JP2012240317A - Method for continuously manufacturing pultrusion molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for continuously manufacturing a pultrusion molded article impregnated with a thermoplastic resin in which impregnating ability with a reinforced fiber is excellent by using a cyclic polymerization component, coloration due to oxidation hardly occurs, and the mechanical property is excellent.SOLUTION: In the method for continuously manufacturing a pultrusion molded article by continuously supplying the following component (A) and passing a mold for pultrusion molding filled with the following molten component (B), a process (II) is performed after the following process (I). The component (A) is 10-90 wt.% of reinforce fiber, and the component (B) is 90-10 wt.% of cyclic polymerization component (the total amount of the component (A) and the component (B) is 100 wt.%). The process (I) is a process in which the component (B) is supplied, and the component (B) is impregnated with the component (A) by passing the component (A) in a mold filled with the molten component (B). The process (II) is a process in which the component (B) impregnated with the component (A) is polymerized in the same mold as that in the process (I).

Description

  The present invention relates to a method for producing a pultruded product. More specifically, the present invention relates to a continuous production method of a pultruded article impregnated with a thermoplastic resin, which has good impregnation into a reinforcing fiber and is less colored by oxidation and has excellent mechanical properties by using a cyclic polymer component.

  Resin compositions comprising reinforcing fibers and thermoplastic resins are widely used in sports equipment applications, aerospace applications and general industrial applications because they are lightweight and have excellent mechanical properties. Reinforcing fibers used in these resin compositions reinforce molded products in various forms depending on the intended use. These reinforcing fibers include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers and PBO fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers. Carbon fibers are preferred from the viewpoint of the balance between rigidity and lightness, and among them, polyacrylonitrile-based carbon fibers are suitably used. In addition, polypropylene resin, polyamide resin, polyester resin, polyphenylene sulfide resin, etc. are used as the thermoplastic resin used as the matrix resin. (Hereinafter abbreviated as PPS resin) are attracting attention as electrical / electronic equipment members and automobile equipment members.

  Furthermore, as a method for producing a molded product using reinforcing fibers and a thermoplastic resin as a matrix, methods such as an injection molding method, an extrusion molding method, a prepreg method, an autoclave method, and a pultrusion method are applied.

  However, it is well known that the higher the melt viscosity of the thermoplastic resin, the more difficult it is to impregnate the reinforcing fiber bundle. Thermoplastic resins with excellent mechanical properties such as toughness and elongation are high molecular weight polymers, have high viscosity, and require higher process temperatures, making molding materials easy and productive. It was unsuitable for that. On the other hand, when a low molecular weight, that is, a low-viscosity thermoplastic resin is used for the matrix resin due to the ease of impregnation, there is a problem that the mechanical properties of the obtained molded product are significantly lowered.

As a method for impregnating a continuous reinforcing fiber with a thermoplastic resin, for example, a crystalline thermoplastic resin film is arranged on both sides of a sheet-like reinforcing fiber bundle, and a temperature of 150 ° C. is higher than the melting point of the resin. There has been proposed a method in which a reinforcing fiber bundle is impregnated with a thermoplastic resin by pressurizing at a pressure of ˜30 kg / cm ² (about 0.5 to 3 MPa) (see Patent Document 1). However, this method requires severe temperatures for impregnation of the thermoplastic resin, so that the properties of the molded product cannot be sufficiently improved to cause thermal decomposition of the resin, and the molded base material is produced economically. It is difficult to manufacture with good quality.

  Among the production methods, the pultrusion method is a continuous pultrusion mold filled with a thermoplastic resin in which reinforcing fibers are melted, impregnated with a thermoplastic resin, and continuously drawn by a tension machine. It is a manufacturing method and has the advantage that a fiber-reinforced composite material can be formed continuously.

  Patent Document 2 proposes a method for producing a tape in which a continuous reinforcing fiber bundle is easily impregnated with a thermoplastic resin. However, in this method, only a thin base material can be manufactured, and in order to increase the thickness, it is necessary to stack the base material, heat and melt the thermoplastic resin, and to mold it. This is difficult, and since the number of moldings is large, the number of times of contact with oxygen increases, and coloring and deterioration due to oxidation may occur.

  As described above, a method for easily and continuously producing a molded article obtained by impregnating a reinforcing fiber with a thermoplastic resin has not been sufficiently proposed.

JP-A-8-118489 JP 2007-118216 A

  In view of the background of the prior art, the present invention is a pultrusion molding impregnated with a thermoplastic resin that has good impregnation into reinforcing fibers, little coloring due to oxidation, and excellent mechanical properties by using a cyclic polymer component. It aims at providing the manufacturing method of goods.

  As a result of intensive studies to achieve the above object, the present inventors have found the following method for producing a pultruded product that can achieve the above-described problems.

(1) When manufacturing a pultruded product by continuously supplying the following component (A) and passing the molten pultrusion mold filled with the following component (B), the following step (I) Followed by step (II) and a continuous production method of a pultruded product.
Component (A) Reinforcing fiber 10 to 90% by weight
Component (B) 90 to 10% by weight of a component containing a compound of the following structural formula (1) (the sum of components (A) and (B) is 100% by weight)

(Here, Ar is aryl, and X is one selected from ether, ketone, sulfide, sulfone, amide, carbonate and ester. M represents an integer of 2 to 50.)
Step (I) Step of supplying component (B) and impregnating component (A) with component (B) by passing component (A) through a mold filled with molten component (B) (II) A step of polymerizing component (B) impregnated in component (A) in the same mold as in step (I)

  The method for producing a pultruded product of the present invention is a pultrusion molding with a thermoplastic resin impregnated with a cyclic polymer component, which has good impregnation into reinforcing fibers, little coloring due to oxidation, and excellent mechanical properties. The product can be manufactured continuously. The pultruded product of the present invention is extremely useful for various parts and members such as electrical / electronic equipment, OA equipment, home appliances, or automobile parts, internal members and housings, civil engineering and building applications.

