MXPA98005442A - Molding material and process for preparing the same - Google Patents

Abstract

A molding material which is easy to prepare and in which reinforcing fiber bundles are well dispersible in the step of, e.g., injection molding;a process for preparing the same;a polyamide resin composition having a good fluidity, and moldings prepared therefrom. The molding material is characterized by comprising at least the following constituent elements (A), (B), and (C), the constituent element (C) being arranged so as to be in contact with a composite composed of the constituent elements (A) and (B):(A) a continuous reinforcing fiber bundle;(B) a thermoplastic polymer having a weight-average molecular weight of 200 to 50,000 and a lower melt viscosity than the constituent feature (C);and (C) a thermoplastic resin having a weight-average molecular weight of not less than 10,000.

Description

MOLDING MATERIAL AND A PROCESS FOR THE PRODUCTION OF SAME TECHNICAL FIELD The present invention relates to a thermoplastic resin material reinforced with long fiber. In more detail, the present invention relates to a molding material k that can be easily produced and allows a bundle of reinforcing fiber to is well dispersed in a molded product obtained by molding, such as injection molding and also to a production process thereof, a resin composition with good flowability and molded products obtained therefrom.

ART BACKGROUND 15 Fiber reinforced composite materials obtained using a continuous reinforcing fiber bundle or relatively long discontinuous reinforcing fibers as reinforcing fibers and a thermoplastic resin as a matrix are publicly known. Composite materials have aspects such as high tenacity, easy capacity of recycling and short molding cycle because of the applicability of molding, injection molding and stamping methods, but which have not been widely used in this way. The reasons are as described below. It is well known that the impregnation of a resin cast in a fiber bundle is more difficult when the viscosity of resin melting is superior. A thermoplastic resin excellent in properties or molecular and a very high melt viscosity. A fiber-reinforced composite material with such a high molecular thermoplastic resin as the matrix has problems that productivity is low and that the production cost is very high, since it is difficult to impregnate a fiber bundle with a thermoplastic resin. On the other hand, the use of a thermoplastic resin with a low molecular weight (low viscosity), allows easy impregnation since the matrix greatly reduces the mechanical properties of the composite material, and therefore can not be a solution to the problem. According to a method for impregnating a continuous fiber bundle with a highly viscous thermoplastic resin, for example, extrusion is generally adopted by stretching in which the fiber bundle is immersed, opened and rubbed into a molten resin, with a Pressure applied to the resin for mechanical impregnation. In such a method for impregnation with a resin with a high viscosity, that is, exceeding 500 poises, the fiber bundle must be introduced at a very low speed of 10 meters per minute or less. Various methods of mechanical impregnation are known but these can not fundamentally solve the problem of impregnation, and do not allow an admission speed of more than 10 meters per minute. Other proposed impregnation methods include the following, a The solution in which a thermoplastic resin is diluted by a solvent, to be reduced in viscosity, is impregnated in a continuous fiber bundle, and the solvent is removed in the subsequent stage. An emulsion or dispersion of thermoplastic resin is impregnated in a continuous fiber bundle, and the medium is removed. A powder of thermoplastic resin is placed in a bundle of fiber in a flatulent bed, and heated to be melted for impregnation.

However, this can be generally judged that these methods are low in productivity. On the other hand, methods to improve the problem of impregnability by modifying the fiber surfaces are also proposed. This is intended to improve the wetting capacity between the fibers and a thermoplastic resin at the time of impregnation of the resin, by modifying the surfaces of the fibers by means of a gluing or coupling agent, etc. According to one of these methods, Japanese Patent Laid-Open No. 61-236832 discloses that a composite material with improved mechanical properties can # obtained by allowing a second thermoplastic polymer to exist between a polymer standard thermoplastic and fibers, to improve its wettability. However, this gazette does not establish the specific amount of the second thermoplastic polymer that exists between the standard polymer and the fibers, and does not clarify the effect of promoting the impregnation, although it is established that the mechanical properties can be improved when a thermoplastic polymer is impregnated with low wettability Also, even when viscosity is concerned The melting of the second thermoplastic polymer specific scales of molecular weights and melt viscosities of the second thermoplastic polymer are not specified and it can not be known if the productivity of the material can be really improved. Moreover, although this method can improve the wettability between the fiber bundle and the matrix, this is not established completely if the method is intended to improve the dispersion capacity of the fiber. the reinforcing fibers in the molded product. It is also attempted to achieve the molding, the impregnation of a thermoplastic resin in a bundle of reinforcing fiber and the dispersion of the fibers simultaneously in the molding step towards a shape of the final product, to elevate the productivity of a composite material. thermoplastic in the total process that varies from the preparation of the material until the molding. When a thermoplastic molding material is molded, a relatively high temperature and pressure is again applied. For example, in the case of injection molding, the molding material is heated in a cylinder in a plasticizing step, and kneaded and pressurized by a screw. Also in pressure molding, a high temperature and pressure are similarly applied. This provides a relatively favorable condition for impregnating a fiber bundle with a thermoplastic resin and the idea of supplying a reinforcing fiber bundle and a high molecular weight thermoplastic resin destined to be a matrix, in molding machines respectively, to achieve impregnation, dispersion # and molding the fiber simultaneously exist for a long time, for example, as direct injection molding. According to this method, since it is not necessary to produce a molten material such as granules, in which the fibers are impregnated with a resin, it can be considered that the productivity can be greatly improved. However, normally in the case of direct injection molding, the impregnation and dispersion of the fibers are not sufficient or to achieve sufficient fiber impregnation and dispersion, must use a molding machine with a special screw shape extremely high in the effect of the kneading. Thus, a general purpose injection molding machine can not be used, and further, since the material is powerfully kneaded, the desirable long fibers are broken into short fibers by the high shear force, and the molded product can not manifest the pretended elevated mechanical properties. As described above, the thermoplastic composition material reinforced with long fibers which is very excellent in the productivity of the production of the material and the molding and which has high mechanical properties was not present. It is publicly known to modify a thermoplastic resin using any additive. The use of an aromatic modified terpene resin, as an additive is set forth in the Japanese patent open to the public (Kokai) Nos. 2-199164 and 7-11066. In these techniques, it was attempted to improve the adhesiveness or spreadability of the polyphenylene ether resin or polyolefin which is poor in adhesiveness or spreadability. In the case of a polyamide resin, such modification is not required as much as the resin has high adhesiveness and stability. However, when a polyamide resin with a high molecular weight is used, or when a polyamide resin is used it contains a large amount of a load people or a flame retardant to achieve a higher elastic modulus or a higher flame retardancy. , the flow capacity during molding often becomes insufficient. It has not been practiced to use a resin similar in structure to a resin of Aromatic modified terpene, as an additive, to improve the flowability during molding without greatly imparting the physical properties peculiar to a polyamide. An object of the present invention is to provide a fiber-reinforced thermoplastic resin molding material, which allows easy impregnation of a thermoplastic resin (low viscosity), low molecular weight (high productivity), and allows high mechanical properties are achieved when using a high molecular weight thermoplastic resin, such as the matrix, and which allows it to be impregnated in a matrix of high viscosity in the fibers when the material is plasticized during molding and allows the fibers they are dispersed in the molded product, and also provide a production process thereof. Other objects of the present invention are to provide a resin composition, with good flowability, and molded product obtained from the molding material and the resin composition.

