene ether ketone resin sheet 1. This is because the conversion progresses and the relative crystallinity of the polyarylene ether ketone resin sheet 1 becomes 80% or more, which hinders the softening of the polyarylene ether ketone resin sheet 1 and causes a decrease in thermoformability later. .. Further, in the temperature range of [glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet 1 or more and [glass transition point (Tg) + 50 ° C] or less of the polyarylene ether ketone resin sheet 1, polyarylene ether ketone. This is because the resin sheet 1 does not have a recessed portion where the storage elastic modulus (E') once drops to 2 × 10 ⁸ Pa or less.

The storage elastic modulus (E') of the polyarylene ether ketone resin sheet 1 is at least [glass transition point (Tg) -10 ° C.] of the polyarylene ether ketone resin sheet 1 [glass transition point of the polyarylene ether ketone resin sheet 1 ( In the temperature range of Tg) + 50 ° C.] or less, if the polyarylene ether ketone resin sheet 1 does not have a recessed portion in which the storage elastic modulus (E') of the polyarylene ether ketone resin sheet 1 once drops to 2 × 10 ⁸ Pa or less, the polyarylene It should be noted that the ether ketone resin sheet 1 does not soften, and thermoforming such as vacuum forming, pressure air forming, vacuum pressure air forming, and press forming using the polyarylene ether ketone resin sheet 1 becomes extremely difficult.

Further, during the production of the polyarylene ether ketone resin sheet 1, the polyarylene ether ketone resin sheet 1 may stick to the crimping roll 40 and cause breakage. On the contrary, when the crimping roll 40 is lower than 50 ° C., dew condensation occurs on the crimping roll 40, which is not preferable.
Similar to the cooling roll 30, the temperature adjustment and cooling method of the crimping roll 40 is not limited, and examples thereof include a method using a heat medium such as air, water, and oil, an electric heater, and dielectric heating.

In the above configuration, when producing the polyarylene ether ketone resin sheet 1, first, the molding material 2 is charged into the raw material charging port 11 of the melt extrusion molding machine 10, the molding material 2 is melt-kneaded, and the T-die 20 is melt-kneaded. The polyarylene ether ketone resin sheet 1 is continuously extruded into a band shape. At this time, the water content of the polyarylene ether ketone resin before melt-kneading is adjusted to 2000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less.

This is because if the water content of the polyarylene ether ketone resin before melt-kneading exceeds 2000 ppm, the polyarylene ether ketone resin may foam. The lower limit of the water content of the polyarylene ether ketone resin before melt-kneading is not particularly limited, but is preferably 100 ppm or more.

After extruding the polyarylene ether ketone resin sheet 1, the cooling roll 30, the pair of crimping rolls 40, the tension roll 51, and the winding pipe 61 of the winder 60 are sequentially wound, and the polyarylene ether ketone resin sheet 1 is cooled. If the polyarylene ether ketone resin sheet 1 is slidably contacted with the roll 30 and cooled in a short time, both sides of the polyarylene ether ketone resin sheet 1 are cut with a slit blade 50 to adjust the appearance, and the polyarylene ether ketone resin sheet 1 is sequentially wound on the winding tube 61 of the winding machine 60. , Polyarylene ether resin sheet 1 can be manufactured.

At this time, the relative crystallinity and the storage elastic modulus (E') of the polyarylene ether ketone resin sheet 1 can be adjusted by immediately cooling the polyarylene ether ketone resin sheet 1 extruded from the T die 20. can. Further, as a method of bringing the polyarylene ether ketone resin sheet 1 into close contact with the cooling roll 30, the polyarylene ether ketone resin sheet 1 is pressed against the cooling roll 30 by the crimping roll 40 from the viewpoint of handleability and simplification of equipment. It is preferable to use the touch roll method for close contact.

The adhesion time between the polyarylene ether ketone resin sheet 1 and the cooling roll 30 is not particularly limited, but from the viewpoint of instantaneously cooling the polyarylene ether ketone resin sheet 1, 0.1 seconds or more and 120 seconds or less. It is preferably 0.5 seconds or more and 40 seconds or less, and more preferably 1 second or more and 30 seconds or less.

The thickness of the cooled polyarylene ether ketone resin sheet 1 is appropriately selected depending on the intended use, but is preferably in the range of 1 μm or more and 1000 μm or less, preferably 5 μm or more and 750 μm or less. This is because when the thickness of the polyarylene ether ketone resin sheet 1 is less than 1 μm, the mechanical strength of the polyarylene ether ketone resin sheet 1 is significantly reduced, which makes it difficult to mold the polyarylene ether ketone resin sheet 1. Based on the reason that it becomes. On the contrary, when the thickness of the polyarylene ether ketone resin sheet 1 exceeds 1000 μm, crystallization of the polyarylene ether ketone resin sheet 1 proceeds during molding of the polyarylene ether ketone resin sheet 1, and the relative crystallization degree. This is because it becomes difficult to mold the polyarylene ether ketone resin sheet 1 having a value of less than 80%.