It is an example of the manufacturing apparatus used for the continuous manufacturing method of the pultruded article which concerns on this invention. It is a figure which shows the example of the shape of the exit side of the pultrusion metal mold | die used for the continuous shaping | molding method of the pultrusion molded article which concerns on this invention.

  The present invention relates to a reinforcing fiber (A) (hereinafter referred to as a component (A), the reinforcing fiber (A) may be referred to as a component (A), a polymerized component (B) (hereinafter referred to as a component to be polymerized) containing a compound of the following structural formula (1) (B) is a method for producing a pultruded product using component (B)) First, these components will be described.

  Although it does not specifically limit as a component (A) reinforced fiber used for this invention, For example, high intensity | strength and high elastic modulus, such as carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, etc. Fibers can be used, and these may be used alone or in combination of two or more. Among these, PAN-based, pitch-based, rayon-based carbon fibers and the like can be mentioned. From the viewpoint of the balance between the strength and elastic modulus of the obtained molded product, PAN-based carbon fibers are more preferable. For the purpose of imparting conductivity, reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be used.

  Further, as the carbon fiber, the surface oxygen concentration ratio [O / C] which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy is 0.05 to What is 0.5 is preferable, More preferably, it is 0.08-0.4, More preferably, it is 0.1-0.3. When the surface oxygen concentration ratio is 0.05 or more, the functional group amount on the surface of the carbon fiber can be secured, and a stronger adhesion to the thermoplastic resin can be obtained. Moreover, although there is no restriction | limiting in particular in the upper limit of surface oxygen concentration ratio, Generally it is preferable to set it as 0.5 or less from the balance of the handleability of carbon fiber, and productivity.

The surface oxygen concentration ratio of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, after cutting the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface with a solvent was cut to 20 mm and spreading and arranging on a copper sample support base, using A1Kα1,2 as the X-ray source, The sample chamber is maintained at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

Here, the surface oxygen concentration ratio is calculated as an atomic number ratio from the ratio of the O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, model ES-200 manufactured by Kokusai Electric Inc. is used, and the sensitivity correction value is set to 1.74.

  The means for controlling the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited. For example, techniques such as electrolytic oxidation, chemical oxidation, and vapor phase oxidation are used. Among these, electrolytic oxidation treatment is preferable.

  The average fiber diameter of the carbon fibers is not particularly limited, but is preferably in the range of 1 to 20 μm and preferably in the range of 3 to 15 μm from the viewpoint of the mechanical properties and surface appearance of the obtained molded product. More preferred. There is no restriction | limiting in particular in the number of single yarns at the time of setting it as a carbon fiber bundle, It can use within the range of 100-350,000, It can be used especially within the range of 1,000-250,000. preferable. Further, from the viewpoint of productivity of carbon fibers, those having a large number of single yarns are preferable, and it is preferable to use them within a range of 20,000 to 100,000.

  In addition, by applying a sizing agent to the carbon fiber, it is possible to improve the adhesion and composite overall characteristics by adapting to the surface characteristics such as functional groups on the surface of the carbon fiber. In addition, it improves bundling, bending resistance, and abrasion resistance, and suppresses the occurrence of fluff and yarn breakage in the high-order processing step. It can also improve the high-order workability as a so-called paste and bundling agent. it can.

  The sizing agent adhesion amount is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, based on the mass of the carbon fiber alone, 0.1% More preferably, it is applied in an amount of from 2% by weight to 2% by weight. If it is 0.01% by mass or less, the effect of improving adhesiveness is hardly exhibited, and if it is 10% by mass or more, the physical properties of the matrix resin may be lowered.

  Examples of the sizing agent include a bisphenol type epoxy compound, a linear low molecular weight epoxy compound, polyethylene glycol, polyurethane, polyester, an emulsifier, or a surfactant. Moreover, these may use together 1 type, or 2 or more types.

  The means for applying the sizing agent is not particularly limited. For example, there are a method of immersing in a sizing liquid through a roller, a method of contacting a roller to which the sizing liquid is adhered, and a method of spraying the sizing liquid in a mist form. . Moreover, although either a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the carbon fiber is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the carbon fiber with ultrasonic waves when applying the sizing agent.

  The drying temperature and drying time should be adjusted according to the amount of the compound attached, but the time required for complete removal of the solvent used to apply the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented and sizing is performed. From the viewpoint of preventing the carbon fiber bundle formed of the treated carbon fibers from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, preferably 180 ° C. More preferably, it is 250 degrees C or less.

  Examples of the solvent used for the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylallylacetamide, and acetone. Water is preferable from the viewpoint of easy handling and disaster prevention. Accordingly, when a compound insoluble or hardly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse in water. Specifically, as an emulsifier and a surfactant, styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, anionic emulsifier such as sodium polyacrylate, Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc. can be used. A nonionic emulsifier having a small size is preferable because it hardly inhibits the adhesive effect of the polyfunctional compound.

  Here, the pultruded product of the present invention is composed of 10 to 90% by mass of the component (A). If it is less than 10% by mass, the mechanical properties of the obtained molded product may be insufficient, and if it exceeds 90% by mass, it may be difficult to impregnate when forming a pultruded product, and voids may remain. Preferably it is 20-80 mass%, More preferably, it is 30-70 mass%.

  The compound of the structural formula (1) used in the present invention has a repeating unit of-(Ar-X)-as a main constituent unit, and preferably contains 80 mol% or more of the repeating unit. The component (B) to be polymerized contains at least 50% by weight of such a compound, preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. Ar includes units represented by the following structural formulas (2) to (10), among which the following formula (2) is preferable. Examples of X include esters, carbonates, amides, ethers, ketones, sulfides, and sulfones, which can be selected according to the characteristics of the resulting composite cured product. For example, esters, carbonates and amides have excellent impact resistance, ethers and ketones have excellent durability and water resistance, and sulfides and sulfones tend to have excellent mechanical properties and flame retardancy.

