CN110669338B - Porous molded article and method for producing same - Google Patents
Porous molded article and method for producing same Download PDFInfo
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- CN110669338B CN110669338B CN201910590792.5A CN201910590792A CN110669338B CN 110669338 B CN110669338 B CN 110669338B CN 201910590792 A CN201910590792 A CN 201910590792A CN 110669338 B CN110669338 B CN 110669338B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/24—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by surface fusion and bonding of particles to form voids, e.g. sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
- B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2391/02—Vulcanised oils, e.g. factice
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- Polymers & Plastics (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention provides a porous molded body having excellent strength and low dielectric constant, and a method for producing the same. The above problems are solved by producing a porous molded article having a porosity of 20% or more and 60% or less, which is obtained by using a polyarylene sulfide resin powder having an average particle diameter of 5 [ mu ] m or more and 100 [ mu ] m or less and a melting point Tm1 measured by a differential scanning calorimeter of 250 ℃ or more and 300 ℃ or less. The polyarylene sulfide resin powder preferably has an average circularity of 0.70 to 1.00 as measured by a dynamic image analysis method.
Description
Technical Field
The present invention relates to a porous molded body and a method for producing the same.
Background
A porous molded article using a resin powder, which is cured by heat treatment in a porous state in which voids remain at the interface where particles overlap with each other, is used for various applications such as filters, sound absorbing materials, impregnating materials, coating materials, medical-related components, information-related components, and electronic components. Since polyarylene sulfide resins have high mechanical strength and are excellent in heat resistance, chemical resistance, and the like, it is expected that resin powders containing polyarylene sulfide resin fine particles can be formed into porous molded bodies that can be used in high-temperature environments, environments in contact with acidic solutions, and the like. As one of porous molded articles using polyarylene sulfide resin fine particles, a porous molded article using polyphenylene sulfide particles having an average particle diameter of 150 μm or more is known (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 02-298527
Disclosure of Invention
Problems to be solved by the invention
However, in the porous molded article comprising polyphenylene ether particles having an average particle diameter of 150 μm or more, the adhesion of the fine resin particles to each other is low, and thus the initial strength may be insufficient. The adhesion of the resin fine particles to each other greatly affects the performance and strength of the porous molded article in use. That is, when the adhesion of the resin fine particles is poor, pores may become large in use or the porous molded body may be damaged. When press molding is performed at a high temperature exceeding 300 ℃ or a high pressure exceeding 1500MPa in order to improve the adhesion between the resin fine particles, the porosity decreases although the strength is improved. If the porosity is reduced and deviates from the predetermined range, the dielectric characteristics, air permeability, and other characteristics may be insufficient.
The present invention addresses the problem of providing a porous molded body having excellent strength and a low dielectric constant, and a method for producing the same.
Solution for solving the problem
The present invention relates to the following.
[1] A porous molded body which is produced using a polyarylene sulfide resin powder having an average particle diameter of 5-100 [ mu ] m and a melting point Tm1 measured by a differential scanning calorimeter of 250-300 ℃ and has a porosity of 20-60%.
[2] The porous molded article according to [1], wherein the polyarylene sulfide resin powder has an average circularity of 0.70 to 1.00 as measured by a dynamic image analysis method.
[3]According to [1]]Or [2]]The porous molded body is characterized in that the barrel temperature and shear rate of the polyarylene sulfide resin powder are 1200sec at 30 ℃ higher than the melting point Tm1 measured by a differential scanning calorimeter -1 The melt viscosity measured below is 25 Pa.s to 5000 Pa.s.
[4] The porous molded article according to any one of [1] to [3], wherein a ratio of a maximum particle diameter to an average particle diameter (maximum particle diameter/average particle diameter) of the polyarylene sulfide resin powder is 6.5 or less.
[5] The porous molded article according to any one of [1] to [4], which has a relative dielectric constant of 1.0 or more and 2.5 or less at a frequency of 1 MHz.
