JPH0324159A - Preparation of high strength, heat-and chemical-resistant polyarylene sulfide composite - Google Patents

Abstract

PURPOSE:To improve the strength and heat and chemical resistance of a composite comprising a high-strength fibrous material and a polyarylene sulfide by irradiating the composite with rays of light. CONSTITUTION:A composite comprising a fibrous material (having a strength of 20g/d or higher, an elastic modulus of 400g/d or higher, and an aspect ratio of at least 10; e.g. glass fiber or carbon fiber) and a polyarylene sulfide (e.g. polyphenylene sulfide) and contg. at least three fibers of 10mum in diameter or thinner in each 1000 square mum of the cross section of the composite is irradiated with ultraviolet or visible rays at an illuminance of pref. 5lx or higher at above the glass transition point of the polyarylene sulfide (pref. in the range of from 50 deg.C above the glass transition point to about the m.p.) in an oxygen-contg. atmosphere until the surface of the composite becomes infusible or insol. in alpha-chloronaphthalene. Thus is obtd. a high-strength, heat- and chemical-resistant composite.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention... High intensity (12) light irradiation is involved in the preparation of arylene sulfide complexes. For more details. Reinforced with high-strength fibers, and moreover. Polyarylene sulfide is insoluble and infusible in solvents. High-intensity (12) light irradiation relates to a method for producing arylene sulfide composites. [Prior art] Polyarylene sulfide has become popular in recent years due to its heat resistance, chemical resistance, flame retardancy, etc. In particular, the expansion is expanding. However, its low strength was a major drawback. It can also be melted by heat. It has the disadvantage that it dissolves in high-temperature solvents. In order to eliminate such drawbacks, the present inventors. Japanese Patent Publication No. 1-98
Publication No. 633 proposes making it infusible by using metals, etc. However, this method has the disadvantage that it is difficult to remove metals, etc. On the other hand, regarding high strength. Reinforcing polyarylene sulfide with glass fibers, etc. is widely practiced. but. There was nothing that simultaneously satisfied both high intensity and (12) light irradiation. [Problems to be Solved by the Invention] The purpose of the present invention is to
At the same time, it improves strength, (2) heat resistance, and (3) chemical resistance. ■Clean composite manufacturing method free of unnecessary materials. The goal is to provide the following. [Means for Solving the Problems] In view of the current situation, the present inventors have arrived at the present invention as a result of intensive studies without being bound by conventional research concepts. The present invention aims to solve the above problems. It has the following configuration. <<1>> Strength 2 0 g/d. High strength (12) characterized in that a composite consisting of a fibrous material having an elastic modulus of 400 g/d or more and an aspect ratio of 10 or more and polyarylene sulfide is irradiated with light at a temperature higher than the glass transition point of the polyarylene sulfide. (12) The light irradiation is performed at high intensity according to the method for producing a polyarylene sulfide composite (2) wherein the fibrous material is selected from at least 1 fffi of the following A to F. Manufacturing method A. Glass fiber, B. Carbon fiber, C. Ceramink fiber, D. Arabido fiber. E. aromatic polyimide fiber,
F. The polyarylate fiber and/or polyesteramide fiber (3) composite is. A fiber, and the fiber contains a fibrous material with a thickness of 10 μm or less. and the number of fibers per cross-sectional area of the complex is 3 or more per iooo square μ.
Alternatively, the high-intensity (12) light irradiation described in 2 is a method for producing a polyarylene sulfide composite. (4) The composite is a fiber and the fiber constitutes a woven structure.(12) A method for producing a polyarylene sulfide composite in which the high intensity light irradiation is performed according to any one of 1 to 3. (5) Polyarylene sulfide. The high-intensity (12) light irradiation according to 1, which is selected from at least one of the following A to G, is performed in the method for producing a polyarylene sulfide composite. A. Polyphenylene sulfide. B. Polyxylylene sulfide. C. Polynaphthalene sulfide, D6 boribiphenylene sulfide, F. Polyphenylene sulfide. G. Polyphenylene sulfide sulfone. <<6>> The formation of the composite consists of (1) the step of melting and composite forming polyarylene sulfide and thermoplastic liquid crystal resin;
2) A step of heat treatment at a temperature above the melting point of the liquid crystal resin -100)°C. A method for producing an arylene sulfide complex in which the high-intensity (12) light irradiation according to item 1 or 5, comprising:

(7) The precept form of the complex is. A step of melt-spinning a polyarylene sulfide and a thermoplastic liquid crystal resin into a composite fiber, (2) a step of heat-treating the composite fiber at a temperature of (melting point -100)C or higher of the liquid crystal resin, and (3) a step of forming the composite fiber into an aggregate. <4) The high-intensity (12) light irradiation described in 1.5.6, which consists of the step of thermally bonding the composite fiber aggregate (steps ■1 and ■.■ can be performed in any order), Method for producing sulfide complexes. (8) The high intensity light irradiation according to 6 or 7, wherein the step of forming the melt composite is melt composite spinning.
Production method of polyarylene sulfide composite. (9) The shape of the complex is one of the following: 1. The high-intensity (12) light irradiation described in 67 was applied to the polyarylene phide complex. A. Board, B. Sheet, C. ta fiber. The high strength (12
) Light irradiation is a method for producing polyarylene sulfide composites. (Step 1) The high strength (
12) A method for producing a polyarylene sulfide composite in which light irradiation is performed. (12) The high intensity light irradiation described in 1 or 11, wherein the light irradiation is performed until at least the surface layer of the polyarylene sulfide becomes insoluble in α-chlornaphthalene. (12) The method for producing a polyarylene sulfide composite. ) High intensity according to any one of 1, 11 and 12, wherein the light irradiation atmosphere is an oxygen-containing atmosphere. The polyarylene sulfide according to the present invention is mainly composed of aromatics, and at least a portion of the bonds in the main chain are composed of sulfide bonds.In the present invention, if such a polymer is used, there are no particular limitations. Polyphenylene sulfide and its copolymers, polyphenylene sulfide sulfone and its copolymers are particularly preferred. Phenylene sulfide ketone and its copolymers, polyphenylene sulfide sulfone ketone and its copolymers, polynaphthalene sulfide and its copolymers, polybiphenylene sulfide and its copolymers, polyxylylene sulfide and its copolymers Combination etc.

These resins have excellent shapeability. Also. It is preferable because it has excellent heat resistance and chemical resistance.

When such a resin is irradiated with light at a temperature higher than the glass transition temperature of the resin. It becomes stably infusible. Next, the fibrous material, which is the other material of the present invention, will be described. In the present invention, in order to obtain a high-strength polyarylene-ruphide composite, high strength. A fibrous material with high elastic modulus is used. The strength is 20g/c1 or more, and the elastic modulus is 400g/d. Fibrous materials below this value are undesirable because the reinforcing effect of polyarylene sulfide is weak. Particularly preferred is one with a strength of 25 g/d or more. The elastic modulus is 500 g/d or more. In addition, the aspect ratio of the fibrous material is
Must be IO or higher. More preferably, the aspect ratio is 50.
That's all. What happens when the aspect ratio increases? It is preferable because the i-strong effect is high. It is particularly preferable that the fibrous material is continuous. Note that the aspect ratio here is the ratio of the length of the uIA filament divided by its thickness. For example, a fiber with a diameter of 10μ and a length of 1000μ has an aspect ratio of 100. In addition, it is preferable that the thickness of the fibrous material be thin. More preferably, the thickness is 10μ or less. More preferable is 8
It is less than μ. When si<. This is preferable because it improves the strength of the composite, and especially improves fatigue resistance and impact resistance. The form of such fibrous materials may be fibers,
Also. Part of it may be fibrillated. In addition, various cross-sectional shapes can be widely used, including special hollow cross-sections such as narrow cross-sections, nine cross-sections, hollow cross-sections, H-shaped cross-sections, rice-shaped cross-sections, lotus root cross-sections, L-shapes, rectangular cross-sections, triangular cross-sections, etc. ．． The manufacturing method for such fibrous materials does not matter. Conventionally known ones can be widely used. The following are particularly preferred as such fibrous materials. That is. Various glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, tyranno fibers, ceramic fibers such as various ceramic whisker fibers, Arabido fibers such as Kevlar and Technora, aromatic polyamide fibers, etc. Typical examples include various polyarylate fibers that exhibit liquid crystallinity, and polyesteramide fibers that also exhibit liquid crystallinity. It is preferable that three or more such fibrous materials exist per 1000 square μm of the cross-sectional area of the composite. More preferably, there are 5 or more, and particularly preferably 10 or more. This stabilizes the mechanical properties of the composite. What is particularly preferable is that such a composite has a woven or knitted structure. As for the woven fabric, not only conventional woven fabrics but also multiaxial woven fabrics, three-dimensional woven fabrics, etc. are particularly preferable. The shape of the complex is not particularly important. It may be a plate, a sheet, a fiber, or a processed product thereof.