(R1, R2, R3, and R4 are substituents selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and a halogen group. , R1, R2, R3, and R4 may be the same or different, and R5 is an alkyl chain having 1 to 12 carbon atoms, A is selected from ester, carbonate, amide, ether, ketone, sulfide, and sulfone. 1 type.
In the structural formula (1), different — (Ar—X) — repeating units may be included randomly or in blocks, or they may be mixed. Moreover, the repeating units such as the structural formulas (2) to (10) may be included randomly, may be included in blocks, or may be mixed.

  Representative compounds of the structural formula (1) include cyclic polyphenylene sulfide, cyclic polyphenylene sulfide sulfone, cyclic polyphenylene sulfide ketone, cyclic polyphenylene ether ketone, cyclic polyphenylene ether ether ketone, cyclic polyphenylene ether sulfone, cyclic aromatic polycarbonate, Examples include cyclic polyethylene terephthalate, cyclic polybutylene terephthalate, cyclic random copolymers and cyclic block copolymers containing these. Particularly preferred compounds of the structural formula (1) include cyclic compounds containing 80 mol% or more, particularly 90 mol% or more of the p-phenylene sulfide unit of the following structural formula (11) as the main structural unit.

  Although there is no restriction | limiting in particular in the repeating number m in the said Structural formula (1), 2-50 are preferable, 2-25 are more preferable, and 2-15 can be illustrated as a still more preferable range. As will be described later, the conversion to the polymer (B ′) by heating the component (B) is preferably performed at a temperature equal to or higher than the temperature at which the component (B) melts, but when m increases, the melting temperature of the component (B) is increased. Therefore, it is advantageous to set m in the above range from the viewpoint that the conversion of the component (B) to the polymer (B ′) can be performed at a lower temperature.

  Component (B) may contain either a single compound having a single repeating number or a mixture of cyclic compounds having different repeating numbers as the compound of structural formula (1). The mixture of cyclic compounds having a tendency to have a lower melt solution temperature than a single compound having a single number of repetitions, and the use of a mixture of cyclic compounds having different numbers of repetitions can be applied to the polymer (B ′). This is preferable because the temperature during the conversion can be lowered.

  In addition to the compound of the structural formula (1), the component (B) may contain an oligomer having a repeating unit of-(Ar-X)-as a main structural unit. A linear homo-oligomer or co-oligomer containing 80 mol% or more of the repeating unit is preferable. Ar includes units represented by the structural formulas (2) to (10) described above. As long as the repeating unit of-(Ar-X)-is used as a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following structural formula (12).

The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-X)-units. Further, the oligomer may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Typical examples of these include polyphenylene sulfide oligomer, polyphenylene sulfide sulfone oligomer, polyphenylene sulfide ketone oligomer, polyphenylene ether ketone oligomer, polyphenylene ether ether ketone oligomer, polyphenylene ether sulfone oligomer, aromatic polycarbonate oligomer, polyethylene terephthalate oligomer, polybutylene terephthalate. Examples include oligomers, random copolymers thereof, block copolymers, and mixtures thereof. Particularly preferred oligomers include polyphenylene sulfide oligomers containing 80 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units as the main structural unit of the polymer.

  The molecular weight of the oligomer is preferably less than 10,000 in terms of weight average molecular weight. More preferably, it is less than 8,000, and more preferably less than 5,000. On the other hand, the lower limit is preferably 300 or more, preferably 400 or more, and more preferably 500 or more in terms of weight average molecular weight.

  When the component (B) contains the oligomer, the amount of the oligomer is particularly preferably smaller than the compound of the structural formula (1). That is, the weight ratio of the compound of the structural formula (1) to the oligomer in the component (B) (the structural formula (1) / the oligomer) is preferably more than 1, more preferably 2.3 or more, and more than 4 Is more preferable, and 9 or more is even more preferable. By using such a component (B), it is possible to easily obtain a polymer (B ′) having a weight average molecular weight of 10,000 or more.

  Here, the component (B) used by this invention is comprised from 15-99 mass%, It is characterized by the above-mentioned. By using the component (B) in the range of 15 to 99% by mass, a pultruded product having excellent impregnation and no voids can be obtained. Preferably it is 20-90 mass%, More preferably, it is 25-70 mass%.

  The polymer (B ′) obtained by using the component (B) is a homopolymer having a repeating unit of — (Ar—X) — as a main constituent unit, preferably containing 80 mol% or more of the repeating unit. Or a copolymer. Ar includes units represented by the above structural formulas (2) to (10), among which the structural formula (2) is particularly preferable. Examples of X include esters, carbonates, amides, ethers, ketones, sulfides, and sulfones, which can be selected according to the characteristics of the resulting composite cured product. For example, esters, carbonates and amides have excellent impact resistance, ethers and ketones have excellent durability and water resistance, and sulfides and sulfones tend to have excellent mechanical properties and flame retardancy.

  As long as this repeating unit is a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the structural formula (12). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-X)-units.

  In addition, the polymer (B ′) in the present invention may be any of a random copolymer containing the above repeating unit, a block copolymer, and a mixture thereof.

  Typical examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene ether ketone, polyphenylene ether ether ketone, polyphenylene ether sulfone, aromatic polycarbonate, polyethylene terephthalate, polybutylene terephthalate, random copolymers of these, and blocks Examples thereof include copolymers and mixtures thereof. Particularly preferably, as the main structural unit of the polymer, polyphenylene sulfide containing 80 mol% or more, particularly 90 mol% or more of the p-phenylene sulfide unit of the structural formula (11) may be mentioned.

  The preferred molecular weight of the polymer (B ′) is 10,000 or more, preferably 15,000 or more, more preferably 17,000 or more in terms of weight average molecular weight. When the weight average molecular weight is 10,000 or more, properties such as toughness and flame retardancy of the composite cured product become high.

  Further, when the component (B) is converted into the polymer (B ′), the conversion is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. When the conversion rate is 70% or more, a polymer (B ′) having the above-mentioned characteristics can be obtained.

  In addition, the component (B) is polymerized by heating to obtain a polymer (B ′), but the reaction may be promoted by using a compound having a radical generating ability as a polymerization catalyst. As such a polymerization catalyst, a zero-valent transition metal compound or the like is preferable, and a polymer (B ′) can be easily obtained by heating the component (B) in the presence of a zero-valent transition metal compound.