[6] The method for producing a porous molded article according to any one of [1] to [5], comprising the steps of: a powder material containing a polyarylene sulfide resin powder having an average particle diameter of 5 [ mu ] m or more and 100 [ mu ] m or less and a melting point Tm1 measured by a differential scanning calorimeter of 250 ℃ or more and 300 ℃ or less is pressure-molded at a temperature of (melting point Tm 1-15) DEG C or more and (melting point Tm1+15) DEG C or less and a pressure of 0.1MPa or more and 30MPa or less.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a porous molded body having excellent strength and low dielectric constant and a method for producing the same can be provided.
Detailed Description
An embodiment of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within a range that does not hinder the effects of the present invention.
[ porous molded article ]
The present inventors have found in the course of the study that by setting the average particle diameter of the polyarylene sulfide resin powder and the melting point Tm1 measured by a differential scanning calorimeter to be within predetermined ranges, the adhesion of polyarylene sulfide resin fine particles to each other can be improved and a porous molded article having a low dielectric constant can be obtained, and completed the present invention.
(resin powder)
The porous molded body of the present embodiment is a porous molded body formed using polyarylene sulfide resin powder composed of polyarylene sulfide resin fine particles (hereinafter also referred to as "resin powder"). In the present specification, the term "fine particles" refers to particles having an average particle diameter of about 0.1 μm to 1000 μm, and the term "average particle diameter" refers to a volume-based arithmetic average particle diameter obtained by a laser diffraction/scattering particle size distribution measurement method. The average particle diameter can be measured by using, for example, a laser diffraction/scattering particle size distribution measuring apparatus LA-920 manufactured by horiba, inc.
The polyarylene sulfide resin is a resin having a repeating unit represented by the following general formula (I).
-(Ar-S)-···(I)
(wherein Ar represents arylene.)
The arylene group is not particularly limited, and examples thereof include p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p '-diphenylene sulfone group, p' -biphenylene group, p '-diphenylene ether group, p' -diphenylene carbonyl group, and naphthyl group. The polyarylene sulfide resin a may be a homopolymer in which the same repeating unit is used as the repeating unit represented by the above general formula (I), or may be a copolymer containing different repeating units according to the application.
As the homopolymer, a homopolymer having a p-phenylene group as an arylene group and repeating units of a p-phenylene sulfide group is preferable. This is because a homopolymer having a repeating unit of a p-phenylene sulfide group has extremely high heat resistance, and exhibits high strength, high rigidity, and high dimensional stability in a wide temperature range. By using such a homopolymer, a molded article having very excellent physical properties can be obtained.
As the copolymer, a combination of two or more different arylene sulfide groups among the arylene sulfide groups including the above arylene groups may be used. Among these, a combination containing a p-phenylene sulfide group and a m-phenylene sulfide group is preferable from the viewpoint of obtaining a molded article having high physical properties such as heat resistance, moldability, and mechanical properties. More preferably, the polymer containing at least 70mol% of p-phenylene sulfide groups, and still more preferably, the polymer containing at least 80mol% of p-phenylene sulfide groups. The polyarylene sulfide resin having a phenylene sulfide group is a polyphenylene sulfide resin (PPS resin).
It is known that polyarylene sulfide resins generally have a molecular structure that is substantially linear, i.e., has no branched and/or crosslinked structure, and resins having a branched and/or crosslinked structure according to the production method thereof, and this embodiment is effective for any type thereof.
The method for producing the polyarylene sulfide resin is not particularly limited, and it can be produced by a conventionally known production method. For example, it can be produced by synthesizing a low molecular weight polyarylene sulfide resin, and then polymerizing the resin at a high temperature in the presence of a known polymerization auxiliary agent to increase the molecular weight.
