JP2001131418A - Thermoplastic resin composition, molding material, pellet for injection molding and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having a good flow property, an easily prepared molding material which is well dispersed in a molded product of reinforced fiber bundles when molded via injection molding, etc., and yields a molded product having an excellent appearance, and a molded product obtained from these. SOLUTION: A thermoplastic resin composition comprises the following structural elements [A] and [B]. [A]: A thermoplastic polymer having a melt viscosity lower than that of the structural element [B], e.g. a thermoplastic polymer of the formula, [B]: a thermoplastic resin having a weight average molecular weight of >=10,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition and a long fiber reinforced thermoplastic resin molding material. More specifically, a thermoplastic resin composition having both high fluidity and high mechanical properties, easy to manufacture, and good dispersion of the reinforcing fiber bundle in the molded article when molding by injection molding or the like. The present invention relates to a molding material which is excellent in moldability, such as less stain of a mold, and a molded product obtained by molding these and which has excellent surface appearance and mechanical properties.

[0002]

2. Description of the Related Art Fiber reinforced composite materials in which a thermoplastic resin is used as a matrix for continuous reinforcing fiber bundles or discontinuous fibers having a relatively long fiber length are known. Such a composite material has features such as high toughness, easy recycling, and a short molding cycle because molding methods such as injection molding and stamping molding can be applied, but it has not been widely used.

This is based on the following reasons. It is well known that impregnation of a fiber bundle with a molten resin becomes more difficult as the melt viscosity of the resin becomes higher. Thermoplastic resins with good mechanical properties generally have high molecular weights and very high melt viscosities. The fiber reinforced composite material using such a high molecular weight thermoplastic resin as a matrix has a problem that the thermoplastic resin is hardly impregnated in the fiber bundle, so that the productivity is low and the production cost is extremely high. On the other hand, using a low-molecular-weight, that is, low-viscosity thermoplastic resin, which is easily impregnated, as a matrix does not solve this problem because the mechanical properties of the composite material are greatly reduced.

The present inventors have attempted to solve this problem, and have found that the ease of impregnation of a low-molecular-weight (low-viscosity) thermoplastic polymer, that is, high productivity, and that high-molecular-weight thermoplastic resin is used as a matrix. Having the same high mechanical properties, for example, when molding by injection molding, etc.,
A molding material and a method for producing the molding material, in which the impregnation of the fiber and the high-viscosity matrix can be achieved at the stage of plasticizing the material at the time of molding and the dispersibility of the fiber of the molded product is good, have been found (JP-A-10-138378). .

Japanese Patent Application Laid-Open No. 10-138378 discloses the following components [a], [b], and [c].
A molding material in which [c] is arranged so as to be in contact with the composite consisting of [b] is disclosed. [A] a continuous reinforcing fiber bundle [b] a thermoplastic polymer having a weight average molecular weight of 200 to 50,000 and a lower melt viscosity than the component [c] [c] a thermoplastic resin having a weight average molecular weight of 10,000 or more Such a molding material in which carbon fiber is applied to the element [a] is excellent in moldability and has little breakage of carbon fiber at the time of molding. Therefore, molding in which short fibers of existing carbon fiber are dispersed in a thermoplastic resin. It has excellent mechanical properties that can not be obtained with materials at all, such as impact resistance and rigidity, and excellent electromagnetic wave shielding properties that make full use of the conductivity of carbon fiber, such as the case of personal computers and mobile phones. It can be preferably used for the body and the like.

In the case of a material used for a housing of a personal computer, a cellular phone, or the like, an important characteristic is that the surface appearance of a molded product is good. Molded products are often used after post-processing such as surface polishing and painting. However, many steps are required for surface polishing and painting, which causes an increase in cost. For this reason, there is a strong demand for a molding material which can reduce the number of post-processing steps or can omit the post-processing and which can provide a molded article having a good surface appearance.

[0007] By using the molding material disclosed in JP-A-10-138378, a molded article having both the above-mentioned excellent mechanical properties and excellent electromagnetic wave shielding properties can be obtained. The demand level is now increasing, and further improvement is required.

[0008]

SUMMARY OF THE INVENTION The present invention provides a thermoplastic resin composition having both high fluidity and high mechanical properties,
In addition, it has both easy impregnation (high productivity) of low molecular weight (low viscosity) thermoplastic polymer and high mechanical properties when high molecular weight thermoplastic resin is used as matrix, and excellent surface appearance An object of the present invention is to provide a fiber-reinforced thermoplastic resin molding material which gives a molded article having the following. Another object of the present invention is to provide a molded product obtained by molding these.

[0009]

Means for Solving the Problems In order to achieve the above object, the thermoplastic resin composition of the present invention has the following constitution.

That is, at least the following component [A]
And [B].

[A] A thermoplastic polymer represented by the following structural formula (1) and having a lower melt viscosity than the constituent element [B]:

Embedded image (Wherein, Ar is a group selected from the following formulas (2) and (3), R is an alkylene group or a group selected from the following formulas (4) to (7), and T ₁ and T ₂ are each independently Represents any one of a hydrogen atom, a halogen atom, an alkyl group, an aryl group and an aralkyl group, and n represents an integer of 0 or more.)

Embedded image

Embedded image (In the formula, T _{3 to} T ₁₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an aralkyl group.)

Embedded image

Embedded image

Embedded image

Embedded image (In the formula, T _{11 to} T ₃₁ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an aralkyl group.)

[B] Thermoplastic resin having a weight-average molecular weight of 10,000 or more In order to achieve the above object, the molding material of the present invention comprises:
It has the following configuration. That is, a molding material comprising the thermoplastic resin composition of the present invention and reinforcing fibers.