  As the zero-valent transition metal, metals of Group 8 to Group 11 and Period 4 to Period 6 of the periodic table are preferably used. For example, nickel, palladium, platinum, iron, ruthenium, rhodium, copper, silver, and gold can be exemplified as the metal species. Various complexes are suitable as the zero-valent transition metal compound. For example, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 1'-bis (diphenylphosphino) ferrocene, dibenzylideneacetone, dimethoxydibenzylideneacetone, cyclooctadiene, and carbonyl complexes. Specifically, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (tri-t-butylphosphine) palladium, bis [1,2-bis (diphenylphosphine) Fino) ethane] palladium, bis (tricyclohexylphosphine) palladium, [P, P′-1,3-bis (di-i-propylphosphino) propane] [P-1,3-bis (di-i-propyl) Phosphino) propane] palladium, 1,3-bis (2,6-di-i-propylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, 1,3-bis (2,4 , 6-Trimethylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, bi (3,5,3 ′, 5′-dimethoxydibenzylideneacetone) palladium, bis (tri-t-butylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (trifluorophosphine) platinum, ethylenebis (tri Phenylphosphine) platinum, platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, Examples thereof include bis (1,5-cyclooctadiene) nickel, dodecacarbonyl triiron, pentacarbonyl iron, dodecacarbonyl tetrarhodium, hexadecacarbonyl hexarhodium, dodecacarbonyl triruthenium and the like. These polymerization catalysts may be used alone or in combination of two or more.

  These polymerization catalysts may be added with a zero-valent transition metal compound as described above, or may form a zero-valent transition metal compound in the system. Here, in order to form a zero-valent transition metal compound in the system as in the latter case, a transition metal compound such as a transition metal salt and a ligand compound are added to form a transition metal complex in the system. And a method of adding a complex formed of a transition metal compound such as a transition metal salt and a compound serving as a ligand. Since transition metal salts other than zero valence do not promote the conversion of component (A), it is necessary to add a compound serving as a ligand. Examples of transition metal compounds and ligands used in the present invention and complexes formed of transition metal compounds and ligands are given below. Examples of the transition metal compound for forming a zero-valent transition metal compound in the system include acetates and halides of various transition metals. Examples of the transition metal species include nickel, palladium, platinum, iron, ruthenium, rhodium, copper, silver, gold acetate, halide and the like. Specifically, nickel acetate, nickel chloride, nickel bromide. , Nickel iodide, nickel sulfide, palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium sulfide, platinum chloride, platinum bromide, iron acetate, iron chloride, iron bromide, iron iodide, ruthenium acetate, chloride Examples include ruthenium, ruthenium bromide, rhodium acetate, rhodium chloride, rhodium bromide, copper acetate, copper chloride, copper bromide, silver acetate, silver chloride, silver bromide, gold acetate, gold chloride, and gold bromide. Moreover, as a ligand added simultaneously in order to form a zerovalent transition metal compound in a system, if a component (A) and a transition metal compound are heated and a zerovalent transition metal is produced | generated, Although there is no particular limitation, basic compounds are preferable, for example, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino). ) Ferrocene, dibenzylideneacetone, sodium carbonate, ethylenediamine and the like. Moreover, as a complex formed with the compound used as a transition metal compound and a ligand, the complex which consists of the above various transition metal salts and a ligand is mentioned. Specifically, bis (triphenylphosphine) palladium diacetate, bis (triphenylphosphine) palladium dichloride, [1,2-bis (diphenylphosphino) ethane] palladium dichloride, [1,1′-bis (diphenylphosphine) Fino) ferrocene] palladium dichloride, dichloro (1,5′-cyclooctadiene) palladium, bis (ethylenediamine) palladium dichloride, bis (triphenylphosphine) nickel dichloride, [1,2-bis (diphenylphosphino) ethane] nickel Examples include dichloride, [1,1′-bis (diphenylphosphino) ferrocene] nickel dichloride, dichloro (1,5′-cyclooctadiene) platinum and the like. These polymerization catalysts and ligands may be used alone or in combination of two or more.

  The valence state of the transition metal compound can be grasped by X-ray absorption fine structure (XAFS) analysis. The transition metal compound used as a catalyst in the present invention or a mixture of the transition metal compound and the component (B) or a mixture of the transition metal compound and the polymer (B ′) is irradiated with X-rays, and the absorption spectrum is normalized. This can be grasped by comparing the peak maximum values of the absorption coefficient.

  For example, when evaluating the valence of a palladium compound, it is effective to compare the absorption spectrum of the L3 end X-ray absorption near edge structure (XANES), and the X-ray energy is 3173 eV as a reference, 3163 to 3168 eV. This can be determined by comparing the peak maximum value of the absorption coefficient when the average absorption coefficient in the range of 0 and 3191 to 3200 eV is normalized to 1. In the example of palladium, the peak value of the absorption coefficient when normalized with the zero-valent palladium compound tends to be small compared to the divalent palladium compound, and further promotes the conversion of the cyclic polyarylene sulfide. A transition metal compound having a larger effect tends to have a smaller peak maximum value. The reason for this is presumed that the absorption spectrum for XANES corresponds to the transition of core electrons to empty orbitals, and the absorption peak intensity is affected by the electron density of d orbitals.

  In order for the palladium compound to promote the conversion of the component (B) to the polymer (B ′), the peak maximum value of the absorption coefficient when normalized is preferably 6 or less, more preferably 4 or less, More preferably, it is 3 or less, and conversion of a component (B) can be accelerated | stimulated within this range.

  Specifically, the peak maximum value is 6.32 for divalent palladium chloride that does not promote conversion of component (B), zero-valent tris (dibenzylideneacetone) dipalladium that promotes conversion of component (B), and Tetrakis (triphenylphosphine) palladium and bis [1,2-bis (diphenylphosphino) ethane] palladium are 3.43, 2.99 and 2.07, respectively.