BRIEF DESCRIPTION OF THE INVENTION In order to achieve the above objects, the molding material of the present invention is constituted as follows. A molding material, comprising at least the following components (A), (B), and CC), wherein the component CC), is arranged to contact a composite material consisting of the components CA) and ( B). CA), a continuous reinforcing fiber bundle CB) a thermoplastic polygomer with a weight average molecular weight of 200 to 50,000, and with a melt viscosity lower than that of the CC component), a thermoplastic resin with an average molecular weight in weight of 10,000 or more • The process for producing the molding material of the present invention is constituted as follows. A process for producing the molding material, comprising the steps of impregnating the component CA) with the component CB), heated and melted to have a viscosity of 100 poise or less, to form a composite material, arranging the component (C) , melted so that it has a viscosity of 500 poises or more in contact with the composite material; and cooling the total material to room temperature. The polyamide-based resin composition of the present invention is constituted as follows. A polyamide-based resin composition consisting of the following components (D), and CE), with the component (D), contained by 0.5 to 40 parts in 20 weight against 100 parts by weight of the total resin composition. CD), an oligomer obtained by condensing phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b). CE), a polyamide resin The molten product of the present invention is obtained by molding the molding material or the polyamide-based resin composition.

# The granules that are injection molded of the present invention comprise the molding material or the polyamide-based resin composition. The molded product of the present invention according to another version is obtained by injection molding the granules which are injection molded.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an illustration showing a section of the composite material in the molding material of the present invention as an example. Figure 2 is an illustration showing a section of the molding material of the present invention, as an example. Figure 3 is an illustration showing a section of the molding material of the present invention, according to another example. Figure 4 is an illustration showing a section of the molding material 15 of the present invention, as another example. Figure 5 is an illustration showing a section of the molding material of the present invention, as to one other example. Figure 6 is an illustration showing a section of the molding material of the present invention as one other example. Figure 7 is an illustration showing a section of molding material of the present invention as more in accordance with another additional example. In the drawings, 1 means a simple filament of the component CA), 2, the component (B), 3 the composite material consisting of the components (A) and [B] and 4, the component [C]. 25 VERY PREFERRED MODALITIES THE INVENTION The present invention is described below in greater detail. The molding material of the present invention consists of at least the following three components: the component [A] is a bundle of continuous reinforcing fiber, to provide high mechanical properties to a molded product as a reinforcing material of a composite material . Component [C] is a matrix resin with relatively high viscosity and high physical properties such as toughness. The component [C] is impregnated in the component [A] after the molding, to be joined to the reinforcing material, which acts to keep it firmly. The component [B] is a thermoplastic polymer or oligomer with a relatively low viscosity and forms a composite material with the component [A], and aids in the impregnation of the matrix resins (component [C]), in the fiber bundle of reinforcement (component [A]) during the molding, and also aids in the dispersion of the reinforcing fibers in the matrix, acting as a so-called impregnation and dispersion aid. Components [A] and [B] form a composite material. The style of the composite material is as shown in Figure 1, and the clearances between the respective single filaments of the continuous fiber bundle (component [A]) are filled with the component [B]. That is, component [A] is dispersed as islands in the sea of component [B]. Specifically, the component [B] is thermally fused and impregnated in the component [A], to form the composite material. Figures 2 to 7 typically show the shapes of the sections of the molding materials of the present invention as examples. The shape of the section of each molding material is not limited to those illustrated here, until component [C] is arranged to contact the composite material consisting of two components [A] and [B]. It is preferable that, as shown in Figures 2 to 5, that the component [C] be arranged to cover the circuambiente of the composite material, or that as shown in Figures 6 and 7, the composite material and the component [C] ] are arranged in layers. When a plurality of filaments composed with the component [C] is covered as shown in Figure 4, it is desirable that the number of filaments of the composite material be from two to about 6. It is desirable that the composite and the component [C ] be united on the shore. A state where the component [C] partially penetrates the composite material near the shore in a compatible condition is acceptable, or a state of component [C] 10 is impregnated in the component [A]. It is required that the molding material be continuous with almost the same sectional shape maintained in the longitudinal direction. Depending on the molding method, the continuous molding material can also be cut to a certain length. The molding material of the present invention can be formed in a final molded product mixing the components [A], [B] and [C] by a method such as 'm molding by injection or injection molding. In view of the convenience of handling the molding material, it is important that the respective components are not separated and that they maintain any shape, even if molding is performed. Since component [B] has a low molecular weight, it is often a relatively fragile solid and exposed to be crushed or broken at room temperature or a liquid. In such a way it is desirable that the component [C] with a low molecular weight is arranged to protect the composite material, such that the component [B] is not crushed or scattered by bumps or abrasion, etc., during transport or handling of the material. For this purpose, it is preferable that, as shown in Figures 2 through 5, 25, component [C] covers the circumambient of the composite material consisting of components [A] and [B], or that, as shown in Figures 6 and 7, the composite material and component [C] are arranged in layers. If the components are arranged as described herein, the molding material is likely to retain its shape, since the component [C] with a high molecular weight surrounds the component [B] that is likely to be broken by compression or be disposed on the surface that is likely to be worn. The respective components of the molding material of the present invention are further described below. Component [B] is a thermoplastic polymer or oligomer with a weight Molecular weight average of 200 to 50,000 and with a melt viscosity less than that of the component [C], and the component [A] is impregnated, to form the composite material. When the thermoplastic resin with a high viscosity is impregnated as the matrix in a fiber bundle, the component [B] acts as an auxiliary of the dispersion to aid in the impregnation and dispersion of the fibers in the matrix. The fiber bundle of reinforcement (component [A]), is impregnated with component [B], with a low viscosity. In this way, in the case of molding in the final form by injection molding or pressure molding, etc., when it is heated, the molding material is pressurized and kneaded, the component [B] assists the matrix (the component [C]) impregnated in the fiber bundle (component [A]) and improves the dispersibility of the reinforcing fibers in the matrix.