Fine irregularities can be formed on the surface of the polyarylene ether ketone resin sheet 1 without losing the effect of the present invention, and the friction coefficient of the surface of the polyarylene ether ketone resin sheet 1 can be reduced.

As a method for forming the fine irregularities, (1) the polyarylene ether ketone resin is melt-kneaded by the melt extrusion molding machine 10, and the melt-kneaded polyarylene ether ketone resin is melt-kneaded from the T die 20 on the peripheral surface. A method of forming fine irregularities by spitting out onto the provided cooling roll 30 and bringing it into close contact with the crimping roll 40 by sandwiching the polyarylene ether ketone resin sheet 1, (2) minute amounts on the polyarylene ether ketone resin sheet 1. A method of spraying an inorganic compound such as zirconia, glass, or stainless steel, a polycarbonate resin, a polyamide resin, or an organic compound such as a plant seed to form fine irregularities. An example is a method of forming fine irregularities by press molding with a provided mold.

Among these methods, the method (1) is most suitable from the viewpoints of simplification of equipment, accuracy of uneven size, uniform formation of unevenness, facilitation of formation of unevenness, and continuous formation of unevenness. be.

Explaining the method (1) in more detail, (1-1) the polyarylene ether ketone resin is discharged from the T-die 20 of the melt extrusion molding machine 10 onto a cooling roll 30 provided with fine irregularities on the peripheral surface, and at the same time. A method in which this discharged material is sandwiched between a cooling roll 30 and a crimping roll 40 having fine irregularities on the peripheral surface and molded at the same time as melt extrusion molding of the polyarylene ether ketone resin sheet 1, (1-2) molded polyarylene. A method of forming the unevenness by sandwiching the ether ketone resin sheet 1 between a cooling roll 30 having fine irregularities on the peripheral surface and a crimping roll 40 having fine irregularities on the peripheral surface can be mentioned. Among these, the method (1-1) is preferable from the viewpoint of simplification of equipment.

Next, the manufactured polyarylene ether ketone resin sheet 1 is set on the jig 70 shown in FIG. 4, stretched, brought close to the heater 71 and the like, and preheated for a predetermined time. The time for preheating the polyarylene ether ketone resin sheet 1 is not particularly limited as long as the polyarylene ether ketone resin sheet 1 is softened, but is generally 1 second or more and 600 seconds or less, preferably 600 seconds or less. 5 seconds or more and 60 seconds or less, more preferably around 30 seconds.

Preheating of the polyarylene ether ketone resin sheet 1 is performed at [glass transition point (Tg) -10 ° C] or higher of the polyarylene ether ketone resin sheet 1 [glass transition point (Tg) + 50 ° C] of the polyarylene ether ketone resin sheet 1. The following temperature range, preferably the glass transition point (Tg) of the polyarene ether ketone resin sheet 1 or more and the [glass transition point (Tg) + 30 ° C.] or less of the polyarene ether ketone resin sheet 1, more preferably the polyarylene ether ketone resin. The temperature range above the glass transition point (Tg) and below [glass transition point (Tg) +20] of the polyarylene ether ketone resin is good. This is because when the preheating temperature of the polyarylene ether ketone resin sheet 1 is less than [glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet 1, the polyarylene ether ketone resin sheet 1 softens. This is based on the reason that thermoforming such as vacuum forming, pressure forming, vacuum forming and press forming becomes difficult.

When the temperature exceeds the [glass transition point (Tg) + 50 ° C.] of the polyarylene ether ketone resin sheet 1, crystallization of the polyarylene ether ketone resin sheet 1 proceeds before thermoforming, and the relative crystallization degree is 80%. As described above, the storage elasticity (E') of the polyarylene ether ketone resin sheet 1 is equal to or higher than the [glass transition point (Tg) -10 ° C.] of the polyarylene ether ketone resin sheet 1 [glass transition] of the polyarylene ether ketone resin sheet 1. In the temperature range below the point (Tg) + 50 ° C.], the concave portion that once drops to 2 × 10 ⁸ Pa or less disappears, so that the polyarylene ether ketone resin sheet 1 does not soften, and is vacuum formed or pneumatically formed. This is because thermoforming such as vacuum pressure air forming and press forming becomes difficult.

It should be noted that when the polyarylene ether ketone resin sheet 1 is preheated at a temperature equal to or higher than the melting point of the polyarylene ether ketone resin sheet 1, drawdown occurs and molding becomes impossible.