Various fibrous, powdery, plate-like inorganic and organic fillers may be blended with the polyarylene sulfide resin. Examples of the fibrous filler include inorganic fibrous materials such as glass fibers, milled glass fibers, carbon fibers, asbestos fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, fibers of silicates such as wollastonite, magnesium sulfate fibers, aluminum borate fibers, and fibrous materials of metals such as stainless steel, aluminum, titanium, copper, and brass. A particularly representative fibrous filler is glass fiber. It is to be noted that a high-melting-point organic fibrous substance such as polyamide, fluororesin, polyester resin, and acrylic resin may be used.
Examples of the particulate filler include silicates such as carbon black, graphite, silica, quartz powder, glass beads, glass spheres, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite; oxides of metals such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, and aluminum oxide; carbonates of metals such as calcium carbonate and magnesium carbonate; sulfates of metals such as calcium sulfate and barium sulfate; and ferrite, silicon carbide, silicon nitride, boron nitride, various metal powders, and the like.
Examples of the plate-like filler include mica, glass flakes, talc, and various metal foils.
These inorganic fillers and organic fillers may be used singly or in combination.
The filler may be contained in an amount of 5 to 200 parts by mass based on 100 parts by mass of the polyarylene sulfide resin. In addition, additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, pigments, and crystal nucleating agents may be blended as other components in the polyarylene sulfide resin.
The melting point Tm1 of the polyarylene sulfide resin powder measured by a differential scanning calorimeter is 250 ℃ or more and 300 ℃ or less, preferably 255 ℃ or more and 300 ℃ or less, and more preferably 260 ℃ or more and 300 ℃ or less. By setting the melting point Tm1 to 250 ℃ or higher and 300 ℃ or lower, the heat resistance of the porous molded article can be improved, and when the average particle diameter described later is satisfied, a porous molded article having excellent dielectric characteristics, air permeability and permeability in addition to high strength can be produced.
Note that, the melting point Tm1 is set as: peak top temperature among endothermic peaks of 1st run observed when (1 st run) was heated at a temperature rising rate of 10 c/min from room temperature by a method based on JIS K-7121 (1999).
Barrel temperature and shear rate of polyarylene sulfide resin powder at 30 ℃ higher than melting point Tm1 measured by differential scanning calorimeter are 1200sec -1 The melt viscosity measured below is preferably 25pa·s to 5000pa·s, more preferably 25pa·s to 1000pa·s. By setting the melt viscosity of the polyarylene sulfide resin powder to the above range, a homogeneous porous molded body can be obtained. The melt viscosity can be adjusted by adjusting the monomer feed ratio in polymerization of the polyarylene sulfide resin, controlling the polymerization time, blending the polyarylene sulfide resins having different melt viscosities, and the like.
The polyarylene sulfide resin powder has an average particle diameter of 5 μm or more and 100 μm or less, preferably 10 μm or more and 90 μm or less, more preferably 15 μm or more and 80 μm or less. By setting the average particle diameter to 5 μm or more and 100 μm or less, the adhesion of the polyarylene sulfide resin fine particles to each other can be improved, and when the above-described melting point Tm1 is satisfied, a porous molded article having high strength can be obtained even if the pressure molding is not performed at a high temperature exceeding 300 ℃ or at a high pressure exceeding 1500 MPa. Since the high temperature or the high pressure is not required during the press molding, the porosity of the obtained porous molded article can be prevented from decreasing. As a result, a porous molded article having excellent dielectric characteristics, air permeability and permeability in addition to high strength can be produced. In contrast, when the average particle diameter exceeds the above range, it is difficult to obtain a porous molded body having high strength unless the temperature or pressure is high. The method for measuring the "average particle diameter" is as described above.