The mechanism is as described below. The diameter of the single filaments that make up the bundle of reinforcing fibers is as small as 7 to 10 μ in the case of carbon fibers, and 20 μm even in the case of glass fibers. This means that the fiber bundle has a very large surface area that it appears to have. The impregnation of the fiber bundle with a substance melted with a certain viscosity is to compress the molten substance in the small free spaces between the simple filaments, moistening the entire width of the surface area of the fibers while extracting the air that exists in the free spaces between the single strands, outwardly of the texture. The difficulty (the time taken for impregnation) can simply be considered to be to provide the viscosity of the molten substance. In the present invention the fiber bundle is moistened previously by the material (component [B]) with a lower melt viscosity than the material (component [C]) that is to be finally impregnated, and it has to be consolidated within the free spaces between the simple filaments, that is, it is impregnated with it. In such a way even if the substance * melted (component [C]) is finally impregnated, has a high viscosity up to some point, impregnation is very easy. The reason is that the impregnation can be achieved by simply replacing or mixing the previously impregnated material in the fibers and the material to be impregnated, without the problem of expelling the air out of the texture. If the chemical affinity of the component [B] for the reinforcing fiber bundle (component [A]), and the thermoplastic resin (component [C]) as the matrix is taken in account, you can improve the effect. Especially, when the component [B] has a nature of a surfactant, the effect to homogeneously disperse the reinforcing fibers in the molded product when the molding material is plasticized during molding, can be highly obtained. Component [B] is different in concept of the coupling agent or the sizing agent generally used for the surface treatment of reinforcing fibers. That is, the amount of the coupling agent or sizing agent used for the treatment is usually as small as about 0.05 to 10% by weight and it is intended to be applied only to the surface of the fibers. Therefore, the coupling agent or sizing agent is not impregnated in the fiber bundle previously. The component [A] can be subjected to any publicly known surface treatment or can be coated with a coupling agent or sizing agent to achieve the intended effect as conventionally achieved. However, since the fiber bundle is impregnated with the component [B], which is a thermoplastic polymer or oligomer, the amount of the sizing agent, etc., used for the treatment can be a minimum required. When the molding material is produced, component [A] is impregnated in component [B] previously. The component [B] can be easily impregnated in the continuous fiber bundle (component [A]), and in the process for continuously impregnating the fiber bundle, the fiber bundle can be introduced at a high speed of, i.e. meters per minute or more, excellently in view of productivity. In addition, also in the impregnation process, it is not necessary to use a complicated apparatus to greatly open the fibers or rub the fibers against the bars as much as to damage the fibers, or to apply a high pressure to the polymer or thermoplastic oligomer. It is not necessary either to adopt a method with low productivity such as diluting the polymer and thermoplastic oligomer to reduce its viscosity for impregnation and then removing the solvent, or producing an emulsion or dispersion for impregnation and then removing the medium. If the impregnation apparatus is used, it is sufficiently possible that the fiber bundle is introduced at a rate of 10 meters per minute when the thermoplastic polymer or oligomer (component [B]) is melted and impregnated, to provide a great advantage in that way when the molding material is produced, the impregnability of the resin determines the productivity. If the weight average molecular weight of the component [B] is less than 200, it volatilizes easily when heated, to cause defects such as voids in the molded product and to greatly reduce the physical properties of the matrix resin after completing the molding On the contrary, if the weight average molecular weight is • greater than 50,000, the melt viscosity becomes high, making impregnation in the fiber bundle difficult, reducing the productivity of the molding material. A more desirable scale of the weight average molecular weight of component [B] is from 200 to 14,000, and still the most desirable scale from 200 to 1000. To measure the weight average molecular weight, gel permeation chromatography is used ( GPC), and is used, a low-angle light scattering photometer (LALLS) that uses a laser as a detector. Regarding the relationship of the viscosity of the fusion, it only requires that the melting viscosity of the component [B] is lower than that of the component [C] at the temperature of # molding. It is desirable that the melt viscosity of component [B] be 100 or less. More desirable is 20 poises or less. If the melt viscosity is greater than 100 poises, impregnation in the component [A] becomes difficult by reducing the productivity of the molding material. It is desirable that the melting viscosity of component [C] be 500 poises or more. The melt viscosity refers to the viscosity at the temperature of Vicat enlargement of the sample at + 30 ° C from the melting point + 30 C. If the material is When the crystalline temperature has a constant melting point, the melting point plus 30 ° C must be adopted, and in other cases, the softening temperature plus 30 ° C must be adopted. The melt viscosity is measured using a capillary rheometer according to JIS K 7199. The shear stress coefficient for the measurement is 103 s "1. The Vicat softening temperature is measured according to JIS K 7206, and the melting point is measured according to DSC. The component [B] is mixed and disseminated in the component [C] (matrix), in the molded product. If components [B] and [C] are a combination to allow easy mixing, component [C] is excellent in melting as an auxiliary of impregnation and dispersion. More specifically, if the components [B] and [C] have chemical affinity and are desirably compatible, the effect is greater. If both have chemical affinity and # * ^ moderate reactivity even in a non-compatible combination the component [B] is microdispersed in component [C] to manifest a practically sufficient effect as an auxiliary of impregnation and dispersion. If the components [B] and [C] have chemical affinity and tend to be compatible with each other, it can be judged up to a point, 5 using the solubility parameter. The solubility parameter is described in detail in Saburo Akiyama, Takashi Inoue and Toshio Nishi, "polymer blends" (CMC). Various methods are known for deciding the solubility parameter of a polymer, and in comparison, the same method is required to be used. Specifically, it is desirable to use the # Today's method that facilitates the calculation (see the previous book). If the values of the parameter The solubility of the two liquids are close, the combination can be said to be more compatible with each other. From this point of view, if the solubility parameter of the component [B] is 61 and the solubility parameter of the component [C] is 62, then it is preferable that the absolute value of the difference between the parameter values of solubility 61 = 6s2 is less than 3.5. 15 During the mixing of the component [B] with a low viscosity and the component [C], if the component [B] is not suitable as an impregnation and dispersion aid, especially the impact resistance can be greatly reduced. From this point of view, when the content of the component [B] and the molding material is 10% by weight, it is preferable that the Izod impact value of the molded product obtained molding the counting material of 60% or more of the Izod impact value of the molded product excluding the component [B] of the components of the molding material. More preferably it is 75% more. The Izod impact values are measured, according to JIS K7110. Component [B] may contain a flame retardant, an improver of wear due to atmospheric agents, antioxidant, thermal stabilizer, ultraviolet light absorber, plasticizer, colorant, lubricant, compatibility improver, conductive filler, etc., to adapt the required properties of the molded product to be obtained. It is desirable that the component [A] be impregnated perfectly with the component [B]. Theoretically, if the fibers (component [A]), are arranged to form a hexagon in the most compact and the clearances between the fibers are not consolidated with the component [B], then the amount of component [B] is less. Assuming that the fibers are to be of full circle section and of equal diameter, the volumetric content of component [A] is 90.7% (p / 2 x 3 1 2)). It is technically difficult to actually achieve this volumetric content is to form no gap. However, even when a certain quality of voids exists or when the volumetric content is so high, as to form portions not impregnated in calculus, the present invention has an effect of promoting fiber impregnation and dispersion. Considering this, in order to prevent the mechanical properties of the molded composite from decaying, it is preferable that the volumetric content of the component [A] in the composite material is 40% or more. If the volumetric content exceeds 95%, the clearances between the single strands contain more non-compacted parts with the component [B] to severely reduce the impregnation-promoting effect as a result. Thus, it is preferable that the volumetric content of component [B] be 95% or less. A more preferable volumetric content scale is 80 to 95%. As described above, it is desirable that the component be perfectly impregnated with the component [B], but really this is difficult. In this way, the composite material consisting of the components [A] and [B], contain some holes. Especially when the content of component [A] is greater, there are more voids, and even if there are some voids, the present invention may manifest the effect of promoting fiber impregnation and dispersion. However, if the void volume exceeds 40%, the effect of promoting the impregnation of fiber dispersion is markedly reduced. Thus, it is preferable that the hollow volume is from 0 to 40% a more desirable hollow volume scale is 20% or less. The hollow volume is obtained by measuring the part of the composite material according to the test method of ASTM D 2734. The chemical composition of the suitable material as the component [B] is described below. The surface of the reinforcing fibers as the component [A] are normally treated, considering the adhesiveness to the matrix resin, etc., and in addition, usually coated with a highly polar coupling agent and a sizing agent. For this reason, considering the affinity with the surfaces of the fibers, it is desirable that the thermoplastic polymer or oligomer as the component [B] have polar groups. The polar groups include, for example, amino groups, hydroxyl groups, carboxyl groups, etc., and can be selected, considering the affinity with the functional groups, etc., on the surfaces of the fibers. If the polarity of the matrix resin as the component [C] is low as in the case of a polyolefin, etc., it is desirable that the component [B] has portions of an aliphatic hydrocarbon with low polarity, as well as the groups polar. Since the component [B] is previously arranged at the interfaces between the fibers and the matrix, the component [B] with both elevated polar portions and low polar portions as this also functions as a surfactant, and especially contributes to improve the dispersibility of the fiber at the time of molding. As described above, the compatibility between components [B] and [C] is an important factor. Considering the affinity between the components [B] and [C], if the ratio of the highly polar molecules and the low polar molecules in the component [B] is established appropriately, the component [B] has a high affinity with the surfaces of both the fibers and the matrix (the component [C]). An especially excellent compound such as component [B], is an oligomer obtained by adding phenol or a phenol derivative (precursor A), and an aliphatic hydrocarbon with two double bonds (precursor b). The addition reaction can be carried out in the presence of a strong acid or a Lewis acid. In addition the component [B] can be obtained by allowing the precursor a and a compound capable of producing the precursor b in the reaction system, react with each other under the same conditions. It is preferable that the phenol derivative used as the precursor to have * one to 3 substituent groups selected from the alkyl group (particularly those with 10 1 to 9 carbon atoms), halogen atoms (particularly chlorine and bromine), and hydroxyl groups, in the benzene nucleus of the phenol. These phenol derivatives include, for example, cresol, gyleneol, ethylphenol, butylphenol, te-butylphenol, nonylphenol, 3,4,5-trimethylphenol, chlorophenol, bromophenol, chlorocresol, hydroquinone, resorcinol, orcinol, etc. Especially preferred compounds as the precursor a are phenol and cresol. Two or more compounds can be used as the precursor a. f Precursor b is an aliphatic hydrocarbon with two double bonds, and may have one or more cyclic structures. Compounds without any cyclic structure that can be used as the precursor b include butadiene, isoprene, pentadiene, hexadiene, etc. Compounds with one or more cyclic structures that can be used as the precursor b, include monocyclic compounds, such as cyclohexadiene, vinylcyclohexene, cycloheptadiene, cyclooctadiene and monocyclic monoterpene represented by the molecular formula C10H16 (dipentene, limonene, terpinolene, terpinene, phellandrene) , dicyclic compounds such as 2,5-norbornadiene, tetrahydroindane and dicicyclic sesquiterpene represented by the molecular formula C15H24 (cadinena, selinena, caryophyllene, etc.), tricyclic compounds such as diclopentadiene, etc. The compounds that can produce the precursor b in the reaction system include pinene and camphene which can produce dipentene by isamerization. As the precursor b, a compound with 6 to 15 carbon atoms is preferable, and a compound with one or more cyclic structures is also preferable. A compound with one or more cyclic structures is moderately limited in molecular movement and becomes relatively rigid. If component [B] is used with such a structure, the molded product with component [B] dispersed in component [C] does not decay greatly in the elastic modulus. Especially preferable compounds as the precursor b include monocyclic monoterpene represented by the molecular formula C10H16 and dicyclopentadiene. A general molecular structure of the addition product of monocyclic monoterpene and phenol is shown in formula 1 as an example.