After preheating the polyarylene ether ketone resin sheet 1, the preheated polyarylene ether ketone resin sheet 1 is inserted into the female mold 73 of the prepared molding die 72 by a male hollow plug 74 (see FIG. 5). ), Compressed with this male plug 74 (see FIG. 6) and compacted, and then a gas such as air is pressed into the hollow plug 74 to vacuum pump the inside of the female mold 73 of the molding die 72. When the pressure is reduced (see FIG. 7), the deformed polyarylene ether ketone resin sheet 1 adheres to the cavity in the mold, and a predetermined molded product can be thermoformed. In the molding die 72, for example, the female mold 73 is formed in a bottomed tubular shape or the like, and the male plug 74 is formed in a hollow pillar shape or a cone trapezoidal shape.

During thermoforming, the temperature of at least the female mold 73 of the female mold 73 and the plug 74 of the molding mold 72 is equal to or higher than the glass transition point (Tg) of the polyarylene ether ketone resin sheet 1 of the polyarylene ether ketone resin sheet 1. A range below the melting point, preferably [glass transition point (Tg) + 30 ° C.] of the polyarylene ether ketone resin sheet 1 or more, and [melting point -50 ° C.] or less of the polyarylene ether ketone resin sheet 1, more preferably polyarylene ether ketone resin. The temperature is set in a temperature range of [glass transition point (Tg) + 30 ° C.] or higher of the sheet 1 and [melting point −100 ° C.] or lower of the polyarylene ether ketone resin sheet 1. This is because when the temperature of the female mold 73 is in the range of the glass transition point (Tg) of the polyarylene ether ketone resin sheet 1 or more and less than the melting point of the polyarylene ether ketone resin sheet 1, crystallization proceeds during thermoforming. Therefore, it is possible to obtain a molded product with excellent properties such as low water absorption, mechanical strength, electrical insulation properties, heat resistance, chemical resistance, gas barrier properties, radiation resistance, hydrolysis resistance, slidability, and light weight. Because it can be done.

On the other hand, when the temperature of the female mold 73 is lower than the glass transition point (Tg) of the polyarylene ether ketone resin sheet 1, crystallization of the molded product does not proceed, and the obtained molded product has low water absorption and a machine. Properties such as strength, heat resistance, chemical resistance, gas barrier property, radiation resistance, hydrolysis resistance, slidability, and light weight will be deteriorated. Further, when the operating temperature of the molded product exceeds the glass transition point (Tg) of the polyarylene ether ketone resin molded product, crystallization proceeds locally during use, which causes the molded product to be deformed. .. Further, when the temperature of the female mold 73 exceeds the melting point, the polyarylene ether ketone resin sheet 1 is melted and a molded product cannot be obtained.

The molded product thermoformed at a temperature lower than the glass transition point (Tg) of the polyarylene ether ketone resin sheet 1 is heated in a temperature range equal to or higher than the glass transition point (Tg) of the polyarylene ether ketone resin molded product and lower than the melting point. It is conceivable to adopt a method of proceeding with crystallization, but in this case, since crystallization progresses locally, deformation of the molded product or the like occurs, which is not preferable.

The molding time of the molded product is not particularly limited as long as the crystallization of the polyarylene ether ketone resin proceeds sufficiently and the relative crystallization degree reaches 100%, but in general, 0. It is preferably 1 second or more and 600 seconds or less, preferably 0.5 seconds or more and 120 seconds or less, more preferably 1 second or more and 60 seconds or less, and further preferably 3 seconds or more and 30 seconds or less.

According to the above, since it is not necessary to add any acrylic polymer or a predetermined copolymer to the molding material 2, the excellent properties of the polyarylene ether ketone resin, specifically, heat resistance, low water absorption, and mechanical strength. , Electrical insulation, chemical resistance, hydrolysis resistance, gas barrier property, slidability, molding processability, and light weight are not lost. In addition, the polyarylene ether ketone resin sheet 1 having excellent properties can be thermoformed to stabilize a wide variety of molded products and to manufacture them at low cost.

Further, it is possible to prevent the production of the polyarylene ether ketone resin sheet 1 from becoming complicated and reduce the cost. Further, since it is possible to promote the crystallization of the molded product made of polyarylene ether ketone resin during thermoforming, the heat treatment after thermoforming can be omitted. Further, even if the polyarylene ether ketone resin sheet 1 is long, easy molding can be expected.

In the above embodiment, the polyarylene ether ketone resin sheet 1 is pressed against the cooling roll 30 by the crimping roll 40 to bring it into close contact with the cooling roll 30, but the present invention is not limited to this. For example, the polyarylene ether ketone resin sheet 1 may be brought into close contact with the cooling roll 30 by using, for example, an electrostatic application method (pinning method) or an air knife. Further, when cooling the polyarylene ether ketone resin sheet 1, the polyarylene ether ketone resin sheet 1 is brought into close contact with a metal belt or the like, water is sprayed on the polyarylene ether ketone resin sheet 1, or poly is submerged in water. A method of charging the arylene ether ketone resin sheet 1 or the like may be adopted.

