JP2002088259A - Molding material, its manufacturing method and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material which can obtain a molded article having well-balanced mechanical properties, particularly impact strength and rigidity and, in addition, has excellent moldability, particularly flowability on molding and high productivity as well, its manufacturing method, and a molded article to be obtained therefrom. SOLUTION: The molding material comprises at least reinforcing fibers and two types of resins (A) and (B), and the resin (A) forms its domain in the matrix of the resin (B) and, simultaneously, has an islands-sea structure having a domain diameter of 0.4-15 mm. Further, the method for manufacturing the molding material comprises previously opening reinforcing fibers, preheating them, and impregnating the bundle of the reinforcing fibers with the resin (A) to form a composite of the reinforcing fibers with the resin (A), then coating the above composite with at least resin (B), and subsequently taking up the coated composite at a rate of >=10 m/min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molding material having excellent moldability, particularly excellent fluidity during molding, and having high productivity, a method for producing the same, and mechanical properties formed by using the molding material. In particular, the present invention relates to a molded product having a good balance of impact strength and rigidity.

[Detailed Description of the Invention]

2. Description of the Related Art Conventionally, in a molding material having high productivity, for example, a compound pellet (short fiber pellet) obtained by kneading a reinforcing fiber and a resin by an extruder, the reinforcing fiber in the obtained molded product is not used. Due to the shortening, the impact strength of the molded article is particularly low, and it is almost impossible to obtain a molded article having good mechanical properties.

[0003] In order to obtain a molded article having a good balance of mechanical properties, it is effective to lengthen the reinforcing fibers in the molded article. Therefore, a long fiber pellet in which the reinforcing fibers are aligned in one direction is used. Attempts have been made to use it. Generally, the long fiber pellets are described in, for example, JP-B-63-376.
As described in Japanese Unexamined Patent Publication No. 94 (Prior Art Example 1), it is manufactured by impregnating a reinforcing fiber with a resin using a pultrusion method using a crosshead die or an impregnation bath. However, in the prior example 1, since the resin is impregnated into the reinforcing fiber only by a mere mechanical force, the reinforcing fiber is significantly damaged when passing through the manufacturing process, particularly the process of impregnating the resin into the reinforcing fiber bundle, and Not only was it impossible to obtain a molded product having well-balanced properties, but also the productivity of the molding material was extremely deteriorated and the production cost was extremely high.

[0004] From the viewpoint of materials, attempts have been made to obtain a molded article having a good balance of mechanical properties by using a plurality of resins in combination as a matrix resin. For example, JP-A-8-
In Japanese Patent No. 207148 (Prior Art 2), by using a matrix resin forming an islands-in-the-sea structure composed of two types of incompatible resins, the average domain period of the islands-in-the-sea structure and the length of the reinforcing fiber are made to have a specific relationship. Fiber-reinforced thermoplastic resin molded article (molded article) excellent in heat resistance and mechanical properties, etc., structure (molding material) capable of efficiently obtaining the molded article
There is a description about. However, in the prior example 2, there is a problem that it becomes more difficult to impregnate the matrix resin into the reinforcing fiber bundle due to an increase in the melt viscosity of the matrix resin, or a plurality of resins are previously kneaded using an extruder or the like. There is a problem that the cost is increased due to the extra steps. In addition, there is no description or consideration regarding the form of the sea-island structure before molding (structure, molding material) and after molding (molded body, molded product).
Although the mechanical properties are improved to some extent, there is no description about the productivity of the molding material, and there is a problem that the productivity is inferior in practice.

On the other hand, in order to improve the productivity of molding materials, attempts have been made to treat reinforcing fibers in advance with a resin having a lower viscosity than a resin emulsion or a matrix resin. For example, JP-A-11-99519 (Prior art 3) describes a thermoplastic composite material in which a reinforcing fiber is contact-treated with a liquid having a boiling point higher than that of a matrix resin and then impregnated with the matrix resin. . But,
In the preceding example 3, although the productivity is improved to some extent, the use of a liquid material causes not only bleed-out from the molded article after molding, but also the same as in the preceding example 2 before molding (structure, molding, etc.). Material) and after molding (molded product, molded product)
There is no description or consideration of the form of the sea-island structure.

That is, it is possible to obtain a molded article having well-balanced mechanical properties, particularly impact strength and rigidity.
And molding materials with excellent moldability, especially fluidity during molding,
The demand for high productivity has not yet been achieved.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, the present invention can provide a molded product having a good balance of mechanical properties, particularly impact strength and rigidity. It is an object of the present invention to provide a molding material having excellent flowability and high productivity, a method for producing the molding material, and a molded article molded from the molding material obtained therefrom.

[0008]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the molding material of the present invention is a molding material comprising at least a reinforcing fiber and two types of resins (A) and (B), and the resin (A) is contained in a matrix of the resin (B).
Form a domain, and the domain diameter is 0.4 to
A molding material having a sea-island structure in a range of 15 mm.

Further, in the method for producing a molding material according to the present invention, the reinforcing fibers are preliminarily opened and preheated, and the resin (A) is impregnated in the reinforcing fiber bundle, whereby the reinforcing fibers and the resin (A) are mixed. A composite is formed, and then the composite is coated with at least the resin (B), and thereafter, the coated composite is taken off at a speed of 10 m / min or more.

[0010] The molded article of the present invention is characterized by being molded from the molding material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The molding material of the present invention comprises at least a reinforcing fiber and two kinds of resins (A) and (B), and the resin (A) forms a domain in a matrix of the resin (B). And its domain diameter is 0.4 to 15 mm
Which form a sea-island structure. Here, the resin (A) refers to a resin that forms an island structure in a molded article, and the resin (B) refers to a resin that forms a sea structure (matrix) in a molded article. In addition, the sea structure in the present invention is a sea-island structure in a general polymer alloy or polymer blend, in addition to a structure having a plurality of island structures in a region of the sea structure, such that the sea structure wraps around the island structure. The form which is arranged and has only one island structure in the region of the sea structure is also included in the sea structure in the present invention.

When the domain diameter of the resin (A) formed in the matrix of the resin (B) of the molding material is less than 0.4 mm, the resin (A) may be used during the production process of the molding material. Since an extra step of melting and kneading the resin (A) and the resin (B) for finely dispersing the resin to a fine particle size is required, the productivity per unit of production of the molding material is inferior. I can't solve it. Here, the production unit refers to one unit in a form (eg, strand, gut, sheet, etc.) that is taken or extruded in the production process, and particularly when the molding material is a long fiber pellet, one unit is used. Equivalent to. On the other hand, when the domain diameter of the resin (A) exceeds 15 mm, the process of melting and kneading can be omitted, and although the productivity per unit of production of the molding material is excellent, the resin (A) ) And resin (B), or the dispersion of resin (A) in resin (B) is poor, so that the obtained molded article has poor mechanical properties. The domain diameter of the resin (A) in a more preferable molding material is in the range of 0.8 to 13 mm, and further preferably,
It is in the range of 1.2 to 10 mm. In particular, resin (A)
Has a domain diameter in the range of 1.5 to 8 mm.

The domain diameter of the resin (A) in the molding material is an average value of the values measured by the following procedure.

(1) From the molding material, arbitrarily cut (or cut out) ten planes including at least a longitudinal direction of the molding material and a plane perpendicular to the longitudinal direction. The longitudinal direction of the molding material refers to a direction in which a production unit of the molding material is drawn or extruded, and particularly corresponds to the column direction when the molding material has a columnar shape. A typical example is the orientation direction of the reinforcing fibers. In particular, when the molding material is not pulled out or extruded, the longitudinal direction is not defined, and an arbitrary cross section may be cut out or cut out.

(2) The above sections are polished smoothly. Next, each cross section is observed using an optical microscope, and when less than 100 domains are observed in the cross section, all the domains are selected. When 100 or more domains are observed, 100 domains are optionally selected. select. However, when the domain diameter measured by the method described in the following item (3) is 0.
Those with a thickness of 05 mm or less are excluded.

(3) The diameters of the selected domains are measured using an optical microscope. In particular, when the boundaries of the domains are unclear with an optical microscope, use a phase contrast microscope or a polarizing microscope. When the domains are fine (about 0.1 mm or less), resin (A) or After selectively dyeing or etching only one of the resins (B), the measurement is preferably performed using a scanning or transmission electron microscope. Osmic acid (OsO ₄ ) is used for a resin having a double bond, ruthenic acid (RuO ₄ ) is used for a resin having a benzene ring, and a amide group is used as a dye for selectively dyeing. Contains phosphotungstic acid (PTA)
Is often effective. In the present invention, other dyes and dyes such as chlorosulfonic acid may be dyed singly or in combination as appropriate. Also, acids, alkalis,
Various etching methods such as a solvent and an ion are also effective, and in many cases, more effective when used in combination with a dye or a dye. The domain diameter refers to a maximum linear distance in a domain (a straight line passing even outside a part of the domain is excluded), and reinforcing fibers, fillers, and the like described later are arranged in the domain. If so, make them part of the domain as well. However, if they are arranged on the boundary of the sea-island structure, they are not part of the domain. Further, it is preferable that the cross section for measuring the domain is a cross section orthogonal to the orientation direction of the reinforcing fibers. That is, if the domain diameter value is the same, the effect of the present invention is more suitably exerted by a domain diameter defined using a measured value in a cross section orthogonal to the orientation direction of the reinforcing fibers. in this case,
It is ideal to cut out the cross section so as to be perpendicular to each orientation direction of the reinforcing fiber, but simply, the apparent flatness of the reinforcing fiber in the cross section and the true shape of the reinforcing fiber (for example, a perfect circle) By comparing the apparent domain diameters in the cross section, the domain diameter in the cross section perpendicular to the orientation direction of the true reinforcing fibers can be obtained by the comparison.

Conventionally, when a resin (A) having a large domain diameter as described above is present in a molding material, the resin (A) is dispersed in a molded article with a domain diameter in a range described later. It has been considered that the above tendency is remarkable because it is difficult to knead the resin particularly in a long fiber reinforced molding material. Furthermore, even when viewed as a molded article, the fact that the domain diameter is within the range described below is a relatively large range of domain diameters, particularly in a molded article made of resin alone, and is generally considered to be an undesirable range. I have been. However, in the present invention, the domain diameter of the molding material (preferably also the domain diameter in a molded article obtained by molding the molding material) is set to a specific range as in the present invention, and the molding material (and the It was found that the object of the present invention could be unexpectedly solved when fiber reinforced (especially long fiber reinforced) the product.

Preferably, in the molded article obtained by molding the molding material of the present invention, the resin (A) does not form a domain in the matrix of the resin (B), or the resin (B) contains A) forms a domain, and
The domain diameter is in the range of 0.05 to 50 μm.

When the resin (A) in the molded article does not form a domain, it means that the compatibility between the resin (A) and the resin (B) is extremely excellent and the mechanical properties are well-balanced. A molded article can be obtained.

Further, when the resin (A) in the molded article forms a domain and the domain diameter is within the range of the present invention, the compatibility between the resin (A) and the resin (B) can be improved. It means that the dispersibility is excellent to some extent, and it is possible to obtain a molded article having a good balance of mechanical properties. Heretofore, it has been generally considered that when the resin (A) in a molded article forms a domain within the scope of the present invention, mechanical properties cannot be obtained in a well-balanced manner. However, in the case of a fiber-reinforced resin (particularly a resin reinforced with long fibers) as in the present invention, the mechanical properties are largely governed by the reinforcing fibers, so that the mechanical properties are significantly different from those of the resin alone. It has been clarified that if (A) can form a domain diameter within the range of the present invention, it is possible to obtain a molded article having well-balanced mechanical properties. Further, depending on the combination of resins used, the resin (A)
In the present invention, forming a domain diameter within the range of the present invention may be more excellent in moldability (particularly fluidity during molding) than forming a domain without forming a domain.

On the other hand, if the resin (A) in the molded article forms a domain and the domain diameter falls below the lower limit of the present invention, the strong kneading for dispersing the resin (A) more than necessary is required. This means that the reinforcing fiber may be unnecessarily broken at that time, so that the object of the present invention may not be overcome. In addition, exceeding the upper limit
It means that the compatibility and dispersibility of the resin (A) and the resin (B) are inferior. Similarly, the mechanical properties of the obtained molded article are remarkably inferior, and the object of the present invention may not be able to be overcome.

More preferred resin (A) in molded article
Has a domain diameter of 0.1 to 40 μm, and more preferably 0.15 to 30 μm. In particular, it is preferable that the resin (A) has a domain diameter in the range of 0.2 to 15 μm.

The domain diameter of the resin (A) in such a molded article is represented by an average value of the measured values obtained by the following procedure.

(1) At least five sections are arbitrarily cut (or cut out) from the molded article.

(2) The above-mentioned sections are polished smoothly. Next, each cross section is observed using an optical microscope, and when less than 100 domains are observed in the cross section, all the domains are selected. When 100 or more domains are observed, 100 domains are optionally selected. select.