Board because of its ease of light irradiation. Two-dimensional and one-dimensional objects such as sheet-like objects and fibers are particularly preferred. Conventionally known techniques can be widely used for these manufacturing methods. A particularly preferred polyarylene sulfide composite of the present invention is one whose surface is coated with polyarylene sulfide. Polyarylene sulfide becomes heat resistant through this treatment. It also improves chemical resistance. When this is present on the surface, the polyarylene sulfide composite of the present invention exhibits heat resistance, chemical resistance, etc. at the same time.

Next, a particularly preferred method for producing a polyarylene sulfide composite of the present invention will be described. The polyarylene sulfide and thermoplastic liquid crystal resin are melted and shaped to form a fibrous structure in the composite, and then the liquid crystal resin has a melting point of −100°C.
This method involves heat treatment at a temperature above, followed by light irradiation. The liquid crystal resin used in the present invention is not particularly limited, and conventionally known ones can be widely used.

By combining polyarylene sulfide and liquid crystal resin,
The method of making liquid crystal resin into fibers is to reduce the viscosity of both to within twice. This is possible by melt mixing. It is preferable that the viscosities of both be as close as possible. simply.
If the two are simply melt-mixed, the surface of the composite may be formed of a liquid crystal resin other than polyarylene sulfide, so a flow of polyarylene sulfide is created on the outside. It is extremely preferable to merge the two at a mouthpiece or the like so that the surface of the polyarylene sulfide composite has a structure made of polyarylene sulfide. As a composite melt-spinning method, particularly preferred is composite melt-spinning. In the case of melt spinning, the take-up speed can be increased. It has the advantage of being able to highly align the liquid crystal resin. Various methods can be used for composite melt spinning, including the core-one-sheath method and the one-polymer array method. Blend spinning method, split-peel method, and composite split-peel method in which the core is split-peel type and there is an additional sheath. Preferred methods include a composite blend spinning method in which the core is a blend and the outer shell is a sheath. Particularly preferred are the core-sheath method, the polymer array method, the segmented and peeled method, and the composite segmented and peeled method. By adopting such a method, the ratio of the liquid crystal resin component to the polyarylene sulfite component can be made uniform throughout the composite. Also, when spinning. Since it can be spun at high speed, it is possible to achieve high fiber orientation. For this reason, fibers with high strength and high modulus of elasticity can be produced. Next, the composite thus obtained is heat treated at a temperature higher than (melting point -100)C of the liquid crystal resin, if necessary. Heat treatment may be carried out in air, but it is particularly preferable to carry out heat treatment in an inert gas such as nitrogen or under vacuum. By doing this, the strength of the fibrous material made of liquid crystal resin in polyarylene sulfide easily exceeds 20 g/d. Note that the treatment temperature may be near the melting point of the liquid crystal resin or above the original melting point. Liquid crystal resin is produced by heat treatment. Since the melting point increases, heat treatment above the original melting point is also effective. In addition, especially. Composite melt spinning is composite melt spinning, and when the fibers are further processed into rods, plates, sheets, etc.
Appropriately, a large number of fibers are converged to form a tow or a woven fabric. It is preferable to make it into a fiber aggregate such as non-woven fabric and then thermally bond it. Next, we will discuss light irradiation. If the temperature at which the polyarylene sulfide composite is irradiated with light is low, for some reason microscopic cracks often occur in the polyarylene sulfide, which is not desirable as the physical properties of the resulting product are not stabilized. Additionally, light irradiation at low temperatures takes time, making it impractical. The light to be irradiated may be ultraviolet rays or visible light. The temperature of the polyarylene sulfide during irradiation is. The glass transition temperature is higher than the glass transition point of the polymer. If the temperature at the time of irradiation is below the glass transition point, the above-mentioned problem will occur, the effectiveness will be low, and there will be no effect from an industrial perspective. and. The higher the treatment temperature, the higher the effect. It is preferable to irradiate with light at a temperature of (glass transition temperature + 50)°C or higher.
The maximum temperature for processing may be close to the melting point. Also. Since the melting point of polyarylene sulfide may increase when exposed to light, in some cases it may be possible to treat it at a temperature higher than the melting point before irradiation with light. Note that there are some substances, such as polyphenylene sulfide sulfone, that do not exhibit a clear melting point, so the maximum temperature for light irradiation should be determined through sufficient prior testing. In other words, the maximum processing temperature should be selected to be compatible with the polymer type. Also, especially when exposed to light at high temperatures. Resin and resin molded products often deform, so before exposing them to light at sudden high temperatures,