The ratio of the maximum particle diameter to the average particle diameter (maximum particle diameter/average particle diameter) of the polyarylene sulfide resin powder is preferably 6.5 or less, more preferably 5.5 or less. The lower limit is not particularly limited, and may be 1 or more. The "maximum particle diameter" refers to the maximum value among values measured by a laser diffraction/scattering particle size distribution measurement method. By setting the ratio of the maximum particle diameter to the average particle diameter (maximum particle diameter/average particle diameter) to 6.5 or less, the adhesion of the polyarylene sulfide resin fine particles to each other can be further improved, and a porous molded article having higher strength can be produced.
The production of the polyarylene sulfide resin powder having the above average particle diameter is not particularly limited, and the polyarylene sulfide resin obtained by the above production method of polyarylene sulfide resin may be used as the resin powder as it is, or a treated product obtained as follows may be used: the polyarylene sulfide resin is molded into particles, fibers, films, and the like, and then subjected to a pulverization treatment using a dry pulverization, wet pulverization, or freeze pulverization using a jet mill, bead mill, hammer mill, ball mill, chopper, stone-type pulverizer, or the like. In addition, the following methods may also be used: a method of dissolving a polyarylene sulfide resin in a solvent and then spray-drying; a poor solvent precipitation method in which an emulsion is formed in a solvent and then contacted with a poor solvent; and a liquid drying method in which an emulsion is formed in a solvent and then an organic solvent is dried and removed. A method of mixing polyarylene sulfide and thermoplastic resin, and then dissolving and removing the thermoplastic resin with a solvent to obtain polyarylene sulfide resin powder having the above average particle diameter may also be used.
The polyarylene resin fine particles constituting the polyarylene sulfide resin powder preferably have a prescribed circularity. That is, the average circularity of the polyarylene sulfide resin powder measured by a dynamic image analysis method is preferably 0.70 or more and 1.00 or less, more preferably 0.80 or more and 1.00 or less. When the average circularity is within this range, the adhesion of the polyarylene sulfide resin fine particles to each other can be improved, and a high-strength porous molded article can be produced. The average circularity is: the degree of circularity of 4500 particles in the polyarylene sulfide resin powder was calculated from the following formula (II) based on the area a and the circumference P using a dynamic image analysis method/particle state analyzer, and the average value thereof was taken as the average degree of circularity.
Circularity= (4×)π×A)/P 2 ···(II)
The polyarylene sulfide resin powder may be used alone or in combination of two or more. From the viewpoint of easy control of the strength of the porous molded article obtained, it is preferable to blend two or more kinds of polyarylene sulfide resin powder. In the porous molded body, the total amount of the polyarylene sulfide resin powder is preferably 30% by volume or more, more preferably 50% by volume or more. The upper limit is not particularly limited, and may be set to, for example, 100% by volume or less.
(porous molded article)
The porous molded body is formed using the polyarylene sulfide resin powder, and thus has excellent strength and heat resistance. The porosity of the porous molded article is 20% to 60%, preferably 25% to 55%. Since the porosity is 20% or more and 60% or less, excellent dielectric characteristics, air permeability and permeability can be achieved while maintaining high strength. The porosity can be adjusted by setting the temperature and pressure in the press molding step to predetermined ranges.
The method of calculating the porosity can be obtained from the filling amount under pressure of various fluids such as water and mercury, and can be more easily obtained from the relationship between apparent specific gravity and true specific gravity measured by a densitometer by the following formula (III).
Porosity (%) = (1- (apparent specific gravity)/(true specific gravity)) ×100·· (III)
The porous molded article is a heat-resistant porous molded article having high strength, low dielectric constant, and excellent air permeability and permeability, and therefore can be preferably used for various applications such as filters, sound absorbing materials, impregnating materials, coating materials, medical-related parts, information-related parts, and electronic parts. Among them, the porous molded article having a relative dielectric constant of preferably 1.0 to 2.5, more preferably 1.2 to 2.0 at a frequency of 1MHz can be preferably used for electric/electronic parts such as information-related parts and electronic parts.
[ method for producing porous molded article ]
The method for producing a porous molded body according to the present embodiment comprises the following steps: and (3) performing compression molding on the powder material containing the polyarylene sulfide resin powder.