(3) For the selected domains, the diameter of each domain is measured using an optical microscope. In particular, when the boundaries between domains are unclear with an optical microscope, the measurement is performed by the method described in the method for measuring the domain diameter of the resin (A) in the molding material. In particular, in the case of a molded product, the domain diameter of the resin (A) in the molded product can sometimes be measured by observing the fracture surface of the broken molded product with a scanning electron microscope.

The cross section for measuring the domain is preferably a cross section perpendicular to the orientation direction of the reinforcing fibers. In this case, it is ideal to cut out the cross section so as to be perpendicular to each orientation direction of the reinforcing fiber, but simply, the apparent oblateness of the reinforcing fiber in the cross section and the true shape of the reinforcing fiber (for example, By comparing with a true circle, the apparent domain diameter in the cross section can be corrected and the domain diameter in a cross section perpendicular to the orientation direction of the true reinforcing fiber can be obtained.

When at least three types of resins (A), (B), and (C) are used in the molding material of the present invention, those resins have the following form [M
1] and [M2], and in a molded article obtained by molding the molding material, it is preferable that the resin is in the following form [N1] or [N2] and in the form [N3]. [M1]: The resin (A) forms a domain in the matrix of the resin (B), and the domain diameter is 0.4 to 1
Form to form a sea-island structure with a range of 5 mm. [M2]: The resin (C) forms a domain in the matrix of the resin (B), and the domain diameter is 0.1 to 5
A form in which a sea-island structure having a range of 00 μm is formed. [N1]: Form in which the resin (A) does not form a domain diameter in the matrix of the resin (B). [N2]: The resin (A) forms a domain in the matrix of the resin (B), and the domain diameter is 0.05 to
A form that forms a sea-island structure in the range of 50 μm. [N3]: Form in which the resin (C) forms a domain in the matrix of the resin (B) and forms a sea-island structure in which the domain diameter is in the range of 0.05 to 50 μm. Resin (C): A resin that forms an island structure among sea-island structures in a molded product and is different from resins (A) and (B).

The resin (C) in the molded product has the form [N3]
When it is within the range, it means that the compatibility (dispersibility) between the resin (C) and the resin (B) is excellent, and a molded article having well-balanced mechanical properties can be obtained. When the resin (C) in the molded product exceeds 50 μm, it means that the compatibility and dispersibility of the resin (C) and the resin (B) are poor, and the mechanical characteristics of the obtained molded product are poor, In some cases, the problems of the present invention cannot be overcome. In addition, the resin (C) in the molded article is 0.1%.
When it is less than 05 μm, especially the resin (B) and the resin (C)
When the compatibility with is poor, it means that it has gone through the molding step of kneading more than necessary, in the fiber reinforced molded product,
Shortening of the fiber length is not preferable because results such as inferior mechanical properties may be caused. More preferably, the domain diameter of the resin (C) in the molded article is from 0.1 to
40 μm, more preferably 0.15 to 3
The range is 0 μm. Especially, when the resin (C) is 0.2 to
It preferably has a domain diameter in the range of 15 μm.

For this purpose, the resin (C) in the molding material is preferably in the range of the form [M2]. When the domain diameter of the resin (C) in the molding material is less than 0.1 μm or more than 500 μm, it is difficult to bring the resin (C) into the range of the form [N3] in the molded article. The domain diameter of the resin (C) in a more preferable molding material is:
0.15 to 400 μm, more preferably,
It is in the range of 0.2 to 300 μm. In particular, it is preferable that the resin (C) has a domain diameter in the range of 0.25 to 100 μm.

The domain diameter of the resin (C) in the molding material and the molded article conforms to the method of measuring the domain diameter of the resin (A).

In order to obtain desired properties, the molding material of the present invention does not form a domain in each of the resins (A) to (C) or forms an island structure in the resin (A).
Other resins different from the resin (A) and the resin (C) formed in the same range as described above may be further included.

Further, when at least three kinds of resins are used in the molding material of the present invention, those resins are the above-mentioned form [M1] and the following form [M3] in the molding material, and the molding material is molded. In the molded article made of the resin, the resin may have the following form [N4]. [M3]: Form in which the resins (B) and (C) form a sea-sea structure. [N4]: Form in which the resins (B) and (C) form a sea-sea structure. Resin (C): A resin different from resins (A) and (B) that forms a sea structure among sea-sea structures in a molded article.

The resin (C) in the molded product has the above-mentioned form [N
In the case of 4], it means that the compatibility and dispersibility of the resin (C) and the resin (B) are similarly excellent, and a molded article having well-balanced mechanical properties can be obtained. For this purpose, the resin (C) in the molding material is preferably in the form [M3].

The sea-sea structure in the present invention refers to a structure in which one of the resins is not formed as an island as in a sea-island structure, although there is a resin interface, and the shape of the sea structure itself is not particularly limited. Absent.

The molding material of the present invention comprises a molding material containing reinforcing fibers (hereinafter referred to as molding material (a)) and a molding material containing no reinforcing fibers (hereinafter referred to as molding material (b)).
And may be composed of As a specific example, for example, a pellet made of a molding material (a) and a molding material (b)
It is possible to obtain a molded product by mixing with a pellet consisting of and then re-pelletizing it into one type with an extruder or the like, or molding it directly with dry blending without re-pelletizing. it can. Preferably, dry blending as it is is preferable because a molded product can be obtained without an extra step. By molding with such a configuration, not only can the productivity of the molding material of the present invention be improved, but also it is possible to flexibly cope with a case where the mixing ratio of the reinforcing fibers is changed.

In particular, the molding material of the present invention contains at least the resins (A) and (B) as the resin in the molding material (a), and at least the resin (B) and / or the resin in the molding material (b). Alternatively, when (C) is blended, even if the compatibility between the resin (A) and the resin (C) is extremely poor, separate molding materials are interposed with the resin (B) having a certain degree of compatibility with both. It is preferable to adopt the form of mixing because stable molding can be performed even when molding is difficult only with the combination of the resin (A) and the resin (C) alone.

Here, the resin used in the present invention, which contains at least the resins (A) and (B), has the above-mentioned form [M1] in the molding material. It is preferable that (A) is blended in the range of 0.5 to 50% by weight. It is more preferably in the range of 1 to 45% by weight, and even more preferably in the range of 2 to 40% by weight. In particular, it is preferable to be blended in the range of 3 to 30% by weight.

The resin used in the present invention containing at least the resins (A), (B) and (C) has the above-mentioned forms [M1] and [M2] in the molding material. When the weight% is used, the content of the resin (C) is 0.5 to
It is preferred that it is blended in the range of 50% by weight. It is more preferably in the range of 1 to 45% by weight, and even more preferably in the range of 2 to 40% by weight. In particular, it is preferable to be blended in the range of 3 to 30% by weight.

In the present invention, the resins (A), (B) and (C) in the molded article are derived from the resins (A), (B) and (C) in the molding material, respectively. Is generally supported. That is, for example, the resin (A) of the molding material is the resin (A) of the molded product. But,
Rare examples include cases where the above-mentioned origins and correspondences are not established or various forms ([M1] to [M3], [N
1] to [N4]) may not correspond.

As the resin (A) used in the present invention, for example, a phenol resin, a vinyl resin, an amide resin,
At least one selected from urethane-based resins, epoxy-based resins, liquid-crystalline resins, acrylic-based resins, alcohol- or water-soluble resins, and resins having a lower molecular weight than the most compounded resin in the molding material or molded article Preferably it is. When at least one of the above resins is used as the resin (A), not only the moldability (fluidity during molding) but also the productivity of the molding material, which is an effect of the present invention, can be highly exhibited.

The phenolic resin refers to a resin obtained by homogenizing or copolymerizing at least a component having a phenolic hydroxyl group. For example, various phenolic resins (phenol novolak, cresol novolak, octylphenol, phenylphenol, naphthol novolak, phenolaralkyl, Examples thereof include naphthol aralkyl, phenol resole, and the like, and modified phenol resins (alkyl benzene modification (particularly, xylene modification), cashew modification, terpene modification, and the like). Preferred phenolic polymers include phenol novolak resins and phenol aralkyl resins.

Particularly preferred phenolic resins used in the present invention include phenol novolak, xylene-modified phenol (particularly meta-xylene-modified phenol), and terpene-modified phenol. And excellent moldability due to its high affinity.

These phenolic resins preferably have a weight average molecular weight in the range of 200 to 2,000. When the molecular weight is less than 200, thermal stability is inferior, so that it volatilizes during molding and generates defects such as voids in molded articles. On the other hand, if the molecular weight exceeds 2,000, the thin-wall moldability (flowability at the time of molding) is inferior, and the effect of the present invention cannot be sufficiently exhibited. More preferably 300 to
1,800, more preferably 400-150.
It is in the range of 0. Here, the weight-average molecular weight was measured by gel permeation chromatography (GPC) using a low angle light scattering photometer (LALLS) using a laser as a detector.

The vinyl resin refers to a resin obtained by homogenizing or copolymerizing at least a component formed from a vinyl monomer, and includes, for example, a vinyl alcohol resin, a vinylpyrrolidone resin, and a styrene resin. Such a vinyl alcohol-based resin refers to a resin obtained by copolymerizing at least a vinyl alcohol component, for example, vinyl alcohol, vinyl acetate, an olefin such as ethylene, a copolymer resin of aromatic vinyl and the like, and the like. Examples of preferred vinyl alcohol-based resin,
A vinyl alcohol / ethylene copolymer resin having excellent heat resistance is exemplified. Further, such a vinylpyrrolidone-based resin refers to a resin obtained by homogenizing or copolymerizing at least a vinylpyrrolidone component, and examples thereof include polyvinylpyrrolidone. The details of the styrene resin are based on the description of the resin (B) and / or (C).

Representative examples of the amide resin include a water-soluble polyamide and an alcohol-soluble polyamide. Representative examples of such a water-soluble polyamide include polyamide resins containing an alkylene oxide component and a tertiary amine component in the molecular chain. Examples of the polyalkylene oxide component introduced into the molecular chain of the polyamide resin include those obtained by modifying a part of polyethylene glycol, polypropylene glycol, or the like with diamine or dicarboxylic acid and copolymerizing them. Examples of the tertiary amine to be introduced into the molecular chain of the polyamide resin include aminoethylpiperazine and bisaminopropylpiperazine when introduced into the main chain, and α-
Dimethylamino ε-caprolactam.

Examples of the alcohol-soluble polyamide include, for example, nylon 6/66/610, nylon 6/66/612, nylon 6/66/610/12 copolymer, and hydrogen in an amide group substituted with a methoxymethyl group. And nylon 6/66/612 and nylon 6/66/6 which are particularly excellent in solution stability when dissolved in alcohol.
A 10/12 copolymer, nylon 8, is preferred. In addition,
Representative examples of the alcohol include, for example, methanol, ethanol, (iso) propanol, (iso) butanol, etc., and mixtures thereof, mixtures with other organic solvents, and mixtures of these with water. Is also included.

Examples of the urethane resin include isocyanates such as 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, tolylene diisocyanate, and isophorone diisocyanate; Butylene glycol, 1,
Glycols such as 6-hexanediol and bishydroxyethoxybenzene, polyethylene adipate, polycaprolactone, poly (hexamethylene adipate)
Typical examples thereof include polyester diols such as polyesters, and thermoplastic polyurethane resins obtained by reaction with diols such as polyoxytetramethylene glycol.

Such an epoxy resin has an oxirane ring, and may be bifunctional or trifunctional or higher. In order to achieve higher elongation, a bifunctional epoxy resin is used as a main component. The amount is preferably at least 20 parts by weight, more preferably at least 30 parts by weight, based on all epoxy resin components.

Further, the heat resistance is improved by adding a trifunctional or higher functional epoxy resin. However, the elongation decreases when the amount of the trifunctional or higher functional epoxy resin is increased. It is preferably at most 30 parts by weight, more preferably at most 20 parts by weight, based on all epoxy resin components.

As such a bifunctional epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
Brominated bisphenol A type epoxy resin, epoxy resin obtained by reacting dihydroxynaphthalene with epichlorohydrin, epoxy resin obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with epichlorohydrin, 4,4′-dihydroxybiphenyl or An epoxy resin obtained by reacting the substituted derivative with epichlorohydrin is exemplified. Examples of such trifunctional or higher functional epoxy resins include novolak type epoxy resins, epoxy resins made from a copolymer of a phenol compound and dicyclopentadiene, tetrakis (glycidyloxyphenyl) ethane, and tris (glycidyloxyphenyl). Glycidyl ether-type epoxy resins such as methane, glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminocresol, and tetraglycidylxylenediamine are exemplified.

[0052] The epoxy resin used in the present invention may contain a curing agent.
Aromatic amines having active hydrogen such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethylenetriamine, triethylene Aliphatic amines having active hydrogen such as ethylenetetramine, isophoronediamine, bis (aminomethyl) norbornane, bis (4-aminocyclohexyl) methane, dimer acid ester of polyethyleneimine; epoxy compounds to these amines having active hydrogen; Acrylonitrile, phenol and formaldehyde, modified amines obtained by reacting compounds such as thiourea, dimethylaniline, dimethylamine,
Tertiary amines having no active hydrogen such as 2,4,6-tris (dimethylaminomethyl) phenol and 1-substituted imidazole, dicyandiamide, tetramethylguanidine, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, carboxylic anhydrides such as methylnadic anhydride, polycarboxylic acid hydrazides such as adipic hydrazide and naphthalenedicarboxylic acid hydrazide, polyphenol compounds such as novolak resins, esters of thioglycolic acid and polyols And a Lewis acid complex such as a boron trifluoride ethylamine complex, and an aromatic sulfonium salt.