It is heat-treated at high temperatures in advance to suppress deformation caused by heat, and then irradiated with light. To suppress dimensional changes caused by high-temperature light irradiation.
This is a particularly preferred method. Furthermore, it is preferable to irradiate light while gradually raising the temperature from a low temperature to a high temperature. It is also a preferable method to irradiate light in multiple stages, such as a low-temperature irradiation area and a high-temperature irradiation area. These methods produce polyarylene sulfide molded products such as films or porous films. This method is particularly preferable for fibers and their processed products, such as fabrics and porous membranes. In addition. Polymers generally contain low molecular weight substances such as oligomers. This material evaporates from the volima due to high temperature treatment. Do not irradiate light after removing vaporizable substances such as polymer monomers, as they may adhere to light-emitting devices and reduce efficiency. This is particularly important. It is also important to control the diffusion air flow of the evaporated monomer to prevent it from adhering to the light source. That is, the polyarylene sulfide composite is placed in the longitudinal direction or continuously moved in the longitudinal direction, and the airflow near the polyarylene sulfide composite is controlled to flow from below to above, and the light is emitted from the lateral direction. Irradiation is particularly effective. And as for the atmosphere in which the light is irradiated. It is preferable to carry out the test in an atmosphere containing @ elements. In other words, air is a particularly favorable atmosphere. There is no problem even if the test is carried out in high-oxygen air containing a large amount of oxygen or in an atmosphere containing ozone. The amount and time of the next irradiation will depend on the purpose and application. Borima species, shape of Borima articles, ambient temperature, amount of oxygen in the atmosphere, additives in Borima. It cannot be generalized as it varies greatly depending on the wavelength of the light, etc. However, it is preferable to irradiate light of 1 lux or more for 1 second or more. It is more preferable to emit light of 5 lux or more. Irradiation time. Polyarylene sulfide becomes infusible by regulating the irradiation dose and temperature. It is also insoluble in α-chlornaphthalene. In addition. There is no particular problem if all of the polyarylene sulfide in the polyarylene sulfide composite of the present invention becomes insoluble or infusible, but depending on the application, only the surface of the composite may be infusible or chemically resistant. In some cases, it is good even if the properties are improved, so the purpose of light irradiation is
It is preferable to clarify the purpose and implement it. Various pigments may be used in the polyarylene sulfide or liquid crystal resin of the present invention. Fillers such as calcium, fluorescent materials, etc. may be added. Furthermore, it does not matter if light-resistant materials, light-shielding materials, etc. are added to the liquid crystal resin. The highly heat-resistant polyarylene sulfide of the present invention has the characteristics of conventional polyarylene sulfide. At the same time, it has strength, heat resistance, chemical resistance, nitrogen flammability, and insulation properties. It can be deployed in many fields. An example is shown below. Electrical insulation base material. Printed boards, solder-free printed boards, various boards, heat-resistant fabrics. Heat-resistant plate. Chemical resistant plate, heat resistant filter. Structural materials, heat-resistant electrical insulation materials. Moving parts, filters, heat-resistant filters. Chemical-resistant filter, heat-resistant reinforcing material. Flame-retardant materials, fi-flammable wall materials, wall materials for intelligent buildings, heat-resistant and flame-retardant materials, interior materials for aircraft. Wall materials for aircraft, floor materials, chairs, base materials for automobiles, flammable floor materials,
H-flammable wood substitute materials, gaskets, fire prevention materials, fire prevention clothing. Fire extinguishing sheets, etc. Below are examples. Let me explain in more detail. It goes without saying that the present invention is not limited to these embodiments. [Example] Example 1 As shown below, a polymer array fiber was made by using polyphenylene sulfide as the seabed part and liquid crystal polyester as the island part.
Continue making cloth. Next, the fabric is subjected to solid phase polymerization, and then the fabric is made into a plate by heat pressing, and is further irradiated with light to give a high strength (12
) Light irradiation resulted in an arylene sulfide complex. There were no particular problems in each process. A. Polymer array fibers were made under the following spinning conditions. A. Silk spinning conditions■i precepts. Polyphenylene sulfide manufactured by Toray Filimbus Petroleum.