A plurality of compounds can be used as the precursor b or as compounds that produce the precursor b in the reaction system. An especially excellent composition as the component [B] in the molding material of the present invention, is such that a product with one molecule of the precursor b added to two molecules of the precursor a (hereinafter called "2: 1 addition product"). ), attributes 40% by weight more than component [B] Since a molecule of a low polar aliphatic hydrocarbon is added to two molecules of phenol or highly polar phenol derivative, the composition as a whole is relatively high in polarity and it is excellent in affinity with a highly polar polya-mide with amirao groups, etc. it is only required that the 2: 1 addition product be contained as a main ingredient by 40% by weight or more in component [B], and for example, a 1: 1 addition product, a 2: 2 addition product, or other impurities may be additionally contained, as an example of the main ingredient of component [B], the molecular structure of the product of addition between dipentanthus as monoterpene monocyclic and phenol is shown in formula [II].

The reinforcement fibers used as the component [A] are not especially limited. Fibers with a high elastic modulus strength such as carbon fibers, glass fibers, polyaramide fibers, alumina fibers, exilium carbide fibers or boron fibers can also be used. Two or more types can also be used as a mix. Among them, fibers are preferable of carbon since these are excellent in the effect of improving the mechanical properties. 20 The most preferable carbon fibers are from 0.05 to 0.4 in the chemical function of surface (O / C) obtained as a refaction of the number of hydrogen atoms (O) to the number of carbon atoms on the surfaces of the fibers measured by it is X-ray photoelectronic ecrostroscopy. An O / C ratio of less than 0.05 implies that the number of functional groups that contribute to the adhesion to the matrix resin on ia surface of the carbon fibers is very small. If the adhesion between the carbon fibers and the matrix resin is poor. The molded product can not be expected to have high mechanical properties. Conversely, an O / C ratio of more than 0.4 gives attention to the fact that the surface of the carbon fibers are more oxidized than required, and that the crystalline carbon structure is destroyed to form a brittle layer on the surface of the carbon fiber. every fiber. Also in this case, as in the case of the O / C too low, the destruction is prone to occur near the surface layers of the fibers, and the molded product can not be expected to have high mechanical properties. If the O / C ratio is maintained in the above scale, the effects may preferably be provided not only for adhesion between the interfaces between the fibers and the matrix, but also for the affinity for impregnation with the component [B] and the dispersibility of the fibers at the time of molding. The chemical function of surface (O / C) is obtained according to the following procedure by x-ray photoelectron spectroscopy. First, the carbon fibers (bundle), from which the sizing agent is removed, etc., by means of a solvent, are cut and scattered over a sample holder made of copper, and at a 90 ° angle of photoelectron escape, with MgKa 1,2, used as the source of x-rays, the sample chamber is internally maintained at 1 x 10"8. For correction of the peak due to electrification at the time of measurement, synthetic energy is established (K.E.) of the main peak of C1S to 969 eV. This peak area C1S is obtained by tracing a straight baseline on the scale of K.E. from 958 to 972 eV., and the peak area 01 S is obtained by tracing a straight baseline on the scale of 714 to 726 eV. The surface chemical function (O / C) is calculated as a ratio of the numbers of atoms from the ratio of the peak area 01 S to the peak area C1S using a sensitivity correction value peculiar to the instrument. The thermoplastic resin used as component [C] has a weight average molecular weight of 10,000 or more.If the weight average molecular weight is less than 10,000, the mechanical properties of the molded product finally obtained from the composite material decay. Component [C] is not especially limited until it has an average molecular weight of 10,000 or more Compounds that can be used as the component include polyamides (nylon 6, nylon 66, etc.), polyolefins (polyethylene, polypropylene, etc.). ), polyesters (polyethylene terephthalate, polyebutylene terephthalate, etc.), polycarbonates, polyamidimides, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyether sulfones, polyether ether ketones, and polyether midas, polystyrene, ABS, crystalline polyesters, acrylonitrile copolymers , styrene, etc., and their mixtures. can use copolymers such as the nylon 6-nylon 66 copolymer. Furthermore, to satisfy the required properties of the molded product, the component [C] can contain a retarder, a wear enhancer due to atmospheric agents, antioxidants, thermal stabilizer , ultraviolet light absorbers, plasticizer, lubricant, colorants, compatibility improver, conductive filler, etc. The compounds especially suitable for the component [C] of the mold material of the present invention, include polyamides, polyolefins and polycarbonates. Among them, nylon 6, nylon 66 and nylon 6-nylon 66 copolymer are excellent in affinity with oligomer (component [B]), obtained by condensation of phenol or a phenol derivative and an aliphatic hydrocarbon with two double bonds and they are excellent since they do not decay the mechanical properties even after mixing them with this one. It is preferable that the molding material of the present invention be cut to a length of 1 to 50 mm when used. If the molding material is discontinuous, it is superior in flow capacity and very high in molding formability. If the length is shorter, the molding capacity such as formability and flowability is increased, but if the cutting length is less than 1 mm, the reinforcing effect of the fiber severely decays, since the reinforcing fibers They are too short. If the cutting length is greater than 50 mm, the moldability is greatly reduced although the reinforcing effect is increased. A most desirable cut length scale of 3 to 12 mm. The molding material of the present invention can also be used as a continuous long material, depending on the forming method. For example, this can be formed as a prepreg of thermoplastic yarn, and can be wrapped around a mandrel while being heated, to obtain a roll shape. In addition, the material of the present invention as a plurality of filaments can be placed in parallel and heated to be melted, to produce a unidirectional thermoplastic prepreg. The prepreg can be applied in fields where a high resistance and elastic modulus are required. To produce the molding material of the present invention, the component [A] is impregnated with the heated component [B] to be melted so that it has a viscosity of 100 feet less, to form a less composite material, to form a composite material , and then the molten component [C] to have a viscosity of 500 poises or less, are arranged to contact the composite material. Subsequently, the total composition is cooled to room temperature (from about 15 to 25 ° C, for example the production process can comprise 3 steps: a step of depositing the hot and melted component [B] onto the continuous fiber bundle (component [A]) by a predetermined amount per unit length (hereinafter referred to as the auxiliary application stage), a step of adjusting the component [B] deposited on the fiber bundle, so that it has a viscosity of 100 poises or less, for deep impregnation into the fiber bundle to form a composite material (hereinafter the auxiliary impregnation step, and a step of arranging the hot and melted component [C] so that it has a viscosity of 500 pises or more , in order to contact the continuous composite material (hereinafter referred to as the array disposition stage), it is desirable that these three steps be carried out continuously, but these three steps can also be carried out discontinuously. , that is, by winding the mixed material around a coil, etc., after the auxiliary impregnation step, and then feeding the composite material through the dispense stage. position of the matrix outside the line. It is more desirable that the auxiliary application step and the auxiliary impregnation step can be carried out simultaneously by an apparatus. The auxiliary application step can be carried out using a publicly known production method of applying an oil, a sizing agent or a matrix resin to a fiber bundle. For example, on the surface of a hot rotating roll, the molten component [B] is formed, like a film with a certain thickness (coating), and a fiber bundle (component [A]) is fed, so that it is introduced a contact with it, to deposit the component [B], by a predetermined amount per unit length of the fiber bundle. The coating of the roller surface with the component [B] can be carried out by applying the concept of a publicly known coater such as the reverse roller, the regular rotation roller, the friction roller, the spray, the curtain, the extrusion, etc. the devices for coating on a roller are described in detail in "Introduction to Coaters and Operation Techniques" (Gijutsu Sogo Center), etc. If these techniques are applied, the hot and melted [B] component can also be directly applied, not only on the roller surface, to introduce a fiber bundle using any of different coaters. For example, although