[0053] Such a curing agent may be combined with an appropriate curing aid to enhance the curing activity. For example,
To dicyandiamide, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (3-chloro-4-methylphenyl) -1,1 Examples of combining urea derivatives such as dimethyl urea and 2,4-bis (3,3-dimethylureido) toluene as curing aids, combining tertiary amines as carboxylic anhydrides and novolak resins as curing aids Examples are given. Further, a boron trifluoride / amine complex can also be used. Compounds used as curing assistants often have the ability to cure epoxy resins alone.

In the epoxy resin used in the present invention, in addition to an epoxy resin component, a curing agent component, a curing aid, and the like, a polymer compound, organic or inorganic particles, and the like can be used as optional components.

Such a liquid crystalline resin refers to a resin capable of forming anisotropy when melted. Examples of the liquid crystal resin include liquid crystal polyester, liquid crystal polyester amide, liquid crystal polycarbonate, liquid crystal polyester elastomer, and the like. Among them, those having an ester bond in a molecular chain are preferable, and particularly, liquid crystal polyester, liquid crystal polyester amide, etc. Is preferably used. In particular, when the liquid crystal resin is mixed with a resin having a reactivity with the liquid crystal resin (eg, a polyamide resin), the terminal group (eg, an amino terminal group) of the resin having the reactivity is
For example, it is preferable to seal with an acid anhydride or the like.

The liquid crystalline resin which can be preferably used in the present invention is a liquid crystalline polyester containing a structural unit composed of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and a liquid crystalline resin containing an ethylenedioxy unit as an essential component. Polyester can also be used preferably.

The logarithmic viscosity of the liquid crystalline resin used in the present invention can be measured in pentafluorophenol. At this time, 0.5 to 15 dl / g is preferable as a value measured at 60 ° C. at a concentration of 0.1 g / dl, and 1 to 3 dl / g
g is particularly preferred.

Further, the melt viscosity of the liquid crystalline resin in the present invention is preferably 0.5 to 500 Pa · s, particularly 1 to 25 Pa · s.
0 Pa · s is more preferred. When a composition having better fluidity is to be obtained, the melt viscosity should be 50 Pa ·
It is preferably set to s or less.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second). Here, the melting point (Tm) is defined as the endothermic peak temperature (Tm1) observed when the polymerized polymer is measured from room temperature under a heating condition of 20 ° C./min.
After holding at a temperature of Tm1 + 20 ° C. for 5 minutes, once cooling to room temperature under a temperature-lowering condition of 20 ° C./min, and then measuring again at a temperature-raising condition of 20 ° C./min, an endothermic peak temperature (Tm2) observed. Point to. The melting point of the liquid crystalline resin is not particularly limited, but is preferably 3 from the viewpoint of dispersibility in other resins.
It is 40 ° C. or lower, more preferably 330 ° C. or lower.

The method for producing the liquid crystalline polyester used in the present invention is not particularly limited, and it can be produced according to a conventional polyester polycondensation method.

As the acrylic resin, for example, polyacrylic acid, polymethacrylic acid, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate,
Octyl methacrylate, hydroxyl acrylate, hydroxyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, polyacrylamide, styrene / acrylic acid copolymer resin, styrene / methyl methacrylate copolymer resin, ethylene / methacrylic acid copolymer resin, and the like. And copolymer resins and mixtures thereof, and salts thereof (eg, alkali metal salts and alkaline earth metal salts).

As the resin (B) and / or the resin (C) used in the present invention, both a thermosetting resin and a thermoplastic resin can be used. This is preferable because it is possible to perform press molding or injection molding with excellent impact strength of the product and high molding efficiency.

Examples of the thermosetting resin include unsaturated polyester, vinyl ester, epoxy, phenol (resole type), urea melamine, polyimide, etc.
These copolymers, modified products, and resins in which two or more kinds are mixed can be used.

Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and liquid crystal polyester; polyolefin resins; styrene resins; polyoxymethylene, polyamide, polycarbonate, and polymethylene. Methacrylate, polyvinyl chloride, polyphenylene sulfide, polyarylate, polyphenylene ether, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone,
Polyketone, polyetherketone, polyetheretherketone, polyethernitrile, phenol (novolak type, etc.), amide-based, urethane-based, olefin-based, styrene-based, ester-based, butadiene-based thermoplastic elastomers, etc. Merging, denaturing, and
Resins blended with two or more types can also be used. Further, in order to further improve impact resistance, a resin obtained by adding an elastomer or a rubber component to the above resin can be used.

The thermoplastic resin in the present invention may be a crystalline thermoplastic resin (hereinafter referred to as a crystalline resin),
An amorphous thermoplastic resin (hereinafter, referred to as an amorphous resin) may be used, but when the resin is an amorphous resin, the effects of the present invention can be used to the maximum. Amorphous resin is generally superior in dimensional stability to crystalline resin, but has a high melt viscosity, so when used as a resin in a fiber-reinforced molding material, the productivity of the molding material is extremely poor and the cost is high. Was common. However, by adopting the form [N1] or [N2] in combination with the resin (A) of the present invention, the dispersibility of the reinforcing fibers in a molded article, which was difficult with an amorphous resin, is reduced. Not only can a molded article with improved mechanical properties be obtained, but also the productivity of molding material can be remarkably improved.

It is preferable that at least one of styrene resin, polycarbonate resin, and polyphenylene ether resin is blended as the amorphous resin. In addition, two or more amorphous resins may be used in combination,
In some cases, an amorphous resin and a crystalline resin may be used in combination.

The styrenic resin contains a unit formed from styrene and / or a derivative thereof (these may be collectively referred to as an aromatic vinyl monomer).

Preferred examples of the styrene resin include a styrene (co) polymer and a rubber-reinforced styrene (co).
Polymers. Examples of the styrene (co) polymer include polymers obtained by polymerizing one or more aromatic vinyl monomers, and one or more aromatic vinyl monomers that can be copolymerized therewith. And copolymers obtained by copolymerizing one or more monomers. The rubber-reinforced styrene (co) polymer has a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer and a (co) polymer containing a styrene monomer. One having a structure in which the union is non-grafted to the rubbery polymer.

Examples of the graft structure include a rubber-reinforced graft polymer obtained by graft-polymerizing one or more aromatic vinyl monomers onto a rubbery polymer, and an aromatic vinyl-based monomer onto a rubbery polymer. And a graft copolymer obtained by graft-copolymerizing one or two or more monomers and one or two or more monomers copolymerizable therewith.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, pt-butylstyrene, vinyltoluene and o-ethylstyrene. However, styrene is particularly preferred.

Representative examples of the monomer copolymerizable with the aromatic vinyl monomer include a (meth) acrylate monomer, a vinyl cyanide monomer and the like. Examples of the (meth) acrylate-based monomer include methyl, ethyl, propyl, n-butyl and i-butyl esters of acrylic acid and methacrylic acid, and methyl methacrylate is preferably used. Examples of such a vinyl cyanide compound include acrylonitrile, methacrylonitrile, and ethacrylonitrile, and acrylonitrile is preferably used. If necessary, other vinyl monomers such as maleimide, N-methylmaleimide, N
-Maleimide monomers such as phenylmaleimide can also be used.

As the above rubbery polymer, those having a glass transition temperature of 0 ° C. or less are preferable, such as butadiene rubber, styrene / butadiene copolymer rubber (SBR), acrylonitrile / butadiene copolymer rubber (NBR) and the like. Diene rubbers, acrylic rubbers such as polybutyl acrylate, and polyolefin rubbers such as ethylene / propylene / non-conjugated diene terpolymer rubber (EPDM). Among them, polybutadiene, ethylene / propylene / non-conjugated Diene terpolymer rubber (EPDM) is preferably used.

Preferred styrene resins in the present invention include styrene polymers such as PS (polystyrene),
Rubber-reinforced styrene-based polymers such as HIPS (high impact polystyrene), styrene-based copolymers such as AS (acrylonitrile / styrene copolymer), AES (acrylonitrile / ethylene-propylene / non-conjugated diene rubber / styrene copolymer), ABS (acrylonitrile / butadiene / styrene copolymer), MBS (methyl methacrylate /
Rubber-reinforced (co) polymers such as butadiene / styrene copolymer) and ASA (acrylonitrile / styrene / acrylic rubber copolymer). Among them, styrene-based polymers such as PS (polystyrene), and AS ( Styrene-based copolymers such as acrylonitrile / styrene copolymer),
ABS (acrylonitrile / butadiene / styrene copolymer) and ASA (acrylonitrile / styrene / acrylic rubber copolymer) are preferred.

The properties of the vinyl (co) polymer are not limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, 30 ° C.
Measurement) is 0.4 to 0.65 dl / g, especially 0.45 to
In the range of 0.55 dl / g, an N, N-dimethylformamide solvent, when measured at 30 ° C., 0.35 dl / g.
A resin composition in the range of from 0.85 dl / g to 0.45 dl / g, particularly from 0.45 to 0.7 dl / g, is preferred, since a resin composition having excellent impact resistance and moldability can be obtained.

The method for producing the vinyl (co) polymer is not particularly limited, and includes bulk polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization.
Conventional methods such as a suspension polymerization method and a solution-bulk polymerization method can be used.

As such a polycarbonate resin, for example, a viscosity average molecular weight obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester is 10,000 to 1,000,000 (preferably 1 to 1).
5,000 to 30,000) aromatic homo or copolycarbonate resins.

As a specific example of the dihydric phenol compound mentioned herein, 2,2-bis (4-hydroxyphenyl)
Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4 -Hydroxyphenyl)
Butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,
5-diethylphenyl) propane, 2,2-bis (4-
(Hydroxy-3,5-diethylphenyl) propane,
Examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane and 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, which can be used alone or as a mixture.

As such a polyphenylene ether-based resin, a polymer having an intrinsic viscosity of 0.01 to 0.8 dl / g measured at 30 ° C. in chloroform is preferably used. Specifically, poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol /
2,4,6-trimethylphenol copolymer, 2,6-
A dimethylphenol / 2,3,6-triethylphenol copolymer may be mentioned as an example.

Two or more of these amorphous resins may be used in combination. Specifically, ABS resins, ASA resins or combinations of AS resins and polycarbonate resins, polyphenylene ether resins and polystyrene resins or impact-resistant polystyrene resins And a combination of a polycarbonate resin with a polystyrene resin or a high-impact polystyrene resin.

Further, in order to impart other properties, such as chemical resistance and fluidity during molding, a part of those amorphous resins or a combination of two or more amorphous resins (usually resin Up to 70% by weight of the components, preferably 60%
% By weight, particularly preferably 50% by weight or less) can be replaced by a crystalline resin. Examples of such a crystalline resin include a polyamide resin, a polyester resin, a polyphenylene sulfide resin, a polyolefin resin, a liquid crystal resin, and the like. Specifically, a polycarbonate resin or a combination of a polycarbonate resin and an ABS resin or a polycarbonate resin And a combination of an ASA resin and a combination of polybutylene terephthalate and / or polyethylene terephthalate,
Combination of ABS resin with nylon 6 and / or nylon 66 and / or aromatic-containing polyamide resin, combination of polycarbonate resin with nylon 6 and / or nylon 66, polycarbonate resin or combination of polycarbonate resin and ABS resin or polycarbonate resin Preferred examples include a combination of a liquid crystal resin with a combination of a polyphenylene ether resin and a liquid crystal resin, a combination of a polyphenylene ether resin with a nylon 6 and / or a nylon 66, and a combination of a polyphenylene ether resin with a liquid crystal resin.

On the other hand, when a crystalline resin is used, it is possible to further improve the dispersibility of the reinforcing fibers in the molded article and further improve the productivity of the molding material. As the crystalline resin, polyamide resin, polyester resin,
Polyphenylene sulfide resin, polyolefin resin,
At least one of a polyacetal resin and a liquid crystalline resin
It is preferable that the types are blended. Two or more of these crystalline resins may be used in combination. Specifically, a combination of a polyamide resin and a polyolefin resin, a combination of a polyamide resin and a polyester resin, a combination of a polyamide resin and a polyacetal resin, and a polyamide resin Preferred examples include a combination of a liquid crystal resin, a combination of a polyester resin and a polyolefin resin, a combination of a polyester resin and a liquid crystal resin, and a combination of a polyolefin resin and a liquid crystal resin.

Examples of such polyester resins include polycondensates of dicarboxylic acids and glycols, ring-opening polymers of cyclic lactones, polycondensates of hydroxycarboxylic acids, and polycondensates of dibasic acids and glycols. Specifically, polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexane dimethylene terephthalate resin, and polyethylene-1,2-bis (phenoxy) ethane- In addition to 4,4'-dicarboxylate resin, etc., in addition to polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate resin,
Copolymers and mixtures of polyethylene isophthalate / terephthalate resin, polybutylene terephthalate / isophthalate resin, polybutylene terephthalate / decanedicarboxylate resin, and polycyclohexane dimethylene terephthalate / isophthalate resin are exemplified.