(pressure Forming step)
The press molding step includes the steps of: the powder material containing the polyarylene sulfide resin powder is press-molded at a temperature of (melting point Tm 1-15) DEG C or more and (melting point Tm1+15) DEG C or less, preferably at a temperature of (melting point Tm 1-10) DEG C or more and (melting point Tm1+15) DEG C or less, and at a pressure of 0.1MPa or more and 30MPa or less, preferably at a pressure of 0.1MPa or more and 20MPa or less. The melting point Tm1 is the melting point Tm1 of the polyarylene sulfide resin powder. In the press molding step, the polyarylene sulfide resin powder is locally welded while maintaining voids at the interface where the polyarylene sulfide resin fine particles overlap with each other, thereby forming a porous molded body. When the temperature is not within the above range, the adhesion between the resin fine particles in the polyarylene sulfide resin powder is poor, and the porous molded body is easily damaged.
The powder material is a powder material for porous molded bodies, and contains the polyarylene sulfide resin powder. The polyarylene sulfide resin powder may be used in an amount of 1 or two or more thereof may be used in combination. From the viewpoint of easy control of the semi-molten state and improvement of the strength of the porous molded article, it is preferable to blend two or more kinds of polyarylene sulfide resin powder. The powder material may be a material containing only the polyarylene sulfide resin powder, or may be a mixed material obtained by mixing the polyarylene sulfide resin powder with a filler and other additives. As the filler and additive, the same filler and additive as those which can be blended in the polyarylene sulfide resin powder described above can be used. The amount of the polyarylene sulfide resin powder used in the production of the mixed material is preferably 10 mass% or more, more preferably 20 mass% or more, in the powder material. The amount of the filler and the additive may be 90 mass% or less or 80 mass% or less in the powder material. The mixing method may be any conventionally known method, and examples thereof include a mixing method using vibration, a mixing method accompanied by pulverization such as a ball mill, and a mixing method using a stirring blade such as a henschel mixer.
In the present embodiment, since the powder material containing the above-described predetermined polyarylene sulfide resin powder is used, the press molding can be performed in a state where the polyarylene sulfide resin is semi-molten by performing the press molding in the above-described temperature and pressure ranges. By performing compression molding in a semi-molten state, the strength of the porous molded body can be improved. In addition, when the press molding is performed in a semi-molten state, the porosity and strength of the porous molded body can be adjusted by adjusting the press pressure. As a result, the strength, dielectric characteristics, air permeability, and other characteristics of the porous molded body can be controlled. For example, a porous molded article obtained by compression molding in a semi-molten state can have a porosity of 40 to 55% and a relative dielectric constant of less than 2. In contrast, when press molding is performed in an unmelted state using only a pressing pressure, the pressing pressure needs to be set to a high pressure in order to obtain a porous molded article having a desired strength, and at this time, the porosity is excessively reduced, and the characteristics are deteriorated. For example, in the comparative example described later, the desired strength cannot be achieved without setting the pressurizing pressure to 2000MPa, and at this time, the porosity is reduced to less than 20%, and the dielectric characteristics are deteriorated.
The press molding method is not particularly limited, and a conventionally known method can be used. The press molding method includes the following methods: for example, the powder material is filled in a jig, and the powder material is press-molded at a temperature of (melting point Tm 1-15) DEG C or higher and (melting point Tm1+15) DEG C or lower, for example, 270 DEG to 305 ℃, preferably 275 DEG to 300℃, and a pressure of 0.1MPa or higher and 30MPa or lower, preferably 0.1MPa or higher and 20MPa or lower. The melting point Tm1 is the melting point Tm1 of the polyarylene sulfide resin powder. Then naturally cooling, thereby obtaining a porous molded body. The porous molded article thus obtained is formed using a powder material containing the polyarylene sulfide resin powder, and therefore has high strength, low dielectric constant, and excellent air permeability and permeability.