the component [B] is extruded by a certain amount per unit of time from a nozzle, a fiber bundle that is introduced at a constant speed can be brought into contact with the nozzle. It is not necessarily required that the nozzle and fiber bundle be brought into contact with each other perfectly, and simply by allowing the fiber bundle to run close to the nozzle, coating can be achieved. In the auxiliary impregnation stage, at the temperature at which the component [B] is melted, the component [A] with the component [B] deposited is rubbed by the bars, or is scattered and collected repetitively, or pressurized or vibrated, to impregnate the component [B] deep inside the bundle of fibers (component [A]). For example, the fiber bundle in contact with the surface of a plurality of hot rollers or bars is fed to be spread. In this case, unless the viscosity of the molten component [B] is maintained at 100 poise or less by adjusting the temperature, the fiber bundle can not be impregnated with the component [B] at a high speed. In the step of arranging the matrix, the molten component [C] with a viscosity of 500 poises or more is arranged to contact the composite material. For example, an extruder and a coating die used for the protection of electric wires can be used to arrange the component [C] around the continuous composite material as if it were covered. According to another method, the component [C] cast formed as a film by an extruder and a die in T-shape, is arranged on one side or on both sides of the composite material flattened by the rollers, etc., and these are integrated by rollers, etc. The produced molding material can be cut to a certain length by an apparatus such as a filament cutter or granulator, to be used, the cutting step can be continuously arranged downstream of the die disposition stage. If the molding material is flat or a sheet, it may tear slightly and cut. A sheet granulator for tearing and simultaneous cutting can also be used. To produce the aforementioned thermoplastic yarn prepreg in succession to the die disposition step, for example, the disposed matrix resin (component [C] can be melted, and mixed with the component [B] using a press with hot roll, etc., for continuous impregnation in the component [A], and the total composition may be planar in section .. The polyamide-based resin composition of the present invention is described below: The resin composition of the present invention The component [D] is an oligomer obtained by condensation of the phenol or a phenol derivative (precursor a), and an aliphatic hydrocarbon with two double bonds (precursors b), and the component [ E] is a polyamide resin The resin composition may also contain reinforcing fibers The component [B] in this case corresponds to a preferred embodiment of the component [D] The component [D], It has a relatively low molecular weight and a very low viscosity. In such a way when this is added to the component [D], it makes the resin composition highly flowable. Especially when the resin contains a bulking agent such as reinforcing fibers or flame retardants, etc., and is very poor in flowability, the addition component can improve the flowability at the time of melting with heat, to improve the moldabilidad. In general, if a low molecular weight material is added to a resin, it can happen that the mechanical properties of the resin decay greatly compared with those before the addition. However, the resin composition of the present invention is very insignificant in the decay of properties. Against 100 parts by weight in total of the resin composition of the present invention the component is added from 0.5 to 40 parts by weight. If the amount is less than 0.5 parts by weight, the effect of improving the flowability is negligible, and if it is larger than 40 parts by weight, the mechanical properties of the resin composition decay greatly, a more desirable scale is of 5 to 15 parts by weight. Against 100 parts by weight of the resin composition, reinforcing fibers of from 5 to 200 parts by weight may be added. Since the component is this content, the flowability of the resin composition is relatively good even if the reinforcing fs are contained. If the amount of the reinforcing fs is less than 5 parts by weight, the effect of the reinforcement by the fs is negligible, and if it is greater than 200 parts by weight, the flowability and the moldability are poor even if the component [D]. A more desirable scale of the reinforcing f content is 10 to 70 parts by weight. The type of reinforcing fs is not especially limited. Fs with high strength and a high elastic modulus such as fs, carbon fs, glass fs, polyaramide fs, alumina fs, silicon carbide fs, and boron fs can be used. You can also use two or more types of these as a mixture. Among them, carbon fs are preferred since they are excellent in the effect of improving the mechanical properties. It is more preferable that the chemical function of surface (O / C), according to the ratio of the number of oxygen atoms (O) to the number of carbon atoms (C) on the f surfaces measured by the spectroscopy, was a photoelectron of x-rays are on a scale of 0.05 to 0.4. The component [D] is descr below. The component [D] is an oligomer obtained by the condensation reaction between the phenol or a phenol derivative (precursor a), and an aliphatic hydrocarbon with two double bonds (precursor b). It is preferable that the weight average molecular weight of component [D] is 200 or more, to prevent the molded product from being easily volatilized to form such defects as voids, when heated, or in this way the physical properties of the composition of the resin decay. On the other hand, if the molecular weight is too large, the melt viscosity becomes high. In order to effectively improve the flowability of the resin composition, it is preferable that the molecular weight is 1000 or less. The weight average molecular weight in this case is measured according to gel permeation chromatography (GPC), which uses a low angle light scattering photometer (LALLS). The polyamide resin as the component [E] is not especially limited until it is a polymer with its main chain formed by repeats of an amino group, and aliphatic polyamides such as nylon 6, nylon 66, nylon 11, nylon 610, nylon 612 and Polyamides based on dimeric acid, aromatic polyamides such as nylon 6T, etc., can be used. Any of its mixtures or a copolymer consisting of a plurality of polyamides such as the nylon 6-nylon 66 copolymer can also be used. Also a polymer with another type of molecule connected to a polyamide by the reaction of addition or reaction involved in, by the reaction of graft or amino groups to methylene groups, etc., can also be used. Among the polyamides, nylon 6, nylon 66 and nylon 6-nylon 66 copolymer are especially suitable, since these have excellent mechanical properties. The resin composition of the present invention may contain a flame retardant, a wear improver for environmental conditions, an antioxidant, a thermal stabilizer, an ultraviolet light absorber, a plasticizer, a lubricant, a colorant, a compatibility improver, a conductive filler, etc. The resin composition of the present invention is not especially specified in the degree of mixing, until the mixing ratio is in said scale. A composition with the respective components almost homogeneously dispersed kneaded by a separate type composition in which the component [E] is disposed in contact with the reinforcing fs impregnated with the component [D] can also be used. In this case, the component [D] also functions as an auxiliary to allow the reinforcing fs to be easily impregnated with the component [E] when the f reinforced resin composition is molded. The molding material and resin composition descr above, can be processed into products with a final shape by ordinary molding. The molding methods that can be used, include pressure molding, transfer molding, injection molding and combinations thereof. The mouldable products that can be produced include auto parts such as cylinder head covers, support retainers, input manifolds and pedals, tools such as wrenches, and small items such as gears. Since the molding material of the present invention is excellent in flowability, molded products as thin as 0.5 to 2 mm can be easily obtained. Products that require thin molding include parts of electrical and electronic equipment such as housings used for personal computers and keypad and cellphone mounts within personal computers. For parts of electrical and electronic equipment, if conductive carbon fibers such as reinforcing fibers are used, it is desirable that they can protect the electromagnetic zones. The above molding material and the resin composition can be used as granules that are injection molded. In injection molding when the molding material provided as granules is plasticized, it is heated, pressurized and kneaded. Thus, according to the present invention, the component [B] or [D] manifests a great effect as an auxiliary in the dispersion and in the impregnation. In this case, an ordinary inline screw type injection molding machine can be used. Furthermore, even when the effect of kneading by a screw is weak because of the use of a formed screw having a low compression ratio or because of the establishment of a low back pressure for the plasticization of the material, the reinforcing fibers are dispersed well in the matrix resin, to provide a molded product containing fibers well impregnated with a resin.