Particularly preferred polyester resins for the present invention include polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin and polyethylene naphthalate resin, and more preferably polyethylene terephthalate (PE).
T) resin, polybutylene terephthalate (PBT) resin.

The molecular weight of such a polyester resin is not particularly limited, but an intrinsic viscosity of usually 0.1 to 3 measured at 25 ° C. using a phenol / tetrachloroethane 1: 1 mixed solvent can be used. But preferably
It is 0.25 to 2.5, particularly preferably 0.4 to 2.25.

The polyolefin resin is a polyolefin resin having an α-olefin having usually about 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, pentene-1, hexene-1, and octene-1, as a main structural unit. It is united. Also included are homopolymers and copolymers of these α-olefins, and copolymers thereof with vinyl acetate, acrylic acid esters, (anhydrous) unsaturated carboxylic acids, unsaturated silane compounds, and the like. Preferred polyolefin resins include polyethylene, polypropylene, polybutylene, ethylene / propylene copolymer and the like, and these can be used alone or as a mixture.

As the crystalline resin in the present invention, it is particularly preferable to use a polyamide resin from the viewpoint of the interfacial adhesion of the reinforcing fibers. The polyamide resin useful in the present invention is a nylon resin having a melting point of 150 ° C. or more and having excellent heat resistance and strength. Specific examples thereof include nylon 6, nylon 66, nylon 46, and nylon 61.
0, nylon 612, nylon 9T, nylon 66/6
T, nylon 6T / 6, nylon 6I / 6, nylon 6
6 / 6T, nylon 66 / 6I, nylon 12 / 6T,
Nylon 66 / 6T / 6I, nylon 6T / 6I, nylon 6T / M5T, nylon XD6, and mixtures or copolymers thereof can be preferably used. Further, according to the necessity of improving properties (especially impact resistance), acid-modified olefin polymers such as maleic anhydride, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non- Conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, AB
Addition of one or a mixture of two or more selected from elastomers such as olefin copolymers such as S and ASA, polyester polyether elastomers and polyester polyester elastomers, and using a resin further having desired properties. Can also.

The degree of polymerization of these polyamide resins is not particularly limited. However, in order to obtain a thin-walled molded product, those having excellent fluidity during molding are preferable, and the relative viscosity of sulfuric acid ηr is 1.
Polyamide resins in the range of 5-2.7 are preferred. η
When r exceeds 2.7, the fluidity during molding is poor, and the fluidity during molding is not effectively exhibited. In particular, when a thin-walled molded product is molded, a flow mark or reinforced fiber floats on the molded product surface, impairs the surface smoothness, generates a strong weld line, and can provide a product with significantly poor appearance quality. Sex comes out. If ηr is less than 1.5, the fluidity is excellent, but not only the mechanical properties (particularly impact strength, elongation, etc.) are poor, but also a large amount of gas is generated during molding due to the large amount of low molecular weight components. However, it is not preferable because the moldability may be adversely affected. More preferably η
r is in the range of 1.8 to 2.6, more preferably ηr
Is in the range of 2 to 2.5. ηr
Is particularly preferably a polyamide resin having a range of 2.1 to 2.4. Here, the sulfuric acid relative viscosity ηr is obtained by dissolving 98% sulfuric acid so that the solution concentration becomes 1 g / 100 ml, measuring the falling velocity with an Ostwald viscometer in a 25 ° C. constant temperature bath, and obtaining a sample solution for 98% sulfuric acid. Is expressed by a viscosity ratio (ratio of falling seconds).

Further useful as the polyamide resin used in the present invention are aliphatic nylon or a mixture or copolymer of an aliphatic polyamide resin and an aromatic-containing polyamide resin. When an aliphatic polyamide resin is used, thin-wall moldability (fluidity during molding) can be further enhanced, and the resulting molded article has excellent mechanical properties. Further, when an aromatic-containing polyamide resin is used, shrinkage of the molded article after molding is suppressed, and defects in appearance such as sink marks and bulging of weld portions of the obtained molded article can be minimized. When these aliphatic polyamide resins and aromatic-containing polyamide resins are used in combination, the mechanical properties (impact strength, strength, etc.) having both of the above properties
This is preferable because a material having both a balance between the appearance and the appearance quality and having excellent thin-wall moldability can be obtained.

Here, the aliphatic polyamide resin refers to a resin having no aromatic ring in the molecular chain. Particularly useful as such an aliphatic polyamide resin are nylon 6, nylon 66, nylon 46, nylon 610, a copolymer of nylon 6 / nylon 66, and a mixture thereof. 6,
Nylon 66.

The aromatic-containing polyamide resin refers to a resin having an aromatic ring in the molecular chain. Generally, one of the raw materials such as diamine or dicarboxylic acid has an aromatic ring. , The other being α, ω-linear aliphatic. Particularly useful as the aromatic-containing polyamide resin are nylon XD6 and nylon 6T / 6.
I, nylon 6I / 6, nylon 66 / 6I / 6, and mixtures thereof, and particularly useful are nylon 6T / 6I, nylon 66 / 6I /
6. Polymethaxylylene adipamide, which is a condensation polymer of metaxylylenediamide and adipic acid.

As the preferred thermoplastic resin in the present invention, a thermoplastic elastomer (hereinafter referred to as TPE) can also be mentioned. Such TPEs include, for example, polystyrene, polyolefin, vinyl chloride, polyurethane, polyester, polyamide, chlorinated polyethylene, polybutadiene, polyisoprene,
Fluorine-based TPE and the like can be mentioned. Among them, polyurethane, polyester, and polyamide TPEs can be mentioned as TPEs that exhibit the effects of the present invention more highly.

Such a polyurethane-based TPE refers to a polyurethane TPE having a urethane group in a molecular chain, and generally comprises a hard segment composed of an isocyanate component and a soft segment composed of an ester or ether component. Many. In particular, it is preferable that the soft segment is composed of an ester component because the compatibility is excellent when an epoxy resin is used as the resin (A).

The polyester type TPE has an ester group in a molecular chain, and generally has an ester component (eg, polybutylene terephthalate).
And a soft segment composed of an ether component.

The polyamide TPE has an amide group in the molecular chain, and is generally often composed of a hard segment composed of an amide component and a soft segment composed of an ether component.

Many of the basic properties of these TPEs are:
The hardness is determined by the ratio of the hard segment (or the soft segment), which is determined by the type of the component to be used. In the present invention, the type of the component to be used and the ratio of the segment can be arbitrarily selected depending on the application. .

Resins (B) and (C) used in the present invention
There is no particular limitation on the combination with, for example, resin (B)
When both the resin (C) and the resin (C) are thermoplastic resins, as described above, the combination of the resin (B) and the resin (C) both being an amorphous resin, the resin (B) and the resin (C) ) Is a crystalline resin and the other is an amorphous resin, wherein the resin (B) and the resin (C)
Can be selected from combinations in which the desired properties are obtained from combinations in which both are crystalline resins.

The preferred combination of the resin (B) and the resin (C) in the present invention is a combination in which both the resin (B) and the resin (C) are amorphous resins, and a combination of the resin (B) and the resin (B). One of (C) is a crystalline resin and the other is an amorphous resin. In particular, the resin (B) is an amorphous resin and the resin (C) is a crystalline resin. Is preferred. By combining these, the effects of the present invention, such as the productivity and moldability of the molding material, the mechanical properties of the molded article, and the appearance quality, can be further enhanced.

In particular, the above-mentioned phenol resin, amide resin or liquid crystalline resin is used as the resin (A), and the above-mentioned styrene resin, polycarbonate resin, polyphenylene ether is used as the resin (B) and / or the resin (C). It is preferable to use at least one of a resin, a polyamide resin, a polyester resin, a polyolefin resin, and a liquid crystalline resin because the effects of the present invention can be maximized.

Here, examples of preferred combinations of the resin (B) and the resin (C) include the following. 1. 1. Combination of polycarbonate resin and styrene resin (preferably AS, ABS, ASA, PS, HIPS) 2. Combination of polyphenylene ether resin and styrene resin (preferably PS, HIPS) 3. Combination of polyphenylene ether resin and polyamide resin (preferably nylon 6, nylon 66, aromatic-containing polyamide) 4. Combination of polyamide resin (preferably nylon 6, nylon 66) and polycarbonate resin Polyamide resin (preferably nylon 6, nylon 66) and styrene resin (preferably AS, ABS, A
5. Combination with SA, PS, HIPS) 6. Combination of polyamide resin (preferably nylon 6, nylon 66) and polyolefin resin (preferably polyethylene) 7. Combination of polyamide resin and liquid crystal resin (preferably liquid crystal polyester) Combination of polyolefin resin (preferably polypropylene, polyethylene) and liquid crystal resin (preferably liquid crystal polyester) When the above-mentioned epoxy resin is used as resin (A), the above-mentioned TPE is compounded as resin (B). It is also preferable that the effects of the present invention can be maximized.

Further, in addition to the resins (B) and (C), another resin may be contained. In such a case, examples of preferable combinations include the following.

9. Polycarbonate resin, styrene resin (preferably AS, ABS, ASA, PS, HIP
9. S) and a combination with a polyester resin (preferably polybutylene terephthalate, polyethylene terephthalate) 10. Combination with polycarbonate resin, styrene-based resin (preferably AS, ABS, ASA, PS, HIPS) and liquid crystal resin (preferably liquid crystal polyester) Combination with polyphenylene ether resin, styrene resin (preferably PS, HIPS), polyamide resin (preferably nylon 6, nylon 66, aromatic-containing polyamide), and liquid crystal resin (preferably liquid crystal polyester) It is not necessary that the order of B), (C) and the other resins be the same as the order of the above-mentioned combinations (1 to 8, 9 to 11). For example, taking item 1 as an example, even if the resin (B) is a polycarbonate resin and the resin (C) is a combination of a styrene resin, the resin (B) is a styrene resin and the resin (C) is a polycarbonate resin. It may be a combination of resins.

The molding material of the present invention contains reinforcing fibers. In this case, when the weight of the molding material is 100% by weight, the amount of the reinforcing fibers is preferably 3 to 70% by weight. If the amount of the reinforcing fibers is less than 3% by weight, the mechanical properties of the molded product may be insufficient, which is not preferable. On the other hand, when the amount of the reinforcing fiber exceeds 70% by weight, not only molding becomes difficult but also the appearance quality of the obtained molded product may be inferior. More preferably, it is 5 to 55% by weight, and still more preferably 7 to 40% by weight. Especially preferably, it is 9 to 35% by weight.

The reinforcing fibers usable in the present invention include carbon fibers such as polyacrylonitrile (PAN), pitch (isotropic, mesophase, etc.), cellulose (viscose rayon, cellulose acetate, etc.), and vapor phase growth. Fiber, glass fiber such as S-glass, E-glass, aramid fiber, PBO fiber, inorganic fiber such as boron fiber, silicon carbide fiber and silicon nitride fiber, metal fiber such as stainless steel fiber and copper fiber, Examples thereof include organic fibers such as polyester fibers, nylon fibers, and polyphenylene sulfide fibers, and fibers obtained by subjecting these to post-processing such as metal coating. In the present invention, these reinforcing fibers may be used alone or in combination of two or more.

In the case of post-processing such as metal coating of the metal-coated fiber, the metal to be coated can be nickel, copper, silver, gold, or the like. Coated on the fiber. The fibers to be coated are not particularly limited as described above, but among them, strength and elasticity are balanced at a high level,
A carbon fiber having a small specific gravity is preferable. There is no particular limitation on the method of coating the metal fibers, but it is preferable that the metal fibers be coated with high adhesion strength by plating by electrolysis or electroless, CVD, PVD, vapor deposition, or the like.

The reinforcing fiber of the present invention has an average single fiber diameter of 1 to 1.
It is preferably 20 μm, more preferably 2 to 17 μm, and still more preferably 3 to 12 μm. In particular, the thickness is preferably 4 to 10 μm. If the average single fiber diameter is less than 1 μm, it becomes difficult to impregnate the resin into the reinforcing fiber bundle, which causes problems such as poor dispersibility of the reinforcing fiber in the molded product. On the other hand, when the average single fiber diameter is 20
If it exceeds μm, the mechanical properties of the reinforcing fibers are inferior, and the desired reinforcing effect cannot be obtained.

Such reinforcing fibers include coupling agents such as silane coupling agents, aluminate coupling agents, titanate coupling agents, urethane resins, epoxy resins, polyester resins, styrene resins, olefin resins, and amide resins. A resin surface-treated with a resin, an acrylic resin, a phenol resin, a liquid crystal resin, or the like can also be used.

As such a reinforcing fiber, a PAN-based, pitch-based, rayon-based or the like carbon fiber is preferable, and a PAN-based carbon fiber excellent in balance of strength, elastic modulus, price and the like is particularly preferable. In addition, metal-coated carbon fibers in which carbon fibers are coated with a metal such as nickel or copper are also included in the carbon fibers.