  The concentration of the polymerization catalyst used varies depending on the molecular weight of the target polymer (B ′) and the type of the polymerization catalyst, but is usually 0.001 to 20 mol% with respect to X in the component (B), preferably It is 0.005-15 mol%, More preferably, it is 0.01-10 mol%. If it is 0.001 mol% or more, the component (B) is sufficiently converted to the polymer (B ′), and if it is 20 mol% or less, the polymer (B ′) having the above-mentioned characteristics can be obtained.

  The polymerization catalyst may be added as it is, but it is preferable to add the polymerization catalyst to the component (B) and then disperse it uniformly. Examples of the uniform dispersion method include a mechanical dispersion method and a dispersion method using a solvent. Specific examples of the mechanical dispersion method include a pulverizer, a stirrer, a mixer, a shaker, and a method using a mortar. Specific examples of the method of dispersing using a solvent include a method of dissolving or dispersing component (B) in an appropriate solvent, adding a predetermined amount of a polymerization catalyst thereto, and then removing the solvent. In addition, when the polymerization catalyst is dispersed, when the polymerization catalyst is a solid, it is preferable that the average particle size of the polymerization catalyst is 1 mm or less because more uniform dispersion is possible.

  Here, the pultruded product of the present invention is composed of 90 to 10% by mass of the polymer (B ′). If it exceeds 90% by mass, the resulting molded article may have insufficient mechanical properties, and if it is less than 10% by mass, it may be difficult to impregnate when forming a pultruded product, and voids may remain. Preferably it is 80-20 mass%, More preferably, it is 30-70 mass%.

Next, the method for producing a pultruded product of the present invention includes at least the following steps.
Step (I) Step of supplying component (B) and impregnating component (A) with component (B) by passing component (A) through a mold filled with molten component (B) (II) A step of polymerizing the component (B) impregnated in the component (A) in the same mold as in the step (I).

  Each step will be described.

In the step (I), the component (B) is supplied to the mold, and the component (A) is passed through the mold filled with the melted component (B), so that the component (B) is added to the component (A). Is a step of impregnating.
As a method for supplying the component (B), a known device such as an extruder, a plunger, or a melting bath can be used, but a device having a function of transferring the molten component (B) such as a screw or a gear pump. Is preferred.

  For example, by melting the component (B) using an extruder and supplying it into the mold, and passing the component (A) while squeezing it in the mold filled with the melted component (B). The method of impregnation can be illustrated.

  In addition, the mold temperature for impregnating the component (A) with the component (B) is only required to melt the component (B), but is preferably 100 to 350 ° C. More preferably, it includes a step of heating to 150 to 300 ° C, more preferably 170 to 280 ° C. Above 350 ° C., component (B) decomposes and volatilizes, so voids may remain inside the pultruded product. Moreover, since it polymerizes and becomes high molecular weight, impregnation becomes difficult and impregnation may become inadequate. Below 100 ° C., component (B) does not melt, or even when melted, the viscosity is high and impregnation may be insufficient. By impregnating at 100 to 350 ° C., a pultruded product free from voids can be obtained.

  Moreover, it is more preferable to open the component (A) in advance in the previous stage. Opening is an operation of separating the converged component (A), and an effect of further enhancing the impregnation property of the component (B) can be expected. With the opening, the thickness of the component (A) is reduced, the width of the component (A) before opening is b1 (mm), the thickness is a1 (μm), and the width of the component (A) after opening is b2 ( mm) and a thickness of a2 (μm), the spread ratio = (b2 / a2) / (b1 / a1) is preferably 2.0 or more, and more preferably 2.5 or more.

  The method for opening component (A) is not particularly limited. For example, a method in which concavo-convex rolls are alternately passed, a method in which drum rolls are used, a method in which tension variation is applied to axial vibration, and a reciprocating motion in the vertical direction 2 A method of changing the tension of the component (A) by the individual friction bodies and a method of blowing air to the component (A) can be used.

  In addition, it is important to supply the component (A) continuously to the production line for the purpose of producing with good economic efficiency and productivity. The term “continuous” means that the raw material component (A) is supplied without being completely cut, and the supply speed may be constant or supply and stop may be repeated intermittently.

  Also included is the purpose of extracting the component (A) and arranging it in a predetermined arrangement. That is, the continuous component (A) to be supplied may be in the form of a yarn, in the form of a sheet aligned in one direction, or in the form of a preform that has been pre-shaped. Specifically, the component (A) is creeled, the fiber bundle is drawn out, passed through a roller and supplied to the production line, and similarly, a plurality of fiber bundles are arranged in a row and leveled into a sheet, Examples thereof include a method of supplying a production line through a roll bar, and a method of supplying a production line by passing a plurality of roll bars arranged to have a predetermined shape. Furthermore, when the component (A) is processed into a base material, it may be directly supplied to the production line from a folded state or the like. In addition, if a drive device is provided in various rollers and a roll bar, adjustment of a supply speed etc. can be performed and it is more preferable on production.

  Furthermore, you may include the process heated to 50-500 degreeC in the step before supplying a component (A) to a metal mold | die. By heating component (A), the impregnation property of component (B) into component (A) can be improved in step (I). Moreover, the sizing agent etc. which have adhered to the component (A) can also be removed. The heating method is not particularly limited, and examples thereof include known methods such as non-contact heating using hot air or an infrared heater, contact heating using a pipe heater or electromagnetic induction, and the like.

  Further, the different component (A) can be arranged at an arbitrary position in the cross-section of the pultruded product, for example, a glass fiber may be arranged in the outermost layer of the cross-section of the molded product, and a carbon fiber may be arranged in the center layer. it can. When supplying to the pultrusion mold, the reinforcing fibers may be guided in the order of arrangement in the yarn path guide. Moreover, even if it guides so that arrangement | positioning of a reinforced fiber may not change in a metal mold | die, it can be set as the cross section which arrange | positioned the reinforced fiber arbitrarily.