■Shima Ibun: Liquid crystal polyester Vectra A 950 manufactured by Hoechst Celanese. ■Island/sea-35/65 (weight ratio). Number of islands: 36 ■ Spinning temperature: 305°C ■ Spinning speed: 2000 m/min ■ Stretching ratio: None. B. Characteristics of the obtained fiber ■Fineness - 15d ■Strength - 4g/d ■Elongation - 2.1% ■Thickness of island approximately 4μ ■Number of fibers per cross section of polyarylene sulfide composite - per 1000 square μ Approximately 29 pieces ■Aspect ratio Ichishima fibers are continuous fibers, and in fact have an infinite C. Fabric making and solid phase polymerization Next, this fiber was woven into a twill weave. Next, the fabric was wrapped around a perforated stainless steel cylinder, and the fabric was heated for 25 minutes while blowing out nitrogen gas from inside.
Heat treatment was performed at 0°C for 1 hour and then at 270°C for 3 hours. Next, three layers of this fabric were layered and heated to 285°C in a reduced pressure section.
Press with a heated flat plate press. The three sheets were thermally bonded to form a board made of polyarylene sulfide composite. D. Light irradiation: Use a weatherometer for light resistance testing.
The cough plate was heated to 275°C in the air and exposed to light for 5 minutes on each side. The resulting board turned blackish brown. The main board is 3
It retained its shape even when left in air at 50°C. Also. LO■ is 36ε high<. M has excellent flammability. It was also extremely resistant to high-temperature chemicals, as it did not dissolve in alpha chlornaphthalene at 250°C. Next, when I forcibly burned the main board,
The fabric was carbonized while retaining its shape. We also measured its resistance to solder for printed circuit boards and found that there were no particular problems. Also. The bending strength of the VI plate is about 3 times that of a similarly made plate made of only polyphenylene sulfide (3 times that of a plate made of only unirradiated polyphenylene sulfide), and the impact strength is about 25 times. In other words, it was particularly suitable as a thermal printed board. As a comparative example, when the heat resistance of the board before irradiation was investigated, it was found that the board deformed significantly at about 280°C, and at 350°C. In this case, polyarylene sulfide melted and fell off.