The carbon fiber used in the present invention preferably has a crystal size (hereinafter referred to as Lc) measured by a wide-angle X-ray diffraction method in a range of 1 to 4 nm. L
When c is less than 1 nm, carbonization or graphitization of the carbon fiber is not sufficient, and the conductivity of the carbon fiber itself becomes low.
Due to this, the conductivity of the obtained molded product may be poor, which is not preferable. On the other hand, when Lc exceeds 4 nm, carbonization or graphitization of the carbon fiber is sufficient, and the carbon fiber itself is excellent in conductivity, but is fragile and easily broken. Due to this, the fiber length in the molded article becomes short, and high conductivity cannot be expected, which is not preferable. More preferably, it is in the range of 1.3 to 3.5 nm,
More preferably, it is in the range of 1.6 to 3 nm. Particularly preferably, the thickness is in the range of 1.8 to 2.5 nm. The measurement of Lc by the wide-angle X-ray diffraction method was carried out according to the 117th Committee of the Japan Society for the Promotion of Science, Carbon, 36, p25 (196).
This was performed by the method described in 3).

The carbon fiber has a surface functional group content (O / C), which is the ratio of the number of oxygen (O) and carbon (C) atoms on the carbon fiber surface measured by X-ray photoelectron spectroscopy.
It is preferably in the range of 0.02 to 0.2. (O /
When C) is smaller than 0.02, it means that the carbon fiber surface has very few functional groups that contribute to adhesion to the resin. Poor adhesion between the carbon fiber and the resin is not preferable because desired mechanical properties cannot be obtained. Conversely, (O /
When C) is greater than 0.2, the surface treatment of the carbon fiber surface by an electrolytic treatment with an acidic aqueous solution or an alkaline aqueous solution is performed more than necessary, and the crystal structure of carbon or graphite is destroyed. It means that a fragile layer is formed on the fiber surface. In this case, the contact resistance at which the carbon fibers are in contact with each other increases, and it is not preferable because high conductivity cannot be expected in the molded product.

Further, when (O / C) is in the range of 0.02 to 0.2, favorable effects other than the adhesiveness between the carbon fiber and the resin, such as the dispersibility of the carbon fiber in the molded article, are obtained. Bring. (O / C) is more preferably in the range of 0.03 to 0.17, and still more preferably in the range of 0.04 to 0.15. Especially, the range of 0.05 to 0.13 is preferable.

The surface functional group (O / C) was measured by X-ray photoelectron spectroscopy according to the following procedure. In the present invention, measurement was performed using ESCA-750 manufactured by Shimadzu Corporation, and the sensitivity correction value was 2.85.

(1) First, carbon fibers from which a sizing agent or the like has been removed with a solvent are spread and arranged on a copper sample support, the photoelectron escape angle is set to 90 °, and MgK is used as an X-ray source.
Using α1,2, 1 × 10 ⁻⁶ Pa in the sample chamber
(1 × 10 ⁻⁸ Torr).

(2) The kinetic energy value of the main peak of _C1S is used as a correction of the peak accompanying the charging at the time of measurement. E. FIG. To 28
Adjust to 4.6 eV. The C _1S peak area is 282 to 2
It is determined by drawing a straight base line in the range of 96 eV. The O _1S peak area is determined by drawing a linear baseline in the range of 528 to 540 eV.

(3) Here, the surface functional group content (O / C) is calculated from the ratio of the O _1S peak area to the C _1S peak area as an atomic number ratio using a sensitivity correction value unique to the apparatus.

The carbon fiber has a surface functional group (O / C)
Is in the range of 0.02 to 0.2, the carbon fiber may be subjected to electrolytic treatment in an acidic aqueous solution or an alkaline aqueous solution, but it is easier to control (O / C) to a more preferable range. It is preferable that the electrolytic treatment is performed in an acidic aqueous solution. The preferred acidic aqueous solution used is not particularly limited as long as it shows acidity in the aqueous solution, such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, inorganic acids such as carbonic acid, acetic acid, butyric acid,
Examples thereof include organic acids such as oxalic acid, acrylic acid, and maleic acid, and salts such as ammonium sulfate and ammonium hydrogen sulfate. Among them, sulfuric acid and nitric acid which show strong acidity are preferable.

The carbon fiber used in the present invention is preferably a carbon fiber having a tensile elongation at break of at least 1.5%. When the tensile elongation at break is less than 1.5%, the carbon fibers are easily cut in the molding material production step (particularly, the resin impregnation step) and the molding step, and the carbon fiber length in the molding material and the molded article is reduced. , It is not only inferior to high mechanical properties (especially impact strength), but also high productivity of the molding material cannot be achieved. In order to solve the above problem, a carbon fiber having a tensile elongation at break of 1.5% or more, more preferably 1.7% or more, and still more preferably 1.9% or more. It is better to use The tensile elongation at break of the carbon fiber used in the present invention has no upper limit, but is generally less than 5%.

In order for a molded article obtained by molding the molding material of the present invention to have high mechanical properties (impact strength, rigidity, etc.), it is effective to increase the length of the reinforcing fibers in the molded article. is there. For that purpose, when the reinforcing fiber in the molding material is formed by a continuous fiber molding material that is a continuous yarn, or when the reinforcing fiber contained in the molding material is 100% by weight, at least 80% by weight of the reinforcing fiber is used. But 2-26
It is preferable to mold with a long fiber reinforced molding material having a fiber length in the range of mm. When molded using continuous fiber or long fiber molding material, the length of the reinforcing fiber in the molded product can be maintained long, so that the mechanical properties (particularly impact strength) can be dramatically improved. Becomes

In the present invention, it is preferable that the reinforcing fiber is present in the resin (A) in the molding material. By manufacturing the molding material so that the reinforcing fibers are present in the resin (A), the production efficiency (productivity) of the molding material can be significantly improved. A remarkable effect is exhibited in the case of a molding material). However, some reinforcing fibers (preferably 30% by volume or less of the reinforcing fibers, more preferably 20% by volume or less, and still more preferably 5% by volume or less) may be present in addition to the resin (A). Even if there are some domains of the resin (A) having no or almost no reinforcing fibers, there is no great influence on the production efficiency of the molding material described above. In this case, the ratio of (reinforcement fiber cross-sectional area in domain) / (resin (A) domain cross-sectional area) ratio is preferably less than 0.3 for all resin (A) domain cross-sectional areas. 30% of
Or less, more preferably 20% or less.

The molded articles obtained by molding the molding material of the present invention include, for example, press molding, injection molding (injection compression molding, injection expansion molding, gas assist injection molding, insert molding, etc.), blow molding, rotational molding, and extrusion molding. , Transfer molding (RIM, RTM, SCRIMP), filament winding molding, and other known molding methods. The molding materials used for such molding include BMC, SMC, stampable sheets, prepregs (sheets, tapes). And the like, and pellets. More preferred molding methods include press molding and injection molding with high productivity.

When a molded article obtained by molding the molding material of the present invention is formed by press molding, the molding material of the present invention preferably has any form of a strand, a tape, or a sheet. The reinforcing fibers in the molding material having the above-mentioned configuration are arranged substantially parallel to the longitudinal direction of the molding material so that the length of the reinforcing fibers is substantially the same as the length of the molding material using continuous yarn. It may be arranged randomly in a molding material using discontinuous yarns represented by chopped yarns and milled yarns. When the reinforcing fibers in the molding material are continuous yarns, it is preferable because a molded article having higher mechanical properties can be obtained. Here, each component in the present invention including at least the resin may be impregnated in the reinforcing fiber, may be coated, or may be applied on the reinforcing fiber.

When the reinforcing fibers are impregnated, for example, an impregnation tank containing (1) an emulsion, a suspension, a solution or a melt of the resin (A) and the resin (B) and, if necessary, the resin (C) is used. Using a method of impregnating the resin, (2) dispersing the resin (A) and the resin (B) and, if necessary, the powder of the resin (C) in the reinforcing fiber bundle, and then heating the resin to a melt viscosity or higher; Method of impregnating resin, (3)
A method of impregnating the resin (A) and the resin (B) melted by using a crosshead die or the like and, if necessary, the resin (C) can be used. However, when a reinforcing fiber typified by the above-described impregnation method is simultaneously impregnated with the resin (A) and the resin (B) and, if necessary, the resin (C), the strength and elongation of the reinforcing fiber are high. If not, a molded product having mechanical properties in a well-balanced manner cannot be obtained, and also, it is difficult to achieve high productivity of a molding material.

When the reinforcing fiber is coated, it is preferable that the reinforcing fiber has a core-sheath type structure comprising at least a core made of a reinforcing fiber bundle and at least a sheath made of a resin having the largest content. In the case of the core-sheath type, the reinforcing fiber bundle is impregnated in advance with a resin (hereinafter, referred to as a low-viscosity resin) having a melt viscosity equal to or less than that of the resin having the largest blending amount in the molding material. After forming the complex with the viscous resin, it is preferable that the resin is coated with each component in the present invention including at least the resin with the largest amount of compounding. The low-viscosity resin preferably has a melt viscosity ratio represented by (melt viscosity of low-viscosity resin) / (melt viscosity of resin with the largest blending amount) of 0.9 or less, more preferably 0 or less. 0.7 or less, more preferably 0.7 or less.
5 or less. Here, the resin (A) is suitable as the low-viscosity resin.

Here, in the composite of the reinforcing fiber and the low-viscosity resin, it is preferable that the reinforcing fiber is completely impregnated with the low-viscosity resin. This is possible even when voids are present, and does not cause a major problem if the void ratio is the minimum which does not impair productivity. However, if the void ratio exceeds 50%, it is extremely difficult to achieve the above-mentioned dispersibility and impregnation. Therefore, the void ratio in such a composite is preferably 50% or less. It is preferably at most 40%, more preferably at most 30%. In particular, it is preferably at most 20%. In the present invention, the void fraction was measured according to ASTM D2734.

As the molding material of the present invention, those having the above-mentioned core-sheath type structure are particularly preferable because the effects of the present invention can be exhibited to the maximum. In particular, it is particularly preferable that the low-viscosity resin is the resin (A) and the resin having the largest amount is the resin (B) because the effects of the present invention can be maximized.

When a flame retardant is blended with the molding material of the present invention, it may be kneaded with a resin or the like in advance and placed in the sheath, or may be blended separately from the molding material by dry blending, coating or the like. May be.

When the molded article of the present invention is molded by injection molding, the molding material of the present invention preferably has a pellet form. The pellets referred to in the present invention refer to those obtained by cutting the molding material of the present invention having any one of the above-described strands, tapes and sheets into a desired length. Also,
A pellet obtained by dry blending a pellet containing reinforcing fibers and a pellet not containing reinforcing fibers is also referred to as a pellet.

In order for the molded article obtained by molding the pellets used in the present invention to achieve high mechanical properties, particularly impact strength and rigidity, it is necessary to increase the length of the reinforcing fibers in the molded article. Although effective as described above, it is preferred that the pellets be in the form of long fiber pellets. Such long fiber pellets refer to those in which the reinforcing fibers in the strands, tapes and sheets before cutting are continuous yarns arranged in the longitudinal direction. As the long fiber pellets used in the present invention, core-sheath type long fiber pellets obtained by cutting a strand, a tape, or a sheet-shaped molding material having the above-described core-sheath type structure maximize the effects of the present invention. It is particularly preferable because it is possible.

The pellet length of the long fiber pellet used in the present invention is preferably in the range of 2 to 26 mm. It is more preferably in the range of 4 to 15 mm, and still more preferably in the range of 5 to 10 mm.

The blending form is not particularly limited. However, the reinforcing fiber bundle is impregnated with the resin (A) and the pellets containing at least the resin but not containing the reinforcing fibers, and the composite of the resin (A) and the reinforcing fibers is prepared in advance. After the body is formed, at least the resin (B) is preferably dry-blended with the core-sheath type long-fiber pellet coated with the composite, because productivity can be increased. More preferably, at least resin (B), carbon black described below,
A core-sheath coated with a composite containing a reinforcing fiber bundle previously impregnated with a resin (A) and at least a resin (B), carbon black, a flame retardant, etc. Dry-blended with long fiber pellets of a type.

Next, the method for producing a molding material of the present invention will be described in the order of steps.

(1) Impregnation step The pre-opened reinforcing fibers are preheated, and then the resin (A) such as the low-viscosity resin is supplied, and the resin (A) is reinforced with a squeeze roll or the like in a heating atmosphere. By impregnating the inside, a composite of the reinforcing fiber and the resin (A) is formed.

Here, assuming that the melting temperature of the resin (A) is T _MA , the temperature of the reinforcing fiber immediately before the supply of the resin (A) is preheated to a range of T _MA to (T _MA +100) ° C. It is preferable because the resin (A) can be easily impregnated and the take-up speed can be increased.

As for the method of supplying the resin (A), for example, a normal rotation roll, a reverse roll, a gravure, a blade,
Kiss, screen, curtain, spray, extrusion, etc., the method described in "Introduction to Coating Equipment and Operation Techniques (Yuji Harada, published by Sogo Gijutsu Center)" can be used, preferably by a curtain coater method using a gear pump. Good to supply.