EXAMPLES Example 1 On a roller heated to 130 ° C, a hot molten liquid of a phenol terpene oligomer is formed (YP90L adhesion product of monocyclic monoterpene and phenol with a weight average molecular weight of 460, produced by Yasuhara Chemical KK) , in a movie. A soft print coater is used to form the film with a certain thickness on the roll. On the roller, a bundle of continuous carbon fibers ("Torayca" T700SC produced by Toray Industries, Inc., consisting of 12,000 carbon fibers with a denier single fineness of 0.6 denier) was fed into contact with it, to have to the phenol terpene oligomer deposited by a certain amount per unit length of the carbon fiber bundle. The carbon fibers with the deposited oligomer were fed alternately on and below 10 rolls with a diameter of 50 mm, heated to 180 ° C, freely rotated by the gears and arranged on a straight line. This operation causes the oligomer to be impregnated deeply into the fiber bundle, to form a continuous composite consisting of carbon fibers and the terpene phenol oligomer. In this step, the amount of the oligomer was 15% by weight based on the weight of the total composite. The specific gravity of the carbon fibers was 1.80 and the specific gravity of the terpene phenol oligomer was 1.06. In this way, the volumetric content of the carbon fibers in the total composite material was 76.8%. The melt viscosity of YP90L at 130 ° C at a shear stress coefficient of 103 s as measured by a capillary rheometer was about 10 poises.The continuous composite was fed through a coating side to cover electric wires installed in the tip of a single screw extruder with a diameter of 40 mm, and nylon 6 resin ("Amilan" CM1017 produced by Toray Industries, Inc., with a weight average molecular weight of 18,600) melted at 240 ° was discharged. C to the side from an extruder, to be continuously arranged to cover the circumambiente of the composite material.The melting viscosity of nylon 6 to 240 ° C to a coefficient of shear stress 103 s "1 measured by a capillary rheometer was approximately 2000 poises. The molding material obtained by coating the composite with nylon 6 was cooled to about room temperature and cut to a length of 7 mm by a filament cutter. The production of the molding material was continued, and the feed speed of the carbon fiber bundle was 30 m / minute. The granules were used to obtain a molded sheet with dimensions of 150 mm x 150 mm x 1 mm by means of an injection molding machine with a mold holding force of 100 tons. In this molding, the cylinder temperature was set at 250 ° C in a portion near the nozzle, and the mold temperature was 70 ° C. The molded product has a smooth surface, and there are no problems with the dispersibility of the fibers in the molded product. A section of the molded product was observed through a microscope, and no gaps were confirmed. The composition of the molding product was carbon fibers: terpene phenol oligomer: nylon resin 6 = 35: 6: 59. The impact value of cutting Ixod of the molded product was 21 kgf cm / cm.