(other procedures)
In order to widen the temperature range and the pressure range in the press molding step, the method for producing the porous molded article may include the steps of: before the press molding process, the polyarylene sulfide resin powder is heat-treated. As the heat treatment conditions, heat treatment may be performed at 180 ℃ or higher in an oxygen atmosphere, for example. By performing the heat treatment at 180 ℃ or higher, partial non-melting can be promoted, and the temperature and pressure ranges of the press molding step can be widened to, for example, a temperature of (melting point Tm 1-15) ℃ or higher and (melting point tm1+30) ℃ or lower and a pressure of 0MPa or higher and 50MPa or lower.
Further, in order to further improve the adhesion between the polyarylene sulfide resin fine particles, the following sintering step may be provided as another step: the porous molded body obtained in the press molding step is further heated and sintered in an oven or the like. The sintering step may be the following steps: the porous molded body obtained in the press molding step is heated at a temperature of, for example, 270 to 305 ℃, preferably 275 to 300 ℃ for, for example, 1 to 20 hours, preferably 1 to 5 hours, and sintered.
Examples
The present invention is further specifically illustrated by the following examples, which are not intended to limit the explanation of the present invention.
[ polyarylene sulfide resin ]
Polyarylene sulfide resins used in examples and comparative examples were as follows.
PPS1: polyphenylene sulfide resin, "FORTRON KPS" manufactured by KUREHA, inc. (melt viscosity: 30 Pa.s (shear rate: 1216 sec) -1 、310℃))
PPS2: polyphenylene sulfide resin, "FORTRON KPS" manufactured by KUREHA, inc. (melt viscosity: 130 Pa.s (shear rate: 1216 sec) -1 、310℃))
Example 1
PPS1 was dry-pulverized with an air jet MILL (SEISHIN CO., LTD, vertical jet pulverizer SK JETO-MILL) to obtain polyarylene sulfide resin powder. The melting point Tm1, melt viscosity, average particle diameter and maximum particle diameter, and average circularity of the resin powder were measured by the methods described later. The results are shown in Table 1.
3g of the obtained polyarylene sulfide resin powder was packed in an aluminum ring having a diameter of 40mm, and a porous molded article was produced by a hot Press molding machine (Mini Test Press-10 manufactured by Toyo Seisakusho Co., ltd.) at a temperature of 290℃and a pressure of 0.1 MPa. The porosity, strength and relative permittivity of the porous molded article were evaluated by the methods described below. The results are shown in Table 1.
Example 2 and comparative examples 1 to 3
A polyarylene sulfide resin powder was obtained in the same manner as in example 1, except that PPS2 was used instead of PPS 1. Melting point Tm1, melt viscosity, average particle size and maximum particle size, and average circularity of the polyarylene sulfide resin powder were measured in the same manner as in example 1. The results are shown in tables 1 and 2. A porous molded article was produced in the same manner as in example 1, except that the obtained polyarylene sulfide resin powder was used and the conditions of temperature and pressure were as shown in table 1. The porous molded article was evaluated for porosity, strength, and relative permittivity in the same manner as in example 1. The results are shown in tables 1 and 2. In comparative example 2, the porous molded article had low strength and was not able to measure the relative permittivity because of the defect of breakage during measurement.
Example 3
The polyarylene sulfide resin powder obtained in example 2 was heat-treated at 240℃for 8 hours using an air circulation dryer (HIGH-Temp. OVEN PHH-201, manufactured by ESPEC Co., ltd.) to obtain a polyarylene sulfide resin powder. Melting point Tm1, melt viscosity, average particle size and maximum particle size, and average circularity of the polyarylene sulfide resin powder were measured in the same manner as in example 1. The results are shown in Table 1. A porous molded article was produced in the same manner as in example 1, except that the obtained polyarylene sulfide resin powder was used and the conditions of temperature and pressure were as shown in table 1. The porous molded article was evaluated for porosity, strength, and relative permittivity in the same manner as in example 1. The results are shown in Table 1.