When the reinforcing fiber is heated so that the temperature at which the resin (A) is impregnated is in the range of (T _MA +20) to (T _MA +120) ° C., the resin (A) is similarly heated. ) Is preferable because the impregnation becomes easy and the take-up speed can be increased. Regarding the impregnation method of the resin (A), when a squeeze bar is used, it is preferable to repeat the widening and convergence, or to vibrate the bar because the impregnation becomes easy and the take-up speed can be increased. The bar may be fixed or rotated, but in order to provide a self-cleaning function so that fluff of the generated reinforcing fibers is not brought into the next coating step, in the opposite direction to the take-off direction, It is preferable to rotate at a speed of 0.4 to 6 revolutions / minute.

(2) Coating Step The core-sheath type is obtained by coating the composite of the reinforcing fiber and the resin (A) with a resin having the largest blending amount using a coating die or a T die for coating electric wires. A strand, tape, or sheet is formed.

Here, assuming that the melting temperature of the resin having the largest blending amount in the molding material is T _MB , the temperature immediately before the composite is coated with the resin having the largest blending amount is (T _MB
When cooled to a temperature in the range of -100) to (T _MB -10) ° C., the coating of the resin with the largest blending amount is stable and the coating thickness is uniform, and the reinforcing fibers falling off from the molding material are minimized. It is preferable because it can be performed.

(3) Taking-off step One of the core-sheath type strands, tapes and sheets is taken out at a take-up speed of 10 m / min or more to obtain any one of the core-sheath type strands, tapes and sheets.

In particular, when the fiber-reinforced molding material of the present invention is in the form of a core-sheath type long-fiber pellet, it is preferably produced through the following steps. Preferably, the steps are each performed continuously online.

(4) Cutting Step Any one of the core-sheath type strand, tape and sheet taken out after cooling is cooled to 2 to 26 mm, more preferably 4 to 26 mm.
It is cut to a length of 15 mm, more preferably 5 to 10 mm. In particular, in the case of a sheet, it may be cut after slitting in the long axis direction.

In the molding material of the present invention, it is preferable that reinforcing fibers are blended in the range of 0.3 to 12 g / m per production unit in the take-off step in the production process. 0.3g of reinforcing fiber to be blended per unit of production
/ M is not preferred because the productivity of the molding material is poor. In addition, the reinforcing fiber to be compounded is 12 g per production unit.
If it exceeds / m, the productivity is excellent, but the dispersion of the reinforcing fibers in the molded article is poor, and the mechanical properties of the obtained molded article are inferior. More preferably 0.6 to 10 g
/ M, more preferably 1 to 8 g / m. In particular, the range of 1.5 to 7 g / m is preferable because the productivity of the molding material and the high mechanical properties of the obtained molded product can be well balanced.

The molding material of the present invention may contain carbon black. Examples of the carbon black used in the present invention include furnace black (produced by burning raw oil in a high-temperature furnace), acetylene black (produced by exothermic decomposition of acetylene gas), thermal black, channel black, lamp black, and the like. Alternatively, carbon black obtained by blending two or more of these may be used.

The compounding ratio of carbon black used in the present invention is 0.5% when the total amount of the molding material is 100% by weight.
It is preferably from 10 to 10% by weight, more preferably from 1 to 8% by weight, and still more preferably from 1.5 to 7% by weight. If the compounding ratio of carbon black is too small or too large beyond the above range, a material having good balance of mechanical properties such as conductivity, moldability, impact resistance and strength in a molded product can be obtained. Not so desirable.

According to the purpose, such a molding material has:
Filler, flame retardant (for example, phosphorus-based (preferably ammonium polyphosphate, aromatic phosphate, red phosphorus), metal hydroxide-based (preferably aluminum hydroxide, magnesium hydroxide), halogen-based, nitrogen-based (preferably Melamine cyanurate salt, melamine phosphate), silicon-based (preferably polyorganosiloxane resinous polymer or copolymer), etc., flame-retardant auxiliary (eg, fluorine-based (preferably PTFE), etc.), coloring agent , Pigments, dyes, lubricants (such as metal soaps), release agents, compatibilizers,
Dispersant, crystal nucleating agent (eg, mica, talc, kaolin, etc.), plasticizer (eg, phosphate ester, etc.), heat stabilizer, antioxidant, anti-coloring agent, ultraviolet absorber, flow modifier, foaming agent , Antibacterial agent, vibration damping agent (eg, graphite), deodorant, slidability modifier (eg, powdered graphite, flaky graphite, expanded graphite, etc.), conductivity imparting agent, antistatic agent (eg, polyetheresteramide) ) Can be used alone or as a blend of two or more.

As used herein, the term “filler” refers to mechanical properties (eg, strength, elastic modulus, elongation, impact strength, linear expansion coefficient, thermal deformation temperature, etc.) and thermal properties (eg, thermal expansion coefficient, thermal conductivity, etc.). ), Molding processability (for example, screw biting, viscosity,
It is blended to give effects according to the application to the molding material of the present invention, such as control of filling degree, molding shrinkage, burr, sink mark, surface smoothness, etc., specific gravity, anisotropy, etc., and cost reduction. . Such fillers include, for example, mica, talc,
Kaolin, sericite, bentonite, zonotrite,
Sepiolite, smectite, montmorillonite, wallastenite, silica, calcium carbonate, glass fiber, glass beads, glass flake, glass microballoon, clay, molybdenum disulfide, titanium oxide, zinc oxide, tin oxide, antimony oxide, calcium polyphosphate,
Graphite, zinc sulfide, barium sulfate, magnesium sulfate, zinc borate, calcium borate, aluminum borate whiskers, potassium titanate whiskers, polymers and the like can be used. These fillers may be used alone or as a blend of two or more. The shape of the filler may be any shape such as particle (solid, hollow), powder, scale, flake, balloon, whisker (two-dimensional, three-dimensional), fibrous, etc. depending on the purpose. You can choose. Also, such a filler may be a natural type or a synthetic type,
It can be arbitrarily selected according to the purpose. Walastenite, titanium oxide, and potassium titanate are preferred from the viewpoint of balance between dispersibility in resin, mechanical properties, and cost.

The conductivity-imparting agent refers to a substance having conductivity, such as a metal (eg, particles, flakes, ribbons, etc.), a metal oxide (eg, particles), carbon (E.g., powder-like), graphite (e.g., flake-like, expanded particle-like, fine powder-like, etc.), a filler itself having conductivity, or a non-conductive filler coated with a conductor on the surface, Examples thereof include a conductive polymer, and these may be used alone or in combination of two or more.

The conductor covered with the above-mentioned filler means a substance having conductivity, such as a metal, a metal oxide, or carbon. Among them, a metal or a metal having the highest conductivity is used. Metal oxides (hereinafter sometimes collectively referred to as metals) are preferred. As the metal, for example, nickel, titanium, aluminum, chromium, zinc, antimony, copper, silver, gold, and the like can be used alone or in combination, and the metal is used as a filler in at least one layer and, if necessary, a plurality of layers. It is preferably coated with

The method for coating the above-mentioned filler with a conductor is not particularly limited, but is preferably a plating method by electrolysis or electroless, an ion plating method, a CVD method, or a PVD method.
It is preferable that the coating is performed with high adhesion strength by a method, a vapor deposition method, or the like.

As the conductivity-imparting agent used in the present invention, it is preferable that the conductivity-imparting agent itself has high conductivity in order to exhibit a higher conductivity-imparting effect. It is preferable to use at least one of oxide and graphite.

Examples of such metals include nickel, titanium, aluminum, chromium, iron, stainless steel, tin,
Lead, antimony, zinc, cadmium, magnesium, tungsten, lithium, molybdenum, beryllium, cobalt, vanadium, manganese, copper, brass, silver, gold, platinum, and alloys combining two or more of these, with these as the main components Alloys, compounds of these and phosphorus, and the like may be mentioned, and these may be used alone or in combination of two or more. Among them, silver, nickel, and titanium are preferred because of their large conductivity-imparting effect.

As such a metal compound, for example, ITO
(Indium tin oxide), ATO (antimony tin oxide), and oxide compounds such as zinc oxide.

The metal can be in any form such as a particle, a flake, a ribbon and the like, but is preferably in a particle and / or flake form in view of the effect of imparting conductivity. . Especially when it is particulate
Can take any shape such as spherical powder, granular powder, dendritic powder, flaky powder, horny powder, spongy powder, irregular powder, etc., among which dendritic powder, flaky powder, horny powder Is preferred because it has excellent conductivity-imparting effects and processing cost suppressing effects.

The graphite can be in any form such as a scale, expanded particles, fine powder, etc.
From the viewpoint of the conductivity imparting effect, it is preferably in the form of flakes or fine powder.

Such fillers, conductivity-imparting agents, flame retardants and the like may be surface-treated with a surface-treating agent or may be untreated. Examples of the surface treatment agent include saturated higher fatty acids such as stearic acid, unsaturated higher fatty acids such as oleic acid, alkali metal salts thereof, and mono- or diesters of orthophosphoric acid and stearyl alcohol, and these acids, or And phosphoric acid partial esters such as alkali metal salts. In order to improve the adhesiveness with the resin, a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, a urethane-based resin, an amide-based resin, or the like may be coated. Urethane resin, epoxy resin, polyester resin,
It may be covered with a styrene resin, an olefin resin, an amide resin, an acrylic resin, a phenol resin, a liquid crystal resin, or the like. More preferably, the surface treatment is performed with a surface treatment agent that does not cause a chemical interaction with the resin during molding. When a surface treatment that causes a chemical interaction during molding is performed, the effects of the present invention may not be sufficiently exhibited. The surface treatment amount of the surface treatment agent is
0.1 to 100 parts by weight of filler or conductivity imparting agent
10 parts by weight is preferable, and 0.5 to 5 parts by weight is more preferable.

The filler and the like may be swollen by a swelling agent or may be organized by an organic agent. The swelling agent and the organic agent are not particularly limited as long as they can swell or organize the filler or the like by ion exchange or the like. Specifically, ε-caprolactam, 12-aminododecanoic acid, 12-aminolauric acid And alkylammonium salts (such as dimethyldialkylammonium). In particular, when a swelled or organic filler (preferably montmorillonite, mica, saponite, hectorite, sepiolite) is blended with polyamide resin, polypropylene resin, polyacetal resin, styrene resin, acrylic resin, etc. Dispersion of materials on the nano order becomes possible,
It is preferable because desired characteristics can be obtained with a smaller amount.

When the above-mentioned filler, conductivity-imparting agent, flame retardant and the like are mixed with the molding material of the present invention, they are kneaded with a resin or the like in advance by an extruder or the like and placed in the sheath or the core. It may be blended by dry blending or coating separately from the molding material. Further, they may be mixed in advance during the polymerization of the resin. The carbon black may be previously mixed in the reinforcing fiber bundle, may be previously mixed in the sizing agent of the reinforcing fiber, or may be mixed in the resin (A).

As described above, the preferable molding method of the molded article of the present invention is injection molding with high productivity. In order to achieve high mechanical properties (particularly strength and impact strength) in a molded article obtained by injection molding using the pellets, it is effective to increase the length of the reinforcing fibers in the molded article. In this case, it is necessary to consider especially the molding conditions and the effects of the injection molding machine and the mold. Speaking of molding conditions, the lower the back pressure, the lower the injection speed, the lower the screw rotation speed, the longer the reinforcing fibers in the molded product tend to be,
In particular, it is preferable to set the back pressure as low as possible so that the measurement performance does not become unstable. The preferred back pressure is 0.1
１1 MPa. As for the injection molding machine, the length of the reinforcing fiber in the molded product tends to be longer as the nozzle diameter is larger, the nozzle taper angle is smaller, the screw groove depth is larger, and the compression ratio is lower. As for the mold, as the diameter of the runner, the diameter of the sprue, and the diameter of the gate are increased, the length of the reinforcing fibers in the molded article tends to be longer.

In order for the molded article of the present invention obtained by the above-mentioned molding method to achieve high mechanical properties, at least when the total amount of reinforcing fibers contained in the molded article is 100% by weight, Preferably, 3% by weight has a fiber length in the range from 1 to 15 mm. More preferably, at least 5% by weight thereof has a fiber length in the range of 1 to 10 mm, and even more preferably at least 5% by weight has a fiber length in the range of 1 to 7 mm. Particularly preferred is when at least 8% by weight thereof has a fiber length in the range from 1 to 7 mm.

The molded article of the present invention is particularly useful when carbon fibers are used as reinforcing fibers (in some cases, a conductivity-imparting agent such as graphite or carbon black can be used alone or in combination). Since it has high conductivity due to fibers (in some cases, a conductivity-imparting agent, etc.), the volume resistivity is 100Ω.
・ Suitable for obtaining molded articles having a size of not more than cm. When the volume specific resistance exceeds 100 Ω · cm, it is difficult to adapt to applications such as electromagnetic wave shielding materials, and there is a problem that the applications are limited. A more preferable volume resistivity is 1
It is 0 Ω · cm or less, and the more preferable volume specific resistance value is 5 Ω · cm or less. Particularly preferably, 1Ω · c
m or less.