Comparative Example 1 The same continuous carbon fiber bundle as used in example 1, was fed through a coating die to coat electric wire installed on the tip of a single screw extruder with a diameter of 4 0 mm , and nylon 6 resin ("Amilan" CM1017 produced by Toray Industries, Inc.), melted at 240 ° C, was discharged from an extruder, to be continuously arranged to coat the circumambient of the composite material. The molding material in which the carbon fiber bundle is coated with * nylon 6 was cooled to approximately room temperature, and cut to a length of 10 7 mm by a filament cutter, to make granules that are injection molded. The carbon fiber bundle was introduced at a rate of 30 ° per minute. The granules were used to obtain a molded sheet with dimensions of 150 x 150 mm x 1 mm by means of an injection molding machine with a mold holding force of 100 tons. The same molding conditions were used as used in example 1. The material was insufficient in flowability, and the molded product was partially fired insufficiently in a separate portion of the bridge of the mold. On the surface of the molded product, an unopened and non-impregnated fiber bundle was exposed, and a fin was formed in the portion. A section of the molded product was observed through a microscope and a non-open fiber beam 20 and not impregnated and voids were observed. The composition of the molded product was carbon fibers: nylon resin 6 = 35: 65. The Izod impact value of cutting of the molded product was 25 kgf cm / cm. Industrial Applicability 25 the molding material of the present invention is easy to produce, and when molded by injection molding, etc., the reinforcing fiber bundle can be well dispersed in the molded product. In addition, the polyamide-based resin composition of the present invention has excellent flowability. Moreover, from them, molded products with excellent quality can be obtained.