Hereinafter, examples of the molding method for a polyarylene ether ketone resin sheet according to the present invention will be described together with comparative examples.
[Example 1]
First, a commercially available polyetheretherketone resin [product name: Ketaspire PEEK KT-851NL SP (hereinafter abbreviated as "KT-851NL SP") manufactured by Solvay Specialty Polymers] was prepared as a polyetherketone resin, and this poly was prepared. The ether etherketone resin was dried for 12 hours in a dehumidifying hot air dryer heated to 160 ° C.

After confirming that the content of the dried polyetheretherketone resin was 300 ppm or less, the dried polyetheretherketone resin was subjected to uniaxial melt extrusion molding of φ40 mm equipped with a T-die having a width of 900 mm as shown in FIG. It was set in a machine and melt-kneaded, and the melt-kneaded polyetheretherketone resin was continuously extruded from the T-die of the uniaxial melt extrusion molding machine to form a resin sheet made of polyetheretherketone resin into a strip shape.

At this time, the water content of the polyether ether ketone resin was measured by the Karl Fischer titration method using a trace water content measuring device [manufactured by Mitsubishi Chemical Corporation, trade name: CA-100 type]. The single-screw melt extruder had L / D = 32, a compression ratio of 2.5, and a screw: full flight screw type.

The temperature of the uniaxial melt extrusion molding machine was adjusted to 380 to 400 ° C., the temperature of the T die was adjusted to 400 ° C., and the temperature of the connecting pipe connecting the uniaxial melt extrusion molding machine and the T die was adjusted to 400 ° C. The temperature of the molten polyetheretherketone resin was determined to be the resin temperature at the inlet of the T-die, and the measured temperature was 397 ° C. When the polyetheretherketone resin was charged into the single-screw extruder, nitrogen gas was supplied at 18 L / min through the inert gas supply pipe.

After the resin sheet made of polyetheretherketone resin is extruded in this way, both ends of the continuous resin sheet made of polyetheretherketone resin are cut with a slit blade and sequentially wound into the take-up tube of the winder to have a length. A resin sheet made of polyetheretherketone resin having a width of 100 m and a width of 650 mm was produced. At this time, the resin sheet made of polyetheretherketone resin is used for a cooling roll at 130 ° C. having irregularities on the peripheral surface, a pair of crimping rolls made of silicone rubber, and a 6-inch take-up tube located downstream of these. It was wound in sequence and narrowed between the cooling roll and the crimping roll. When the temperature of the crimping roll was measured with a non-contact thermometer, it was 131 ° C.

Once the polyether ether ketone resin sheet is obtained, the sheet thickness, relative crystallinity, glass transition point (Tg), storage elastic modulus (E') and melting point of this polyether ether resin sheet are measured, and the results are shown in the table. Described in 1.

Next, using the produced polyetheretherketone resin sheet, a cup-shaped molded product was molded by a press molding method. Press molding was carried out using a bottomed cylindrical female mold (diameter 20 mm, depth 10 mm) as a molding die and using a male hollow plug of the molding die. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 155 ° C., the molding die temperature: 200 ° C., the plug temperature: 200 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 30 seconds. After molding the cup-shaped molded product, the press formability, relative crystallization degree, and heat resistance of the molded product were evaluated, and the results are shown in Table 1.

-Sheet thickness of polyarylene ether ketone resin sheet The thickness of the polyarylene ether ketone resin sheet was measured using a micrometer (product name manufactured by Mitutoyo Co., Ltd .: coolant proof micrometer code MDC-25PJ). At the time of measurement, the polyarylene ether ketone resin sheet was measured at arbitrary 10 points in the width direction (direction perpendicular to the extrusion direction), and the average value thereof was taken as the sheet thickness.

-Relative crystallinity of the polyarylene ether ketone resin sheet For the relative crystallinity of the polyarylene ether ketone resin sheet, weigh about 8 mg of the measurement sample from the polyarylene ether ketone resin sheet and measure it with a differential scanning calorimeter (SI Nano). The measurement was performed using a product name: EXSTAR7000 series X-DSC7000) manufactured by Technologies Co., Ltd. under the conditions of a temperature rise rate of 10 ° C./min and a measurement temperature range of 20 ° C. to 380 ° C. It was calculated from the calorific value of the crystal melting peak (J / g) and the calorific value of the recrystallization peak (J / g) obtained at this time using the following formula.