The term “volume specific resistance value” as used herein refers to a value obtained by subtracting the contact resistance value of a measuring instrument, a jig or the like from the electric resistance value of both ends of a test piece having a rectangular parallelepiped shape coated with a conductive paste. The value is calculated by multiplying the end area of the test piece and dividing by the test piece length. In the present invention, the unit is Ω · cm. In the present invention, when forming a test piece for measuring a volume specific resistance value, the test piece is basically obtained by orienting the reinforcing fibers in the measurement direction of the test piece. Here, the measurement direction refers to a direction parallel to a straight line connecting both terminals for measuring the volume specific resistance value. Especially when molding by injection molding, a film gate (or fan gate) located on the side perpendicular to the measurement direction of the test piece
Alternatively, a test piece is obtained by molding using a mold that is filled with a fan gate positioned very close to the side in the measurement direction that is orthogonal to the measurement direction. In molding, the cylinder temperature of the injection molding machine is, for example, 26 for a polyamide resin.
Within the range of 0 to 280 ° C., 2 for polycarbonate resin
Molding is performed at a mold temperature of 80 ° C within a range of 70 to 320 ° C.

[0160] The molded article of the present invention not only has high conductivity but also has high conductivity, particularly when carbon fiber is used as the reinforcing fiber.
Since it has high impact strength mainly due to carbon fiber, the Izod impact strength according to the ASTM D256 standard is 60 to 2 at a plate thickness of 3.2 mm (1/8 inch).
It is suitable for obtaining a molded product in the range of 50 J / m.
It is more preferable to use the molded product in the range of 70 to 230 J / m, particularly preferably in the range of 80 to 200 J / m, so that the effects of the present invention can be further exhibited.

[0161] The molded article of the present invention not only has high conductivity but also has high conductivity, particularly when carbon fiber is used as the reinforcing fiber.
Because it has high rigidity mainly due to carbon fiber, it is 6.4 mm (1/4 inch) thick according to ASTM D790 standard (distance between spans L / thickness D = 16).
It is suitable for obtaining a molded product having a flexural rigidity at a thickness of 6 to 40 GPa. The use of a molded product having a range of preferably 8 to 30 GPa, particularly preferably 10 to 25 GPa, can further exert the effect of the present invention.

The molded article of the present invention can impart not only high conductivity and mechanical properties but also high flame retardancy when a flame retardant or a flame retardant auxiliary agent is blended. Suitable for obtaining a molded product having a flame retardancy of V-0 or better at 1.6 mm (1/16 inch) thickness (more preferably 0.8 mm (1/32 inch) thickness) It is.

Here, the flame retardancy of V-0 is defined as UL-94.
Standards (UnderwritersLaboratori)
es Inc. Flame retardant that meets the V-0 condition specified by the burning time and conditions, whether or not there is a fire spread, whether or not there is a drip (drip) and the flammability of the dripped material in the United States Combustion Test Method devised in Refers to gender. V-
The flame retardancy better than 0 means flame retardancy indicating a combustion time even shorter than the specified value in the V-0 class, and difficult to satisfy the specified condition of V-0 when the thickness of the test piece is thinner. Refers to flammability.

In the present invention, when molding a UL-94 test piece, the test piece is basically obtained by orienting the reinforcing fibers in a direction perpendicular to the long side direction of the test piece. In particular, when molding by injection molding, a test piece is obtained by molding using a mold filled with a film gate over the entire length in the long side direction of the test piece. In molding, the cylinder temperature of the injection molding machine is, for example, 260 to 2 for polyamide resin.
Within the range of 80 ° C., 270 to 270 for polycarbonate resin
Molding is performed at a mold temperature of 80 ° C. within a range of 320 ° C.

Since the molded article of the present invention has not only high conductivity but also thin moldability (fluidity during molding), it is possible to make the molded article thinner than conventional molded articles. Is in the range of 0.3 to 4 mm. Preferably, it is used as a molded product having a wall thickness of 0.5 to 3 mm, more preferably 0.6 to 2 mm, and particularly preferably a wall thickness of 0.7 to 1.6 mm, so that the effects of the present invention can be further exhibited. . The thickness here refers to the thickness of a flat portion of a molded product excluding protrusions such as a rib portion and a boss portion.

The molded article of the present invention can be used for housings and casings for electronic / electric equipment, OA equipment, home electric appliances, or automobiles, which require high mechanical properties (particularly rigidity), moldability and conductivity. And the like. Since the molded article of the present invention can achieve high rigidity, light weight, electromagnetic wave shielding properties, and the like, it is particularly effective for applications such as housings and casings of portable electronic and electric devices. More specifically, housings for large displays, notebook computers, portable telephones, PHSs, PDAs (portable information terminals such as electronic organizers), video cameras, digital still cameras, portable radio cassette players, inverters, switches, etc. It is preferably used for casings and the like.

The molded article of the present invention has an appropriate conductivity, particularly when carbon fibers are used as reinforcing fibers (in some cases, a conductivity-imparting agent such as graphite or carbon black can be used alone or in combination). Therefore, the addition of a small amount of carbon fiber (in some cases, a conductivity-imparting agent, etc.) can impart antistatic properties and self-discharge properties, and members requiring such properties, such as IC trays and silicon wafers It is also useful for transport baskets and various sliding members.

[0168]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

First, in carrying out each of the examples, the evaluation items of the molding material and the molded product obtained by molding the molding material and the method thereof were as follows.

(A) Productivity of molding material Regarding the volume blending ratio of the reinforcing fibers to be blended with the molding material and the production amount per production unit that can be produced stably when the kind of resin is the same, ◎ (5 kg / Hour excess), ○ (5-3 kg / hour), △ (3-1 kg / hour)
Hour), × (less than 1 kg / hour).

(A) Impact Strength of Molded Product The product was evaluated by Izod impact strength with a mold notch according to ASTM D256 standard (unit: J / m). The test specimen used was 3.2 mm (1/8 inch) thick,
The test was performed at a moisture content of 0.1% or less.

(C) Flexural rigidity of molded product ASTM D790 standard (distance between spans L / thickness D =
Evaluated by flexural rigidity based on 16) (unit is GP)
a). The test pieces used were 6.4 mm (1/4 inch) thick and were subjected to a test with a water content of 0.1% or less.

(Examples 1 to 9) First, a continuous reinforcing fiber bundle was opened while being heated, and the molten resin (A) was applied by a spray coater (temperature of the reinforcing fiber bundle immediately before application). Is the melting temperature of the resin (A) + about 30 ° C.). Then, the heated atmosphere (the melting temperature of the resin (A) + about 50)
C)), the resin (A) is sufficiently impregnated into the reinforcing fiber bundle by passing through 5 to 10 squeeze bars arranged in the squeezing bar to obtain a composite of continuous reinforcing fibers and the resin (A) (impregnation). Process). The squeeze bar refers to a bar having an effect of opening the reinforcing fiber bundle.

Next, a resin composition in which the resin (B) and, in some cases, the resin (C), other resins, fillers, and the like are sufficiently kneaded with a twin-screw extruder is used. At the same time as extruding in a state of being sufficiently melt-kneaded into an electric wire coating die attached to the tip thereof, the obtained composite is continuously supplied into the coating die, thereby melting the molten resin into the composite. To obtain a continuous fiber reinforced resin strand (coating step).

Thereafter, the continuous fiber-reinforced resin strand was cooled to 100 ° C. or lower, and cut into 7 mm using a cutter to obtain a core-sheath type long fiber pellet (cutting step).
The production of the core-sheath type long-fiber pellets was continuously performed on-line in each of the impregnation step, the coating step, and the cutting step.
m / min or more). That is, it can be said that the core-sheath type long fiber pellets are very excellent in productivity. In addition, the obtained molded product also shows high mechanical properties, and can be said to be a molding material that has overcome the conventional problems. The void ratio of the composite of the reinforcing fiber and the resin (A) obtained in the impregnation step was 20% in all Examples.
It was below.

(Comparative Example 1) First, the resin (B) and the reinforcing fiber bundle formed into a chopped yarn were extruded by a twin screw extruder while impregnating the molten resin (B) into the reinforcing fiber bundle. To obtain a discontinuous fiber reinforced resin gut obtained as described above containing only discontinuous ones (impregnation step).

Thereafter, the discontinuous fiber reinforced resin gut was cooled to 100 ° C. or less, and cut into 5 mm using a cutter to obtain pellets (cutting step). As a result of continuously performing the impregnation step and the cutting step on-line in the production of the above-mentioned long fiber pellet, it was possible to produce the pellet at a high take-off speed of 20 m / min or more. That is, it can be said that the pellets produced by the production method using the chopped yarn-made reinforcing fibers are very excellent in productivity. However, since the reinforcing fibers in the obtained molded article are shorter than the long fiber pellets in the examples, the mechanical properties of the obtained molded article are inferior, and it cannot be said that the conventional problems can be overcome.

(Comparative Examples 2, 5, and 7) First, the resin (B) is extruded by a single-screw extruder while being sufficiently melt-kneaded into a crosshead die attached to the tip of the extruder. At the same time, the reinforcing fiber bundle is continuously supplied into the crosshead die while being heated, and the resin is sufficiently impregnated into the reinforcing fiber bundle to obtain a continuous fiber-reinforced resin strand containing no resin (A) (impregnation step). . The crosshead die refers to a device in which a reinforcing fiber bundle is opened by passing through a plurality of squeeze bars or the like disposed therein, and a molten resin is impregnated in the reinforcing fiber bundle.

Thereafter, the continuous fiber reinforced resin strand was cooled to 100 ° C. or less, and cut into 7 mm using a cutter to obtain an impregnated long fiber pellet containing no resin (A) (cutting step). As a result of continuous production of the impregnated long fiber pellets in the impregnation step and the cutting step, the impregnation failure of the resin (B) and the breakage of the reinforcing fiber frequently occurred. In Comparative Examples 2 and 7, the length was 5 m. / Min or less, and Comparative Example 5 could only be manufactured at a low take-off speed of 10 m / min or less. In other words, it can be said that the impregnated long fiber pellets produced by the above-described production method are very poor in productivity.

(Comparative Examples 3, 4, 6) First, the resins (A) and (B) are extruded while being melt-kneaded by a twin-screw extruder to obtain master pellets.

Next, the master pellets are extruded by a single-screw extruder while being sufficiently melt-kneaded into a crosshead die attached to the end thereof. At the same time, the reinforcing fiber bundle is continuously supplied into the crosshead die while being heated, and the resin is sufficiently impregnated into the reinforcing fiber bundle to obtain a continuous fiber-reinforced resin strand (impregnation step). With the crosshead die, the reinforcing fiber bundle is spread by passing through a plurality of squeeze bars and the like arranged therein,
A device for impregnating a molten resin into a reinforcing fiber bundle.

Thereafter, the continuous fiber reinforced resin strand was cooled to 100 ° C. or lower, and cut into 7 mm using a cutter to obtain an impregnated long fiber pellet (cutting step). As a result of continuous production of the above-mentioned impregnated type long fiber pellets continuously in the impregnation step and the cutting step, resin impregnation failure and reinforcing fiber breakage frequently occur, and
It could only be manufactured at a low take-off speed of less than m / min. In other words, it can be said that the impregnated long fiber pellets produced by the above-described production method are very poor in productivity.

After the obtained pellets were sufficiently dried, they were subjected to the tests described in the above (A) to (F). Tables 1 and 2 show the mixing ratios of the components in the molding materials used in Examples 1 to 8 and Comparative Examples 1 to 7, and the evaluation results.

The molding conditions were the same as in Examples 1-3, 7, 8,
In Comparative Examples 1 to 5, the injection molding machine cylinder temperature was 280 ° C. and the mold temperature was 80 ° C., and Examples 4 and 5 and Comparative Example 6 were in the injection molding machine cylinder temperature of 320 ° C. and the mold temperature was 80 ° C. In Comparative Example 7, the cylinder temperature of the injection molding machine was 340 ° C., and the mold temperature was 8
Performed at 0 ° C.

[Table 1]

[Table 2] In addition, the description of each component in Tables 1-2 is based on the following. Resin (A) LCP1: Liquid crystalline resin [aromatic oxycarbonyl unit 4]
Melting point 208 ° C., melt viscosity 1 consisting of 2.5 mol%, aromatic dioxy unit 7.5 mol%, ethylene dioxy unit 50.0 mol%, and aromatic dicarboxylic acid unit 57.5 mol%
5Pa · s] LCP2: liquid crystalline resin [aromatic oxycarbonyl unit 8]
Melting point 314 ° C., melt viscosity 2 consisting of 0.0 mol%, aromatic dioxy unit 7.5 mol%, ethylene dioxy unit 12.5 mol%, and aromatic dicarboxylic acid unit 20.0 mol%
0 Pa · s] T / P1: Terpene / phenol copolymer resin [YP90L manufactured by Yashara Chemical Co., Ltd.] T / P2: Terpene / phenol copolymer resin [Mighty Ace G-150 manufactured by Yashara Chemical Co., Ltd.] Resin (B) N6: Nylon 6 [ηr = 2.35] N66: Nylon 66 [ηr = 2.78] PC: Polycarbonate [Panlite L-1250 manufactured by Teijin Chemicals Ltd.] m-PPE: Modified polyphenylene ether [Asahi Chemical Industry Co., Ltd.] Zylon X-9102] Resin (C) LCP2: Liquid crystalline resin [aromatic oxycarbonyl unit 8]
Melting point 314 ° C., melt viscosity 2 consisting of 0.0 mol%, aromatic dioxy unit 7.5 mol%, ethylene dioxy unit 12.5 mol%, and aromatic dicarboxylic acid unit 20.0 mol%
0 Pa · s] ABS: acrylonitrile / butadiene / styrene copolymer resin [acrylonitrile unit 30 mol%, butadiene unit 15 mol%, styrene unit 55 mol%] Reinforcing fiber GF: glass fiber [Tex = 2300 g / 1000 m,
Average single fiber diameter = 17 μm, tensile elongation at break = 4%] CF: PAN-based carbon fiber [Tex = 1650 g / 100
0 m, average single fiber diameter = 7 μm, tensile elongation at break = 2.0
%, Lc = 1.9 nm, surface functional group (O / C) = 0.0
7] The following is clear from the results in Table 1.