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Claims (6)

1. CLAIMS 1. - A molding material, comprising at least the following components [A], [B] and [C], with the component [C] arranged to contact a composite material comprising the components [A] and [B] ] [A] a continuous reinforcing fiber bundle [B] a thermoplastic polymer or oligomer with a weight average molecular weight of 200 to 50,000 and a melt viscosity lower than that of component [C] [C] a thermoplastic resin with a weight average molecular weight of 10,000 or more.
2. 2. A molding material, according to claim 1, wherein the molding material is cut to a length of 1 to 50 mm.
3. 3. A molding material, according to claim 1, wherein the component [C] is arranged to cover the circuit of the composite material.
4. 4. A molding material, according to claim 3, wherein the molding material is cut to a length of 1 to 50 mm.
5. 5. A molding material, according to claim wherein the component [C] is arranged in layers with the composite material.
6. 6. A molding material, according to claim 5, wherein the molding material is cut to a length of 1 to 50 mm. A molding material according to any one of claims 1 to 6, wherein the melt viscosity of component [B] is 100 poises or less, and the melting viscosity of component [C] is 500 poises or more. 8. A molding material, according to any of claims 1 to 6, wherein the absolute value of the difference between the solubility parameter 61 of the component [B] and the solubility parameter 62 of the component [C] is less than 3.5. 9. The molding material according to any of claims 1 to 6, wherein when the content of the component [B] in the molding material is 10% by weight, the Izod impact value of the molded product obtained by molding the material attributes to 60% or more of the Izod impact value of the molded product obtained excluding the component [B] of the components of the molding material. 10. A molding material according to any of claims 1 to 6, wherein the volumetric content of the component [A] in the composite material is from 40 to 95%. 11. A molding material, according to any of claims 1 to 6, wherein the hollow volume of the composite material is from 0 to 40%. 12. A molding material according to any of claims 1 to 6, wherein the component 6 is a polyamide, polyolefin, polycarbonate, or any of the mixtures and copolymers comprising 2 or more of them. 13. A molding material according to any of claims 1 to 6, wherein the thermoplastic polymer or oligomer as the component [D] is an oligomer obtained by adding phenol or a phenol derivative (precursor a), and a aliphatic hydrocarbon with two double bonds (precursor b). 14. A molding material, according to claim 13, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and two double bonds. 15. A molding material, according to claim 14, wherein the precursor b has one or more cyclic structures. 16. - A molding material, according to claim 15, wherein the precursor b is dicyclopentadiene or monoterpene or monocyclic represented by the molecular formula C10H17. 17. A molding material, according to claim 13, wherein the composition with a precursor b molecule added to two precursor molecules a, allocates 40% by weight or more in component [B]. 18. A molding material, according to claim 13, wherein the average molecular weight of the weight of the component [B] is 200 to 1000. 19. A molding material, according to any of claims 1 to 6, wherein the component [C] is nylon 6, nylon 66 or a copolymer of nylon 6-nylon 66. 20. A molding material, according to any of claims 1 to 6, wherein the polymer or thermoplastic oligomer as the component [B] is an oligomer obtained by the addition of phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b), and the precursor c is nylon 6, nylon 66 or a copolymer of nylon 6-nylon 66. 21. A molding material, according to claim 20, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and with two double bonds . 22. A molding material, according to claim 21, wherein the precursor b has one or more cyclic structures. 23. A molding material, according to claim 22, wherein the precursor b is dicyclopentadiene or monocyclic monoterpene represented by the molecular formula C10H16. 24. A molding material, according to claim 20, wherein a composition or a molecule of the precursor b added to two molecules of the precursor a attributes 40% by weight or more of the component [B]. 25. A molding material, according to claim 20, wherein the average molecular weight and the weight of component [B] is 200 to 1000. 26.- A molding material according to any of claims 1 to 6, wherein the reinforcing fibers of component [A] are carbon fibers. 27. A molding material, according to any of claims 1 to 6, wherein the reinforcing fibers of the component [A] are carbon fibers of 0.05 to 0.4 chemical surface function (O / C) as the ratio of oxygen atom numbers (O to that of the carbon atoms (C) of the surface of the fibers measured by x-ray photoelectron spectroscopy 28. A process for producing the molding material set forth in any of the claims 1, 3, and 5, which comprises the steps of impregnating the component [A] with the component [B], heated and melted to have a viscosity of 100 poises, to form a composite material, arranging the molten component [C] for having a viscosity of 500 poises or more to contact the composite material, and cooling the total material to room temperature 29.- A process for producing a molding material set forth in any of claims 2,4, or 6, who buy of the steps of impregnating the component [A] or the component [B] heated and melted to have a viscosity of 100 poise or less, to form a composite material; arranging the molten component [C] to have a viscosity of 500 poises or more, to bring the composite material into contact; cool the total material at room temperature; and cut to a length of 1 to 50 mm. 30. - A resin composition based on polyamide, comprising at least the following components [D] and [E], with the component [D] contained by 0.5 to 40 parts by weight against 100 parts by weight of the total composition of resin, [D] an oligomer obtained by the condensation of phenol a phenol derivative (precursor a), and an aliphatic hydrocarbon with two double bonds (precursor b) [E] a polyamide resin. 31.- A resin composition based on polyamide, according to claim 30, wherein the precursor b is an aliphatic hydrocarbon with six to 15 carbon atoms and with two double bonds. 32. A molding material, according to claim 31, wherein the precursor b has one or more cyclic structures. 33. A molding material, according to claim 32, wherein the precursor b is dicyclopentadiene or monocyclic monoterpene represented by the molecular formula C10H16. 34. A molding material according to any of claims 30 to 33, wherein a composition with a precursor b molecule added to two precursor molecules a attributes 40% or more of the component [D]. 35.- A molding material, according to any of claims 30 to 33, wherein the weight average molecular weight of the component [D] is 200 to 1000. 36.- A molding material, according to any of claims 30 to 33, wherein the component [E] is nylon 6, nylon 66 or a copolymer of nylon 6-nylon 66. 37.- A resin composition based on fiber reinforced polyamide, which it comprises 100 parts by weight of a polyamide-based resin composition set forth in any of claims 30 to 33 and from 5 to 200 parts by weight of reinforcing fibers. 38.- A resin composition based on polyamide reinforced with fiber, according to claim 37, wherein the reinforcing fibers are carbon fibers. 39.- A resin composition based on fiber reinforced polyamide, according to claim 38, wherein the reinforcing fibers are carbon fibers from 0.05 to 0.4 in the oxygen content O / C on the surface of the fibers measured by x-ray photoelectron spectroscopy. 40.- A molded product, obtained by molding the molding material established in any of claims 1 to 6. 41.- A molded product, obtained by molding the polyamide-based resin composition set forth in any of claims 30 to 33. 42.- Granules that are molded by injection, comprising the molding material established in any of claims 2, 4 and 6. 43.- A molded product, obtained by injection molding the granules that are injection molded established in the claim 42. The granules that are injection molded comprising the polyamide-based resin composition set forth in any of claims 30 to 33. 45.- A molded product, obtained by injection molding the granules that are injection molded. in claim 44.