Example 4
50 mass% of the polyarylene sulfide resin powder obtained in example 2 and 50 mass% of the polyarylene sulfide resin powder obtained in example 3 were dry-blended to obtain a polyarylene sulfide resin powder. Melting point Tm1, melt viscosity, average particle size and maximum particle size, and average circularity of the polyarylene sulfide resin powder were measured in the same manner as in example 1. The results are shown in Table 1. A porous molded article was produced in the same manner as in example 1, except that the obtained polyarylene sulfide resin powder was used and the conditions of temperature and pressure were as shown in table 1. The porous molded article was evaluated for porosity, strength, and relative permittivity in the same manner as in example 1. The results are shown in Table 1.
Comparative example 4
A polyarylene sulfide resin powder was obtained in the same manner as in example 1, except that PPS2 was not pulverized and was used as it is, and the conditions of temperature and pressure were set to the conditions shown in table 1. Melting point Tm1, melt viscosity, average particle size and maximum particle size, and average circularity of the polyarylene sulfide resin powder were measured in the same manner as in example 1. The results are shown in Table 2. In an attempt to produce a porous molded article using the resin powder in the same manner as in example 1, the adhesion between particles was insufficient and the molding was impossible.
Comparative example 5
PPS2 was subjected to a heat treatment at 240℃for 4 hours with an air circulation dryer (ESPEC corporation "HIGH-Temp. OVENPHH-201") to obtain polyarylene sulfide resin powder. Melting point Tm1, melt viscosity, average particle size and maximum particle size, and average circularity of the polyarylene sulfide resin powder were measured in the same manner as in example 1. The results are shown in Table 2. A porous molded article was produced in the same manner as in example 1, except that the obtained polyarylene sulfide resin was not subjected to pulverization treatment but was used as it is, and the conditions of temperature and pressure were set to the conditions shown in table 1. The porous molded article was evaluated for porosity, strength, and relative permittivity in the same manner as in example 1. The results are shown in Table 2.
Comparative example 6
PPS1 was subjected to heat treatment at 240℃for 8 hours with an air circulation dryer (ESPEC corporation "HIGH-Temp. OVENPHH-201") to obtain polyarylene sulfide resin powder. Melting point Tm1, melt viscosity, average particle size and maximum particle size, and average circularity of the polyarylene sulfide resin powder were measured in the same manner as in example 1. The results are shown in Table 2. A porous molded article was produced in the same manner as in example 1, except that the obtained polyarylene sulfide resin was not subjected to pulverization treatment but was used as it is, and the conditions of temperature and pressure were set to the conditions shown in table 1. The porous molded article was evaluated for porosity, strength, and relative permittivity in the same manner as in example 1. The results are shown in Table 2.
[ measurement ]
(melting Point Tm 1)
The peak top temperature of the endothermic peak observed when (1 stRUN) was heated from room temperature at a temperature rise rate of 10 ℃/min was measured as the melting point Tm1 using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, DSC 7000X).
(melt viscosity)
Capillary rheometer (Capirograph 1D: piston diameter 10mm, manufactured by Toyo Seisakusho Co., ltd.) was used, and the cylinder temperature and shear rate were 1200sec at 30℃higher than the melting point Tm1 -1 The apparent melt viscosity was determined based on ISO 11443. For the measurement, a hole having an inner diameter of 1mm and a length of 10mm was used.
(average particle size and maximum particle size)
The average particle diameter and the maximum particle diameter were measured using a laser diffraction/scattering particle size distribution measuring apparatus (LA-920, manufactured by horiba, inc.). The average particle diameter is the arithmetic average particle diameter on a volume basis. The maximum particle diameter/average particle diameter was calculated from the obtained average particle diameter and the maximum particle diameter.