(1. Effect of Resin (A) in Molding Material (Comparison between Examples 1 and 2 and Comparative Examples 1 and 2, Comparison between Example 3 and Comparative Example 5, Comparison between Examples 6 and 7) Comparison with Comparative Example 1) in which the resin (A) is not blended in the molding material.
Examples 1 and 2 in which resin (A) is blended in molding material
Can obtain a molded product having extremely high mechanical properties (especially Izod impact strength) while having the same productivity per unit of production of the molding material, and its superiority is apparent.

On the other hand, as compared with Comparative Example 2 (Comparative Examples 5 and 7) in which the resin (A) was not blended in the molding material, Examples 1 and 2 in which the resin (A) was blended in the molding material were used. In Examples 3 and 6, the mechanical properties are equivalent, but the productivity per production unit of the molding material is remarkably high, and the superiority is clear.

(2. Effect of Domain Diameter of Resin (A) in Molding Material (Comparison of Examples 1 and 2 with Comparative Examples 3 and 4, Comparison of Examples 4 and 5 with Comparative Example 6)) Compared with Comparative Examples 3 and 4 (Comparative Example 6) in which the domain diameter of the resin (A) in the material is less than 0.01 mm, the domain diameter is 0.4 to 1
Examples 1 and 2 (Examples 4 and 5) in the range of 5 mm
Although the mechanical properties are the same, the productivity per unit of production of the molding material is extremely high, and the improvement effect on the productivity is enormous.

This is because the resin (A) is used in the embodiment and the domain diameter in the molding material is controlled.
This is because the take-up speed of the molding material can be made faster than in the comparative example.

(3. Effect of Domain Diameter of Resin (A) in Molded Article (Comparison between Examples 1 and 2)) In both Examples 1 and 2, the productivity per unit of production of the molding material and the obtained results were obtained. The mechanical characteristics of the molded products obtained are almost the same, and both productivity and mechanical characteristics are compatible at a high level. However, in Example 1 where the domain diameter is in the range of 0.05 to 50 μm in the molded article, especially in the moldability (fluidity during molding), as compared with Example 2 where the domain diameter is not present in the molded article. Could be further increased. Specifically, □ 150mm × 1m
The injection pressure for molding a thin flat plate having a thickness of m was 6.17 MPa (63 kg / cm ² ) in Example 1, whereas the injection pressure in Example 2 was 11.2 MPa (114 kg / cm ² ).
² ), and Example 1 in which the injection pressure was significantly reduced was superior in moldability.

That is, from the viewpoint of thin-wall moldability, the compatibility between the resin (A) and the resin (B) is controlled, and the domain of the resin (A) is present in the molded product in the range of 0.05 to 50 μm. It can be said that it is preferable to perform the formation, particularly from the viewpoint of moldability.

The injection pressure of Comparative Example 2 was 12.1MP
a (123 kg / cm ² ), which is much higher in moldability than in Examples 1 and ² , and is also significantly inferior in moldability.

(4. Effect of Combination of Resin (C) and Carbon Black (Comparison between Example 2 and Examples 7 to 9))
In Example 2 and Examples 7 to 9, the productivity per unit of production of the molding material and the mechanical properties of the obtained molded product were almost the same, and both the productivity and the mechanical properties were compatible at a high level. are doing. However, as compared with Example 2, Examples 7 to 7 in which carbon black is blended and resin (C) is used in combination.
In No. 9, the appearance quality of the molded product could be further improved. Specifically, for example, the height of the weld portion formed at the time of molding is about 13 μm in Example 2, whereas it is about 6 μm in Example 7, and the height of the weld portion can be significantly reduced. Example 7 was superior in appearance quality (here, flatness).

Further, when carbon fibers are used as the reinforcing fibers, the conductivity of the molded article is remarkably excellent due to a synergistic effect with carbon black. Specifically, the volume resistivity of the molded product was 1.63 Ω · cm in Example 2, whereas the volume resistivity of Example 7 was 0.31 Ω · cm. Example 7, which can be made smaller, was more excellent in electromagnetic wave shielding properties.

That is, from the viewpoint of the appearance quality of the molded product and the conductivity when carbon fibers are used as the reinforcing fibers, the resin (C) is used in combination with the molding material of the present invention.
And the addition of carbon black.

The height of the weld in Comparative Example 2 was 15
μm, the volume resistivity is 2.11 Ω · cm, and both the height of the weld portion and the volume resistivity are significantly higher than those of Examples 2 and 7, and the appearance quality and the volume resistivity are significantly inferior.

[0196]

The molding material of the present invention comprises at least two types of resins (A) and (B), wherein the resin (A) forms a domain in a matrix of the resin (B) in the molding material, and In a molded article obtained by molding the molding material, the resin (A) does not form a domain diameter, or forms a domain, and has a domain diameter of 0.4 to 15 mm. Is 0.05-50μ
By setting the range of m, the resin morphology in the molding material and the molded article was controlled to be optimal.

Further, in the method for producing a molding material of the present invention, the reinforcing fibers are preliminarily opened and preheated, and then the resin (A) is impregnated into the reinforcing fiber bundle, whereby the reinforcing fibers and the resin (A) are mixed. A composite is formed, and then the composite is coated with the resin (B), and thereafter, the coated composite is drawn off at a speed of 10 m / min or more, so that the take-up speed of the molding material and the molding The amount of reinforcing fibers in the material was optimized.

Thus, it is possible to obtain a molded article having a good balance of mechanical properties, particularly impact strength and rigidity, and to provide a molding material having excellent moldability, especially excellent fluidity during molding, and high productivity. It is possible to provide a production method, and a molded article molded from the molding material.

Such a molding material, a method for producing the same, and a molded product obtained therefrom are particularly suitable for electric and
The present invention is suitable for a wide range of industrial fields that require the above characteristics, including electronic devices, OA devices, home electric appliances, housings and casings for automobiles, and members thereof.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of a sea-island structure shown by resins (A) and (B) observed in a molding material of the present invention.

FIG. 2 is a schematic view showing an example of a compatible form that does not form a sea-island structure shown by resins (A) and (B) observed in a molded article of the present invention.

FIG. 3 is a schematic diagram showing an example of a sea-island structure shown by resins (A) and (B) observed in a molded article of the present invention.

FIG. 4 is a schematic diagram showing an example of the form of the sea-sea structure shown by the resins (B) and (C) observed in the molded article of the present invention.

[Explanation of symbols]

1: Resin (A) in molding material 2: Domain diameter of resin (A) in molding material 3: Resin (B) in molding material 4: Components other than resin such as reinforcing fiber and filler in molding material 5: Mixture of resin (A) and resin (B) in molded article 6: Resin (A) in molded article 7: Domain diameter of resin (A) in molded article 8: Resin (B) in molded article ) (Or resin (C)) 9: Resin (C) (or resin (B)) in molded article 10: Components other than resin such as reinforcing fiber and filler in molded article

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 7/02 C08K 7/02 // B29K 105: 08 B29K 105: 08 (72) Inventor Haruo Ohara Ehime 1515 Tsutsui, Matsumae-cho, Iyo-gun F-term (reference) at the Ehime Plant of Toray Industries, Inc. AB24 AC02 AC08 AD02 AD04 AD05 AD12 AD14 AD37 AD41 AD42 AD44 AG03 AG05 AG13 AH04 AH22 AK04 AK05 AK14 AK15 AL02 AL11 4F201 AA24 AA28 AA29 AA37 AA39 AD16 AH17 AH42 BA02 BC01 BC12 BC17 BC29 BD02 BD04 BL06A00 BC02 BC00 A02 CB00X CB00Y CC03W CD00W CF03X CF03Y CF18W CF18X CF18Y CG00X CG00Y CH06X CH06Y CK02X CK02Y CL00W CL00X CL00Y DA016 FA 046 GN00 GQ00

Claims (23)

[Claims] 1. A molding material comprising at least a reinforcing fiber and two kinds of resins (A) and (B), wherein the resin (A) forms a domain in a matrix of the resin (B), and And a molding material forming a sea-island structure whose domain diameter is in the range of 0.4 to 15 mm. 2. The resin (A) and (B) and at least a resin (C), wherein the resin (C) forms a domain in a matrix of the resin (B), and has a domain diameter. The molding material according to claim 1, which forms a sea-island structure in a range of 0.1 to 500 µm. 3. The method according to claim 1, further comprising at least the resins (A), (B), and (C), wherein the resins (B) and (C) form a sea-sea structure. A molding material as described. 4. The molding material according to claim 1, comprising a molding material containing reinforcing fibers and a molding material containing no reinforcing fibers. 5. The resin in the molding material containing the reinforcing fibers has at least the resins (A) and (B), and the resin in the molding material not containing the reinforcing fibers has at least the resin (B). 5) and / or (C). 6. The molding material according to claim 1, wherein the resin (A) is blended in a range of 0.1 to 50% by weight. 7. The molding material according to claim 1, wherein the resin (C) is blended in a range of 0.1 to 50% by weight. 8. The resin (A) is a phenolic resin,
The molding material according to any one of claims 1 to 7, wherein the molding material is at least one selected from the group consisting of a vinyl resin, an amide resin, an epoxy resin, and a liquid crystalline resin. 9. The resin (B) and / or (C)
Comprises a thermoplastic resin.
The molding material according to any one of the above. 10. The resin (B) and / or (C)
Is a styrene resin, a polycarbonate resin, a polyphenylene ether resin, a polyamide resin, a polyester resin, a polyolefin resin, a polyacetal resin, a liquid crystal resin, and at least one selected from the group consisting of a thermoplastic elastomer. Certain claim 1
10. The molding material according to any one of items 1 to 9. 11. The molding material according to claim 1, wherein the reinforcing fibers are blended in a range of 3 to 70% by weight. 12. The molding material according to claim 1, wherein said reinforcing fibers are carbon fibers. 13. A core-sheath type strand, tape or sheet comprising a core part containing the reinforcing fiber and a sheath part containing the resin. A molding material as described in the above. 14. The molding material according to claim 13, which has a form of a core-sheath type long fiber pellet cut into a length of 2 to 26 mm. 15. A molded article molded from the molding material according to claim 1, comprising at least a reinforcing fiber and two kinds of resins (A) and (B). A structure in which the resin (A) does not form a domain in the matrix of the resin (B), or the resin (A) has a domain diameter of 0.05 to 5 in the matrix of the resin (B).
A molded article having a sea-island structure in which a domain having a range of 0 μm is formed. 16. A molded article molded from the molding material according to claim 1, wherein the molded article comprises at least a reinforcing fiber and three types of resins (A), (B), and (C). The resin (C) is contained in a matrix of the resin (B).
Form a domain, and the domain diameter is 0.05
A molded article which forms a sea-island structure having a size in the range of ５０50 μm. 17. A molded article molded from the molding material according to claim 1, wherein the molded article comprises at least a reinforcing fiber and three types of resins (A), (B) and (C). Wherein the resin (B) and the resin (C) form a sea-sea structure. 18. The reinforcing fiber is preliminarily opened and preheated, and the resin (A) is impregnated in the reinforcing fiber bundle to form a composite of the reinforcing fiber and the resin (A). The body is coated with at least the resin (B), after which the coated composite is treated at 10 m / mi
A method for producing a molding material, wherein the molding material is taken off at a speed of n or more. 19. The molding material manufacturing method according to claim 18, wherein a reinforcing fiber is blended with the molding material before being taken up in a range of 0.3 to 12 g / m per production unit. Production method. 20. The coated composite may be any of a strand, a tape and a sheet, and
20. A core-sheath type long fiber pellet is obtained by cutting into a length within a range of 6 mm.
3. The method for producing a molding material according to item 1. 21. A molded product obtained by molding the molding material according to any one of claims 1 to 14 by press molding or injection molding. 22. A method for producing a molded article, comprising molding the molding material according to claim 1 by press molding or injection molding to obtain a molded article. 23. An electric / electronic device, an OA device, a home appliance, a housing, a casing, or a part thereof in an automobile.
22. The molded article according to 5 to 17 or 21.