  In the subsequent step (II), the component (B) impregnated in the component (A) obtained in the step (I) is polymerized by heating to be converted into a polymer (B ′). . It is important that the component (B) is subjected to ring-opening polymerization to form a polymer (B ′) by the heating. The mold temperature at this time is 200-450 degreeC, Preferably it is 230-420 degreeC, More preferably, it is 250 degreeC-400 degreeC, More preferably, it is 280-380 degreeC. If it is less than 200 degreeC, ring-opening polymerization may not fully advance, but it may contain a low molecular-weight component (B) excessively, and may become a pultrusion molded article inferior to mechanical strength. Moreover, when it exceeds 450 degreeC, an undesirable side reaction, such as causing a decomposition reaction of the component (B) and the polymer (B ′), may occur.

  Here, it is important to perform the step (II) with the same pultrusion mold following the step (I). By performing two steps with one pultrusion mold, not only is it excellent in productivity and economy, but the number of times of heating and melting of the component (B) can be reduced by one, so the component (B) is oxidized. This is preferable because coloring, crosslinking reaction, and decomposition reaction can be suppressed.

  The shorter the reaction time until the ring-opening polymerization in the step (II) is completed, the shorter the process length or the higher the take-up speed. preferable. The reaction time is preferably 30 minutes or less, more preferably 10 minutes or less, and even more preferably 3 minutes or less. There is no restriction | limiting in particular about the minimum of reaction time, 0.5 minutes or more can be illustrated.

  Further, in the steps (I) and (II), it is preferable to heat in a non-oxidizing atmosphere from the viewpoint of suppressing the occurrence of undesirable side reactions such as crosslinking reaction and decomposition reaction. Here, the non-oxidizing atmosphere is an atmosphere having an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas atmosphere such as nitrogen, helium or argon. Of these, a nitrogen atmosphere is particularly preferred from the standpoints of economy and ease of handling.

  Similarly, it is preferable to heat under a reduced pressure of 0.1 to 50 kPa. Here, it is more preferable that the atmosphere in the reaction system is once changed to a non-oxidizing atmosphere and then adjusted to a reduced pressure condition. Here, “under reduced pressure” means that the inside of the reaction system is lower than atmospheric pressure, more preferably 0.1 to 20 kPa, and further preferably 0.1 to 10 kPa.

  Specifically, the component (A) is drawn into the pultrusion mold while nitrogen is blown into the system substituted with nitrogen, and the pressure is reduced using a vacuum pump from the vent portion installed in the pultrusion mold. A method of molding can be exemplified.

  Further, as the step (III), the component (B) obtained in the step (I) or (II) or the component (A) impregnated with the polymer (B ′) is shaped into a specific cross-sectional shape. It is a process to do. The cross-sectional shape is not particularly limited, but any cross-section such as a circular cross-section, a Δ cross-section, a Y-shaped cross-section, a □ cross-section, a cross-section, a hollow cross-section, a C-shaped cross-section, a rice-shaped cross-section, or a star-shaped cross-section Can be adopted. In particular, a circular cross section or a square cross section is preferable for maintaining strength during winding. As a method of shaping, the exit portion of the pultrusion mold may be formed into the shape, and more preferably, the shape is tapered from the step (II) toward the exit direction of the pultrusion mold. It is preferable to shape. The taper angle is preferably as small as possible, preferably 60 degrees or less, more preferably 45 degrees or less, and even more preferably 30 degrees or less. When it is larger than 60 degrees, the component (A) is easily rubbed and fluff may be generated.

  Further, the thickness of the obtained pultruded product may be set to an arbitrary thickness, but by using the production method of the present invention, even a thick pultruded product can be produced with less voids. , Preferably, it is 0.4-50 mm, More preferably, it is 1-25 mm, More preferably, it is 2-15 mm. If it is 0.4 mm or less, the strength may be insufficient when used alone, and if it exceeds 50 mm, voids may remain inside the pultruded product.

  Further, following the step (II) or (III), the obtained pultruded product is cooled. The cooling method is not particularly limited, but a method of contacting a roller equipped with a cooling device, a method of cooling by jetting air, a method of spraying cooling water, a method of passing through a cooling bath, A known method such as a method of passing over a plate can be used. Among them, a method of contacting a roller equipped with a cooling device and a method of passing a cooling bath are preferable, and a method of cooling a pultruded product by a roller equipped with a cooling device is particularly preferable. Since it can sometimes pressurize, since the cross-sectional shape of a pultruded product can be manufactured stably, it is preferable.

  Specific examples of the drawing method include a drawing method using a nip roller or a belt conveyor, a winding method using a drum winder, and a method of holding the substrate with a fixing jig and drawing the jig together. Moreover, when pulling out, it may be processed into a predetermined length by a guillotine cutter or the like, or may be a continuous molded product.

  Further, the longer the continuous molding time is, the better the productivity and the economical efficiency are. As continuous molding time, it is 30 minutes or more, Preferably, it is 1 hour or more, More preferably, it is 3 hours or more, More preferably, it is 6 hours or more.

  In addition, the manufacturing method of the pultruded product in this invention can combine another process in the range which does not impair the effect. For example, an electron beam irradiation process, a plasma treatment process, a strong magnetic field application process, a skin material laminating process, a protective film attaching process, an after-cure process, and the like can be given.

  In the pultruded product obtained by the production method of the present invention, the weight ratio of the component (A) and the polymer (B ′) is preferably 10 to 90:90 to 10% by weight, more preferably, from the mechanical properties of the molded product. Is 20 to 80:80 to 20% by weight, more preferably 30 to 70:70 to 30% by weight. These weight ratios can be implemented by controlling the supply amount of the component (A) and the dimensions of the pultrusion mold outlet.

Moreover, the void ratio of the pultruded product obtained by the production method of the present invention is preferably as low as possible, and is preferably less than 30% because mechanical properties are easily exhibited. A more preferable void ratio range is less than 20%, and even more preferably less than 10%. The void ratio is determined by measuring the composite part by the ASTM D2734 (1997) test method, or observing voids present in the cross section of the molding material, and calculating the following formula from the total area of the molding material and the total area of the void portion. Can be used to calculate.
Void ratio (%) = total area of void part / (total area of composite part + total area of void part) × 100.