Relative crystallinity (%) = {1- (ΔHc / ΔHm)} × 100
Here, ΔHc represents the calorific value (J / g) of the recrystallization peak of the polyarylene ether ketone resin sheet under the heating condition of 10 ° C./min, and ΔHm is 10 ° C./min of the polyarylene ether ketone resin sheet. It represents the calorific value (J / g) of the crystal melting peak under the temperature rising condition of.

-Glass transition point (Tg) of polyarylene ether ketone resin sheet
Regarding the glass transition point (Tg) of the polyarylene ether ketone resin sheet, the loss elastic modulus (E ") of the polyarylene ether ketone resin sheet was measured, and the temperature at which the value became maximum was defined as the glass transition point. The elastic modulus was measured in the extrusion direction of the polyarylene ether ketone resin sheet. Specifically, the polyarylene ether ketone resin sheet was cut into a size of 60 mm in the extrusion direction × 6 mm in the width direction, and a viscoelastic spectrometer (TS).・ By tensile mode using Instrument Japan product name: RSA-G2), frequency 1Hz, strain 0.1%, temperature rise rate 3 ℃ / min, measurement temperature range 60 ℃ to 360 ℃ or less, check The measurement was performed under the condition of a gap of 21 mm.

-Storing elastic modulus (E') of polyarylene ether ketone resin sheet
The storage elastic modulus (E') of the polyarylene ether ketone resin sheet was measured by the tensile mode in the extrusion direction of the polyarylene ether ketone resin sheet. Specifically, a polyarylene ether ketone resin sheet is cut into a size of 60 mm in the extrusion direction x 6 mm in the width direction, and a viscoelastic spectrometer (product name: RSA-G2 manufactured by TS Instruments Japan) is used. The measurement was performed under the conditions of a frequency of 1 Hz, a strain of 0.1%, a heating rate of 3 ° C./min, a measurement temperature range of 60 ° C. to 360 ° C., and a check interval of 21 mm, and marked with XX.

◯: [Glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet [Glass transition point (Tg) + 50 ° C] of the polyarylene ether ketone resin sheet
When there is a recessed part that once drops to 2.0 × 10 ⁸ Pa or less in the following temperature range ×: Polyarylene ether above [Glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet [Glass transition point (Tg) + 50 ° C] of ketone resin sheet
When there is no recessed part that once drops to 2.0 x ¹⁰⁸ Pa or less in the following temperature range

-Melting point of polyarylene ether ketone resin sheet For the melting point of polyarylene ether ketone resin sheet, weigh about 8 mg of the measurement sample from the polyarylene ether ketone resin sheet and measure it with a differential scanning calorimeter (Product name manufactured by SII Nano Technologies). The measurement was performed using the EXSTAR 7000 series X-DSC 7000) under the conditions of a heating rate of 10 ° C./min and a measurement temperature range of 20 ° C. to 380 ° C. From the calorific value curve obtained at this time, the maximum value of the endothermic peak was taken as the melting point.

-Press formability of the molded product The cup-shaped molded product was visually observed and evaluated.
-Relative crystallinity of the molded product The relative crystallinity of the molded product was calculated by the same method as the relative crystallinity of the polyarylene ether ketone resin sheet.

Heat resistance of the molded product The obtained cup-shaped molded product was floated in a solder bath at 288 ° C. for 10 seconds, cooled to room temperature, and then the molded product was visually observed for deformation and wrinkles, and marked with XX.
Here, ◯: no deformation, ×: with deformation.

[Example 2]
First, as the polyarylene ether ketone resin, the commercially available polyetheretherketone resin used in Example 1 is prepared, and a resin sheet made of polyetheretherketone resin is formed into a strip by the same method as in Example 1. The sheet thickness, relative crystallinity, glass transition point (Tg), storage elastic modulus (E') and melting point of this extruded resin sheet were evaluated by the same method as in Example 1, and the results are shown in Table 1. Described in. Regarding the temperature of the molten polyetheretherketone resin, the resin temperature at the inlet of the T-die was measured, and the measured temperature was 397 ° C. Moreover, as a result of measuring the temperature of the crimping roll with a non-contact thermometer, it was 130 ° C.

Next, the obtained polyetheretherketone resin sheet was molded into a cup-shaped molded product by a press molding method. The molding die used for press molding was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 150 ° C., the molding die temperature: 170 ° C., the plug temperature: 170 ° C., the molding pressure: 100 kPa, the molding time: It was carried out under the condition of 90 seconds. After molding the cup-shaped molded product, its moldability, relative crystallinity, and heat resistance were evaluated, and the results are shown in Table 1.