(circularity)
Using a dynamic image analysis method/particle state analyzer (SEISHIN co., LTD, PITA-3), the average value of the circularity of 4500 particles in the polyarylene sulfide resin powder was calculated from the following formula (II) based on the area a and the circumference P, and the average value was taken as the average circularity of the resin powder. In table 1, "circularity" indicates average circularity.
Circularity= (4×pi×a)/P 2 ···(II)
[ evaluation ]
The porous molded bodies obtained in examples and comparative examples were evaluated for porosity, strength, and relative permittivity by the following methods. The results are shown in Table 1.
(porosity)
From the apparent specific gravity and the true specific gravity, the porosity was obtained by the following formula (III). The apparent specific gravity was measured using a densitometer (manufactured by Mirage corporation, "electronic densitometer SD-120L"). A nonporous molded article was produced by injection molding, and the true specific gravity was measured by the same gravimeter.
Porosity= (1- (apparent specific gravity)/(true specific gravity)) ×100·· (III)
(intensity)
A80N load was applied to a porous molded article with a glass plate having a diameter of 40mm X a thickness of 3mm mounted thereon by using a Babbitt metal (Barber Colman Company). The strength of the porous body was evaluated based on the following criteria.
Good: is not damaged by
Poor: visible destruction
(relative permittivity)
The relative permittivity at 1MHz was measured by using a permittivity measuring device (manufactured by Novocontrol Technologies Co., ltd., concept 42).
TABLE 1
TABLE 2
As is clear from table 1, the porous molded bodies of examples were not damaged in the strength evaluation, and had excellent strength. In addition, the porosity is 20% to 60%, and the dielectric constant is low. Thus, the porous molded article of the example can maintain high strength and realize excellent dielectric characteristics, air permeability and permeability.
Claims (5)
1. A porous molded article which is produced using only a polyarylene sulfide resin powder having an average particle diameter of 5-100 [ mu ] m, a melting point Tm1 measured by a differential scanning calorimeter of 250-300 ℃,
wherein the polyarylene sulfide resin powder has an average circularity of 0.70 to 1.00 as measured by a dynamic image analysis method.
2. The porous molded article according to claim 1, wherein the polyarylene sulfide resin powder has a barrel temperature and a shear rate of 1200sec at 30 ℃ higher than the melting point Tm1 measured by a differential scanning calorimeter -1 The melt viscosity measured below is 25 Pa.s to 5000 Pa.s.
3. The porous molded article according to claim 1 or 2, wherein a ratio of a maximum particle diameter to an average particle diameter of the polyarylene sulfide resin powder, that is, a maximum particle diameter/average particle diameter is 6.5 or less.
4. The porous molded body according to claim 1 or 2, which has a relative dielectric constant of 1.0 or more and 2.5 or less at a frequency of 1 MHz.
5. A method for producing the porous molded article according to any one of claims 1 to 4, comprising the steps of:
a powder material containing a polyarylene sulfide resin powder having an average particle diameter of 5 [ mu ] m or more and 100 [ mu ] m or less and a melting point Tm1 measured by a differential scanning calorimeter of 250 ℃ or more and 300 ℃ or less is subjected to compression molding at a temperature of 1-15 ℃ or more and a melting point Tm1+15 ℃ or less and a pressure of 0.1MPa or more and 30MPa or less.
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| WO2022137648A1 (en) * | 2020-12-24 | 2022-06-30 | Dic株式会社 | Crosslinked polyarylene sulfide, composition, and method for producing molded article |
| CN116601214A (en) * | 2020-12-24 | 2023-08-15 | Dic株式会社 | Crosslinked polyarylene sulfide, composition, and process for producing molded article |
| CN114989721B (en) * | 2022-04-28 | 2023-05-05 | 浙江新和成特种材料有限公司 | Polyphenylene sulfide compound coating and preparation method thereof |
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