  As a method for controlling the void ratio, the temperature and pressure when impregnating the component (B) in the step (I), and the conversion of the component (B) in the step (II) into the polymer (B ′) It can be adjusted by the temperature and pressure. Usually, the higher the temperature and the applied pressure, the lower the void ratio.

  The pultruded product obtained by the present invention is excellent in heat resistance, chemical resistance, mechanical properties, and flame retardancy, and can be developed for various uses.

  EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to the description of these examples.

(1) Determination of coloring by oxidation The color of the thermoplastic resin on the surface of the molded product was determined visually.

(2) Porosity measurement of molded product The porosity (%) of the molded product was calculated in accordance with ASTM D2734 (1997) test method.

Judgment of the porosity of the composite cured product was performed according to the following criteria, and A to C were regarded as acceptable.
A: 0 to less than 10% B: 10% to less than 20% C: 20% to less than 40% D: 40% or more.

Reference Example 1 (Preparation of cyclic polyphenylene sulfide (B) -1)
A stainless steel autoclave equipped with a stirrer was charged with 14.03 g (0.120 mol) of a 48 wt% aqueous solution of sodium hydrosulfide and 12.50 g (0.144 mol) of a 48 wt% aqueous solution prepared using 96% sodium hydroxide. ), 615.0 g (6.20 mol) of N-methyl-2-pyrrolidone (NMP), and 18.08 g (0.123 mol) of p-dichlorobenzene (p-DCB). The reaction vessel was sufficiently purged with nitrogen, and then sealed under nitrogen gas.

  While stirring at 400 rpm, the temperature was raised from room temperature to 200 ° C. over about 1 hour. At this stage, the pressure in the reaction vessel was 0.35 MPa as a gauge pressure. Next, the temperature was raised from 200 ° C. to 270 ° C. over about 30 minutes. The pressure in the reaction vessel at this stage was 1.05 MPa as a gauge pressure. After maintaining at 270 ° C. for 1 hour, the contents were recovered after quenching to near room temperature.

  The content obtained was analyzed by gas chromatography and high performance liquid chromatography. As a result, the consumption rate of monomer p-DCB was 93%, and the sulfur content in the reaction mixture was assumed to be all converted to cyclic PPS. The formula PPS production rate was found to be 18.5%.

  500 g of the obtained contents were diluted with about 1500 g of ion-exchanged water, and then filtered through a glass filter having an average opening of 10 to 16 μm. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and filtered again in the same manner three times to obtain a white solid. This was vacuum dried at 80 ° C. overnight to obtain a dry solid.

  The obtained solid was charged into a cylindrical filter paper, and Soxhlet extraction was performed for about 5 hours using chloroform as a solvent to separate low molecular weight components contained in the solid.

  The solid component remaining in the cylindrical filter paper after the extraction operation was dried under reduced pressure at 70 ° C. overnight to obtain about 6.98 g of an off-white solid. As a result of analysis, this was a compound having a phenylene sulfide structure, and the weight average molecular weight was 6,300, from the absorption spectrum in infrared spectroscopic analysis.

  After removing the solvent from the extract obtained by the chloroform extraction operation, about 5 g of chloroform was added to prepare a slurry, which was added dropwise to about 300 g of methanol with stirring. The precipitate thus obtained was collected by filtration and vacuum dried at 70 ° C. for 5 hours to obtain 1.19 g of a white powder. This white powder was confirmed to be a compound composed of phenylene sulfide units from an absorption spectrum in infrared spectroscopic analysis. Moreover, this white powder has p-phenylene sulfide unit as the main constituent unit based on the mass spectrum analysis of the component divided by high performance liquid chromatography (apparatus; M-1200H manufactured by Hitachi) and molecular weight information by MALDI-TOF-MS. It was found that the compound contains about 99% by weight of a cyclic compound having 4 to 13 repeating units and is preferably used in the present invention. As a result of GPC measurement, (B) -1 was completely dissolved in 1-chloronaphthalene at room temperature, and the weight average molecular weight was 900.

Example 1
The continuous manufacturing method of a pultruded product is demonstrated using the apparatus shown in FIG.
The pultrusion mold 3 was supplied with the component (B) -1 obtained in Reference Example 1 from the resin supply port 6 and filled with the molten component (B) -1. Moreover, the set temperature of the thermocouple installed in the intermediate part from the pultrusion mold inlet 14 to the center of the pultrusion mold 3 was set to 250 ° C. (Hereafter, the part from the pultrusion mold inlet 14 to the center of the pultrusion mold 3 is referred to as zone 1.) Setting of the thermocouple installed in the intermediate part from the center of the pultrusion mold 3 to the pultrusion mold outlet 15 The temperature was 370 ° C. (Hereinafter, the portion from the pultrusion mold inlet 15 to the center of the pultrusion mold 3 is referred to as zone 2).
Step (I): A plurality of carbon fiber trading cards (registered trademark) T700S-12K (manufactured by Toray Industries, Inc.) are aligned from the reinforcing fiber bobbin 1 so that the distance between the fiber bundles is 1 to 5 mm, and provided to the production line. Then, the fiber bundle was applied to the roll bar 2 for leveling and supplied from the pultrusion mold inlet 3 of the pultrusion mold 3. At this time, in the zone 1, the component (B) -1 was impregnated without voids inside the reinforcing fiber by being immersed in the component (B) -1 melted at 250 ° C. while touching the impregnation roll 5.

  Step (II): The reinforcing fiber impregnated with component (B) -1 obtained in step (I) is drawn into zone 2 heated to 370 ° C., so that impregnated component (B) -1 is polymer (B ') -1 to obtain a molded product.

  Step (III): The pultrusion mold outlet 15 is designed in a circular shape as shown in FIG. 2, and the molded product obtained in the step (II) is pulled out, so that the pultruded product is simultaneously formed with the step (II). Shaped in a circle.

  Step (IV): The pultruded product drawn from the pultrusion mold outlet 15 is solidified on the cooling roller 7 having a temperature of 150 ° C., and the polymer (B ′)-1 is solidified and drawn by the belt conveyor 10 for drawing. The continuous pultruded product 13 was taken up by the winder 12 while being taken up by the nip roller 11 to obtain a pultruded product.