[Example 3]
First, as the polyarylene ether ketone resin, the commercially available polyetheretherketone resin used in Example 1 is prepared, and a resin sheet made of polyetheretherketone resin is formed into a strip by the same method as in Example 1. The sheet thickness, relative crystallinity, glass transition point (Tg), storage elastic modulus (E') and melting point of this extruded resin sheet were evaluated by the same method as in Example 1, and the results are shown in Table 1. Described in. Regarding the temperature of the molten polyetheretherketone resin, the resin temperature at the inlet of the T-die was measured, and the measured temperature was 398 ° C. The cooling roll was adjusted to 70 ° C. Moreover, as a result of measuring the temperature of the crimping roll with a non-contact thermometer, it was 115 ° C.

Next, the obtained polyetheretherketone resin sheet was molded into a cup-shaped molded product by a press molding method. The molding die used for press molding was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 160 ° C., the molding die temperature: 230 ° C., the plug temperature: 230 ° C., the molding pressure: 250 kPa, the molding time: It was carried out under the condition of 45 seconds. After molding the cup-shaped molded product, its moldability, relative crystallinity, and heat resistance were evaluated, and the results are shown in Table 1.

[Example 4]
First, a commercially available polyetheretherketone resin [manufactured by Dycel Ebony Co., Ltd., product name: Vestakeep 3300G (hereinafter abbreviated as "3300G")] is prepared as the polyarylene ether ketone resin, and the same method as in Example 1 is used. , A resin sheet made of polyetheretherketone resin is extruded into a strip shape, and the thickness, relative crystallization degree, glass transition point (Tg), storage elasticity (E') and melting point of the extruded resin sheet are determined. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1. Regarding the temperature of the molten polyetheretherketone resin, the resin temperature at the inlet of the T-die was measured, and the measured temperature was 399 ° C. The cooling roll temperature was adjusted to 110 ° C. When the temperature of the crimping roll was measured with a non-contact thermometer, it showed a value of 127 ° C.

Next, the obtained polyetheretherketone resin sheet was molded into a cup-shaped molded product by a press molding method. The press die used for press molding was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 165 ° C., the molding die temperature: 190 ° C., the plug temperature: 190 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 90 seconds. After molding the cup-shaped molded product, its moldability, relative crystallinity, and heat resistance were evaluated, and the results are shown in Table 1.

[Example 5]
First, as a polyarylene ether ketone resin, a commercially available polyetheretherketone resin [manufactured by Victorec, product name: Victorex Granules 450G] is prepared, and a resin sheet made of polyetheretherketone resin is prepared in the same manner as in Example 1. It was extruded into a strip shape, and the thickness, relative crystallization degree, glass transition point (Tg), and storage elasticity (E') of the extruded resin sheet were evaluated by the same method as in Example 1, and the results were evaluated. Is shown in Table 1. Regarding the temperature of the molten polyetheretherketone resin, the resin temperature at the inlet of the T-die was measured, and when the measurement was performed, the value was 398 ° C. The cooling roll temperature was adjusted to 140 ° C. The temperature of the crimping roll was measured with a non-contact thermometer and found to be 141 ° C.

Next, the obtained polyetheretherketone resin sheet was molded into a cup-shaped molded product by a press molding method. The molding die used for press molding was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 160 ° C., the molding die temperature: 200 ° C., the plug temperature: 200 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 10 seconds. After molding the cup-shaped molded product, its moldability, relative crystallinity, and heat resistance were evaluated, and the results are shown in Table 1.

[Example 6]
First, a commercially available polyetheretherketone resin [manufactured by Victrex, product name: Victrex Granules 381G] is prepared as the polyarylene ether ketone resin, and a resin sheet made of the polyetheretherketone resin is prepared in the same manner as in Example 1. Was extruded into a strip shape, and the thickness, relative crystallization degree, glass transition point (Tg), storage elasticity (E') and melting point of the extruded resin sheet were evaluated by the same method as in Example 1. The results are shown in Table 1.

Regarding the temperature of the molten polyetheretherketone resin, the resin temperature at the inlet of the T-die was measured, and when the measurement was performed, the value was 398 ° C. The cooling roll temperature was adjusted to 150 ° C. As a result of measuring the temperature of the crimping roll with a non-contact thermometer, it was 152 ° C.

Next, the obtained polyetheretherketone resin sheet was molded into a cup-shaped molded product by a press molding method. The molding die used for press molding was the same as in Example 1. Here, the press molding of the polyetheretherketone resin sheet was carried out under the conditions of a preheating temperature: 155 ° C., a molding die temperature: 190 ° C., a plug temperature: 190 ° C., a molding pressure: 150 kPa, and a molding time of 5 seconds. After molding the cup-shaped molded product, its moldability, relative crystallinity, and heat resistance were evaluated, and the results are shown in Table 1.