In addition, it was easily dissolved in alpha chlornaphthalene at 250°C. It should be noted that the strength of the $ilIi fiber made of the liquid crystal resin of the present invention cannot be measured because polyarylene sulfide is infusible and insoluble. When calculated backward from the strength of the polymer array fiber, the strength was -27 g/d. Elastic modulus = 650g/d
Met. Example 2 Glass fibers (diameter: about 6μ, average length: -3
A commercially available plate containing 40% by weight of 00μ) dispersed therein was irradiated with light in the same manner as in Example 1. The resulting board is. It turned blackish brown.
This board can be left in air at 350°C. It maintained its shape. Also, the Lot is high at 36. It had excellent H flammability. It was also extremely resistant to high-temperature chemicals, such as not melting even in alpha chlornaphthalene at 250°C. Next, when the board was forcibly burnt, it carbonized while retaining most of its shape. We also measured its resistance to solder for printed circuit boards and found that there were no particular problems. Note that the temperature of the unirradiated plate is approximately 280℃.
At 350°C, the polyarylene sulfide melted and fell off. Also. It also had no solder resistance. 250
It was easily dissolved in alpha chlornaphthalene at ℃. [Effects of the Invention] The configuration of the present invention brings about the following great effects.

Claims (13)

[Claims] (1) A composite consisting of a fibrous material having a strength of 20 g/d, an elastic modulus of 400 g/d or more, and an aspect ratio of 10 or more and polyarylene sulfide is irradiated with light at a temperature higher than the glass transition point of the polyarylene sulfide. Manufacturing method for characteristic high-strength, heat-resistant and chemical-resistant polyarylene sulfide composites (2) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to claim 1, wherein the fibrous material is selected from at least one of the following A to F. A, glass fiber, B, carbon fiber, C, ceramic fiber,
D, aramid fiber, E, aromatic polyimide fiber, F, polyarylate fiber and/or polyesteramide fiber (3) A claim in which the composite is a fiber, and the fiber has a fibrous substance with a thickness of 10μ or less, and the number of fibers per 1000 square μ of the composite is 3 or more per cross-sectional area of the composite. A method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to item 1 or 2. (4) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to any one of claims 1 to 3, wherein the composite is a fiber and the fiber constitutes a woven structure. (5) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to claim 1, wherein the polyarylene sulfide is selected from at least one of the following A to G. A, polyphenylene sulfide, B, polyxylylene sulfide, C, polynaphthalene sulfide, D, polybiphenylene sulfide, F, polyphenylene sulfide ketone, G, polyphenylene sulfide sulfone. (6) The formation of the composite includes (1) a step of melting and composite molding polyarylene sulfide and thermoplastic liquid crystal resin; (2)
6. The method for producing a high-strength, heat-resistant and chemical-resistant arylene sulfide composite according to claim 1, comprising the step of heat-treating the liquid crystal resin at (melting point -100)C or higher. (7) Molding of the composite is a step of melting and spinning polyarylene sulfide and a thermoplastic liquid crystal resin, (2) a step of heat-treating the composite fiber at a temperature of (melting point -100)°C or higher of the liquid crystal resin, (3) composite (4) Step of thermally bonding the composite fiber aggregate (Steps (2), (3), (
4) can be in any order). Claim 1
A method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite as described in , 5 and 6. (8) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to claim 6 or 7, wherein the step of melt composite forming is melt composite spinning. (9) Claim 1, wherein the shape of the composite body is any of the following:
6. The high-strength heat-resistant and chemical-resistant polyarylene oxide composite described in 6 and 7. A, board, B, sheet, C, fiber. (10) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to any one of claims 1, 6, and 7, wherein the surface of the composite is covered with polyarylene sulfide. (11) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to claim 1, wherein the light irradiation is performed until at least the surface layer of the polyarylene sulfide becomes infusible. (12) The method for producing a high-strength, heat-resistant and chemical-resistant polyarylene sulfide composite according to claim 1 or 11, wherein the light irradiation is performed until at least the surface layer of the polyarylene sulfide becomes insoluble in α-chlornaphthalene. (13) The method for producing a high-strength heat-resistant and chemical-resistant polyarylene sulfide composite according to any one of claims 1, 11, and 12, wherein the atmosphere of light irradiation is an oxygen-containing atmosphere.