  The above processes were all performed online, and pultruded products could be manufactured continuously. The drawing speed was 10 m / min. The resin of the obtained pultruded product was not oxidized and was light brown. The impregnation rate was 95%, and it was a very rigid pultruded product. When the matrix resin was extracted from the pultruded product, the polymer (B ′)-1 had a weight average molecular weight of 42,000. The content of component (A) was 15% by mass, and the thickness of the pultruded product was 2 mm. In addition, it confirmed that it can shape | mold continuously for 2 hours and can produce stably.

Example 2
A pultruded product was obtained in the same manner as in Example 1 except that the content of the component (A) was adjusted to 50% by mass and the shape of the pultrusion mold outlet 15 was changed to an ellipse. The characteristic evaluation results are collectively shown in Table 1.

Example 3
A pultruded product was obtained in the same manner as in Example 1 except that the content of the component (A) was adjusted to 85% by mass and the shape of the pultrusion mold outlet 15 was changed to the star shape shown in FIG. . The characteristic evaluation results are collectively shown in Table 1.

Example 4
A pultruded product was prepared in the same manner as in Example 1 except that the content of the component (A) was adjusted to 50% by mass, the set temperature of the zone 1 was 300 ° C., and the set temperature of the zone 2 was 400 ° C. Obtained. The characteristic evaluation results are collectively shown in Table 1.

Example 5
A pultruded product was obtained in the same manner as in Example 4 except that the preset temperature of zone 1 was 200 ° C. and the preset temperature of zone 2 was 300 ° C. The characteristic evaluation results are collectively shown in Table 1.

Example 6
A pultruded product was obtained in the same manner as in Example 1 except that the content of the component (A) was 50% by mass and the step (IV) was omitted. The characteristic evaluation results are collectively shown in Table 1.

Example 7
Except that the content of the component (A) was 50% by mass, the steps (III) and (IV) were not performed, and the pultruded product was shaped into a quadrangle with the cooling roller 7, the same as in Example 1. A pultruded molded product was obtained. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 1
A pultruded product was obtained in the same manner as in Example 1, except that (Toray Industries, Ltd., polyphenylene sulfide resin, M2588) was used instead of Component (B) -1. The characteristic evaluation results are collectively shown in Table 2.

Comparative Example 2
A pultruded product was obtained in the same manner as in Example 1, except that the content of the component (A) was 50% by mass, and steps (II) to (IV) were not performed. Further, the obtained pultruded product was brought into contact with a roll heated to 370 ° C., thereby converting the component (B) -1 into the polymer (B ′)-1. The characteristic evaluation results are collectively shown in Table 2. In addition, when continuous molding was continued for 10 minutes, the component (A) was wound around the heating roll, so that it could not be taken out and continuous molding was impossible.

  As described above, in Examples 1 to 7, the pultruded molded product according to the present invention was excellent in impregnation property, was not colored by oxidation, and a molded product excellent in mechanical properties could be obtained.

  On the other hand, in the comparative example, there was insufficient impregnation of the pultruded product and coloring due to oxidation, and no pultruded product having excellent mechanical properties was obtained.

  The method for producing a pultruded product of the present invention is a pultrusion molding with a thermoplastic resin impregnated with a cyclic polymer component, which has good impregnation into reinforcing fibers, little coloring due to oxidation, and excellent mechanical properties. The product can be manufactured continuously. The pultruded product of the present invention is extremely useful for various parts and members such as electrical / electronic equipment, OA equipment, home appliances, automobile parts, internal members and housings, civil engineering and building applications.

DESCRIPTION OF SYMBOLS 1 Reinforcing fiber bobbin 2 Roll bar 3 Drawing mold 4 Molten resin 5 Impregnation roller 6 Resin supply port 7 Cooling roller 8 Supply port 9 Chamber 10 Pulling belt conveyor 11 Nip roller 12 Winding winder 13 Continuous drawing product 14 Drawing Mold entrance 15 Pull-out mold exit

Claims (8)

When manufacturing a pultruded product by continuously supplying the following component (A) and passing it through a pultrusion mold filled with the melted following component (B), the following step (I) is followed by a step A continuous production method of a pultruded product characterized by performing (II).
Component (A) Reinforcing fiber 10 to 90% by weight
Component (B) 90 to 10% by weight of a component containing a compound of the following structural formula (1) (the sum of components (A) and (B) is 100% by weight)

(Here, Ar is aryl, and X is one selected from ether, ketone, sulfide, sulfone, amide, carbonate and ester. M represents an integer of 2 to 50.)
Step (I) Step of supplying component (B) and impregnating component (A) with component (B) by passing component (A) through a mold filled with molten component (B) (II) A step of polymerizing component (B) impregnated in component (A) in the same mold as in step (I) The continuous manufacturing method of the pultruded article of Claim 1 which performs the following process (III) following process (I) or process (II).
Step (III) Step of forming a specific cross-sectional shape in the same mold as in step (I) The method for continuously producing a pultruded product according to claim 2, wherein the cross-sectional shape is any one of a circle, an ellipse, and a star. Following step (II) or step (III), the molded product is roller-cooled or water-cooled so that the temperature difference between the surface temperature of the molded product drawn from the pultrusion mold and the pultrusion mold temperature is 50 ° C. or less. The continuous manufacturing method of the pultruded article in any one of Claims 1-3 cooled by this. The thickness of a pultruded product is 0.4-50 mm, The continuous manufacturing method of the pultruded product in any one of Claims 1-4. The continuous manufacturing method of the pultruded article in any one of Claims 1-5 whose mold temperature of process (I) is 200-350 degreeC. The method for producing a pultruded product according to any one of claims 1 to 6, wherein the mold temperature in step (II) is 250 to 450 ° C. The method for producing a pultruded product according to any one of claims 1 to 7, wherein glass fibers are arranged as a component (A) on the outermost periphery in the cross section of the pultruded product.

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