[Example 7]
First, a commercially available polyetherketoneketone resin [product name: KEPSTAN 8002 (hereinafter abbreviated as "8002") manufactured by Alchema Co., Ltd. is prepared as the polyarylene ether ketone resin, and the polyetherketoneketone resin is heated to 160 ° C. It was dried for 12 hours in a hot air dryer.

After the polyetherketoneketone resin was dried for 12 hours, the water content of the dried polyetherketoneketone resin was measured by the same method as in Example 1, and after confirming that the water content was 300 ppm or less, the dried poly was dried. The etherketoneketone resin is set in a φ40 mm single-screw extruder equipped with a 900 mm wide T-die and melt-kneaded, and the melt-kneaded polyetherketoneketone resin is continuously applied from the T-die of the single-screw extruder. A resin sheet made of polyetherketoneketone resin was extruded into a strip shape.

The uniaxial melt extrusion molding machine and the screw were the same as in Example 1. The temperature of the single-screw melt extruder was adjusted to 380 to 400 ° C, the temperature of the T-die was adjusted to 400 ° C, and the temperature of the connecting pipe connecting the single-screw melt extruder and the T-die was adjusted to 400 ° C. After the resin sheet made of polyetherketoneketone resin is extruded in this way, both ends of the continuous resin sheet made of polyetherketoneketone resin are cut with a slit blade and sequentially wound into the take-up tube of the winder to have a length. A resin sheet made of polyetherketoneketone resin having a width of 100 m and a width of 650 mm was produced.

The cooling roll was adjusted to 150 ° C. Moreover, when the temperature of the crimping roll was measured with a non-contact thermometer, it was 152 ° C. Once a resin sheet made of polyetherketoneketone resin is obtained, the thickness, specific gravity, relative crystallinity, glass transition point (Tg), storage elastic modulus (E') and melting point of this resin sheet are evaluated and the results are obtained. Is shown in Table 1.

Next, using the produced polyetherketone ketone resin sheet, a cup-shaped molded product was molded by a press molding method. Press molding was carried out using a cylindrical female die (diameter 20 mm, depth 10 mm) having a bottom as a forming die and using a plug of a male die. Here, the press molding of the polyetherketoneketone resin sheet is carried out under the conditions of the preheating temperature of the sheet: 185 ° C., the molding die temperature: 250 ° C., the plug temperature: 250 ° C., the molding pressure: 200 kPa, and the molding time: 600 seconds. carried out. After molding the cup-shaped molded product, the press formability, relative crystallization degree, and heat resistance of the molded product were evaluated, and the results are shown in Table 1.

[Comparative Example 1]
Using the same polyetheretherketone resin as in Example 1, the polyetheretherketone resin sheet was extruded under the same conditions as in Example 1 except that the temperature of the cooling roll was changed to 210 ° C. After the polyetheretherketone resin sheet is extruded, the sheet thickness, relative crystallinity, glass transition point (Tg), storage elastic modulus (E') and melting point of this polyetheretherketone resin sheet are measured and the results are obtained. It is described in Table 2.

Next, an attempt was made to mold the obtained polyetheretherketone resin sheet into a cup-shaped molded product by a press molding method. The molding die used for press molding was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 160 ° C., the molding die temperature: 200 ° C., the plug temperature: 200 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 30 seconds.

[Comparative Example 2]
An attempt was made to mold the polyetheretherketone resin sheet molded in Example 1 into a cup-shaped molded product by a press molding method. The molding die used in the press molding method was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 210 ° C., the molding die temperature: 230 ° C., the plug temperature: 230 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 30 seconds.

[Comparative Example 3]
An attempt was made to mold the polyetheretherketone resin sheet molded in Example 1 into a cup-shaped molded product by a press molding method. The molding die used in the press molding method was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 155 ° C., the molding die temperature: 380 ° C., the plug temperature: 280 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 30 seconds.

[Comparative Example 4]
The polyetheretherketone resin sheet molded in Example 1 was molded into a cup-shaped molded product by a press molding method. The molding die used in the press molding method was the same as in Example 1. Here, in the press molding of the polyetheretherketone resin sheet, the preheating temperature of the polyetheretherketone resin sheet: 160 ° C., the molding die temperature: 110 ° C., the plug temperature: 110 ° C., the molding pressure: 200 kPa, the molding time: It was carried out under the condition of 30 seconds.

[Result]
In the case of each example, once in the temperature range of [glass transition point (Tg) -10 ° C] of the polyarylene ether ketone resin sheet or more and [glass transition point (Tg) + 50 ° C] or less of the polyarylene ether ketone resin sheet, 2 Since a polyarylene ether ketone resin sheet having a recessed portion having a recessed portion of 0.0 × 10 ⁸ Pa or less was produced and used, the press formability was really good. Further, the crystallinity increased during press molding, the relative crystallinity became 100%, and a molded product having excellent heat resistance could be obtained.

On the other hand, in the case of Comparative Example 1, since the temperature of the cooling roll is 210 ° C., which exceeds the [glass transition point (Tg) + 20 ° C.] of the polyarylene ether ketone resin sheet, crystallization proceeds and the polyarylene ether ketone resin sheet In the recess where the temperature drops to 2.0 x ¹⁰⁸ Pa or less in the temperature range of [Glass transition point (Tg) -10 ° C] or more and [Glass transition point (Tg) + 50 ° C] or less of the polyarylene ether ketone resin sheet. It became a polyarylene ether ketone resin sheet having no part. Therefore, the polyarylene ether ketone resin sheet could not be softened by preheating, and the molded product could not be molded.

In the case of Comparative Example 2, since the polyetheretherketone resin sheet was preheated at a temperature exceeding the [glass transition point (Tg) + 50 ° C.] of the polyetheretherketone resin sheet, the polyarylene ether ketone resin sheet was preheated during the preheating. Crystallization proceeded, the polyetheretherketone resin sheet did not soften, and the molded product could not be molded.

In the case of Comparative Example 3, the temperature of the molding die was set to a temperature exceeding the melting point of the polyetheretherketone resin sheet and press molding was attempted, but the polyarylene ether ketone resin sheet melted in the molding die. As a result, the polyetheretherketone resin sheet did not soften and the molded product could not be molded.

In the case of Comparative Example 4, the temperature of the molding die was set to a temperature lower than the glass transition point of the polyetheretherketone resin sheet, and press molding was performed. As a result, although the moldability of the molded product was good, the crystallization of the molded product could not be sufficiently promoted during press molding, and there was a problem in the heat resistance of the molded product.

The molding method for a polyarylene ether ketone resin sheet according to the present invention is, for example, manufacturing pharmaceuticals, medical equipment, foods, machines, packaging materials, electricity, electronics, home appliances, music equipment, information equipment, automobiles, space / aircraft, and the like. Used in the field.

1 Polyarylene ether ketone resin sheet 2 Molding material 10 Melt extrusion molding machine 20 T die (die)
30 Cooling roll 40 Crimping roll 60 Winding machine 72 Molding mold (mold)
73 Female 74 Plug (male)

Claims (3)

A molding method for a polyarylene ether ketone resin sheet, which molds a predetermined molded product using a polyarylene ether ketone resin sheet.
The polyarylene ether ketone resin sheet has a storage elastic modulus (E') of [glass transition point (Tg) -10 ° C] or higher of the polyarylene ether ketone resin sheet [glass transition point (Tg) +50] of the polyarylene ether ketone resin sheet. In the temperature range of [° C.] or less, it has a recessed portion when it is drawn in a graph by temporarily decreasing to 2.0 × ¹⁰⁸ Pa or less and then increasing, and the relative crystallinity is less than 80%. The thickness of the polyarylene ether ketone resin sheet melt-extruded is 1 μm or more and 1000 μm or less.
This polyarylene ether ketone resin sheet can be used in a temperature range of [glass transition point (Tg) -10 ° C] or higher of the polyarylene ether ketone resin sheet or lower [glass transition point (Tg) + 50 ° C] of the polyarylene ether ketone resin sheet. Preheat and then preheat the polyarylene ether ketone resin sheet in the female mold of the mold in the temperature range above the glass transition point (Tg) of the polyarylene ether ketone resin sheet and below the melting point of the polyarylene ether ketone resin sheet. A molding method for a polyarylene ether ketone resin sheet, which comprises thermoforming a predetermined molded product by inserting it into a hollow male mold and pressurizing a gas into the male mold to reduce the pressure inside the female mold . A molding material containing a polyarylene ether ketone resin is melt-kneaded in a temperature range equal to or higher than the melting point of the polyarylene ether ketone resin and lower than the thermal decomposition temperature of the polyarylene ether ketone resin, and this molding material is melted and kneaded in a temperature range equal to or higher than the melting point of the polyarylene ether ketone resin. A polyarylene ether ketone resin sheet is formed by continuously extruding from a die set in a temperature range lower than the thermal decomposition temperature of the ether ketone resin, and this polyarylene ether ketone resin sheet is used as a [glass transition] of the polyarylene ether ketone resin sheet. The method for forming a polyarylene ether ketone resin sheet according to claim 1, wherein the temperature is cooled to a point (Tg) + 20 ° C. or lower. The second aspect of claim 2, wherein the polyarylene ether ketone resin sheet formed by continuously extruding from the die is sandwiched between a cooling roll and a crimping roll having a polyarylene ether ketone resin sheet having a [glass transition point (Tg) + 20 ° C.] or less. Molding method for polyarylene ether ketone resin sheet.

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