Further, in order to achieve the above-mentioned object, the pellet for injection molding of the present invention has the following constitution. That is, it is an injection molding pellet comprising the thermoplastic resin composition of the present invention or the molding material of the present invention.

In order to achieve the above object, the molded article of the present invention has the following constitution. That is, it is a molded product obtained by molding any one of the molding material of the present invention or the thermoplastic resin composition of the present invention, the molding material of the present invention, and the pellet for injection molding of the present invention.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the thermoplastic resin composition of the present invention will be described. When the component [A] is used in combination with the component [B], the thermoplastic resin composition has high fluidity. In particular, when a reinforcing fiber, a filler, a flame retardant, and the like are added to the resin and the fluidity of the resin is extremely poor, by adding the component [A],
Fluidity at the time of melting can be greatly improved, and moldability is improved.
In general, when such a low-molecular-weight product is added to a resin, the mechanical properties and the like of the resin may be reduced as compared to before the addition, but in the thermoplastic resin composition of the present invention, this property reduction is not likely to occur. It is characterized by being very small.

The component [A] is represented by the following equation (8):
Further, it is a thermoplastic polymer having a lower melt viscosity than the component [B].

Embedded image In the formula, Ar represents a group selected from the following formulas (9) and (10), and R represents an alkylene group or the following formulas (11) to (14).
And T ₁ and T ₂ independently represent any one of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, and an aralkyl group. n is an integer of 0 or more.

Embedded image

Embedded image In the formula, T _{3 to} T ₁₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an aralkyl group.

In the formulas (8) to (10), T _{1 to} T ₁₀ are preferably a hydrogen atom or an alkyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group or an ethyl group Group, n-propyl group, i-propyl group, n-
A butyl group, an i-butyl group and a t-butyl group are more preferred, and a methyl group is more preferred.

When R is an alkylene group, an alkylene group having 1 to 3 carbon atoms, specifically, a methylene group, a dimethylene group, a trimethylene group, a propylene group, -C (CH ₃ ) _2-
Is preferable, and a methylene group is more preferable.

Embedded image

Embedded image

Embedded image

Embedded image In the formulas (11) to (14), T _{11 to} T ₃₁ each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, and an aralkyl group. Among these, a hydrogen atom and an alkyl group are preferable, and as the alkyl group, an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl Group,
An i-butyl group and a t-butyl group are more preferred, and a methyl group is even more preferred.

In the formulas (11) to (14), the formulas (11) and (12) are more preferable, and the formula (11) is more preferable.

The integer n of 0 or more is preferably 30
Or less, more preferably 20 or less, even more preferably 10
It is as follows. If n exceeds 30, the viscosity may increase and the effect of improving the fluidity may decrease.

Preferred specific examples of the above component [B] are thermoplastic polymers as shown below.

For example, a phenol novolak resin represented by the following formula (15) may be mentioned.

Embedded image Various commercial products can be applied to the phenol novolak resin. Examples of commercially available products include Shaunol BRG-558, BRG-5
57 (registered trademark, manufactured by Showa Polymer Co., Ltd.), Phenolite TD
-2131, TD-2106, TD-2093, TD-2090 (registered trademark, manufactured by Dainippon Ink and Chemicals, Inc.), Retop PSM-4261 (registered trademark, manufactured by Gunei Chemical Co., Ltd.), Tamanol 758, 759 (registered trademark, manufactured by Arakawa Chemical Industries, Ltd.).

Further, a cresol novolak resin represented by the following formula (16) may be mentioned.

Embedded image Various commercial products can also be applied to the cresol novolak resin. Examples of commercially available products include Shaunol CRG-951 (registered trademark, manufactured by Showa Polymer Co., Ltd.) and Retop PSM-4261 (registered trademark, manufactured by Gunei Chemical Industry Co., Ltd.). Further, for example, phenol aralkyl resins represented by the following formulas (17) to (19)

Embedded image

Embedded image

Embedded image Is mentioned. Various commercial products can also be applied to the phenol aralkyl resin. Examples of commercially available resins represented by the formula (17) include MILEX XLC-LL, XLC-3L, XLC-4L (registered trademark, manufactured by Mitsui Chemicals, Inc.), SK resin HE100C-10, H
E100C-15, HE100C-30 (registered trademark, Sumikin Chemical Co., Ltd.)
And MEH-7800 (product name, manufactured by Meiwa Kasei Co., Ltd.). An example of a commercially available resin represented by the formula (18) is MEH-7851 (product name, manufactured by Meiwa Kasei Co., Ltd.). Examples of commercial products of the resin represented by the formula (19) include MEH-7860 (product name, manufactured by Meiwa Kasei Co., Ltd.). Also, a naphthol novolak resin represented by the following formula (20)

Embedded image Is mentioned. Also, naphthol aralkyl resins represented by the following formulas (21) and (22)

Embedded image

Embedded image Is mentioned.

Commercial products can be applied to the naphthol aralkyl resin. An example of a commercially available product of the formula (22) includes Kayahard NHN (registered trademark, manufactured by Nippon Kayaku Co., Ltd.).
Further, a thermoplastic polymer represented by the following formulas (23) and (24)

Embedded image

Embedded image Can also be applied.

Among the thermoplastic polymers described above, phenol novolak resins and phenol novolak resins are highly effective in improving fluidity.
Cresol novolak resins and phenol aralkyl resins are more preferred, and phenol aralkyl resins are even more preferred. Among phenol aralkyl resins, the formula (1)
What is represented by 7) is more desirable.

The relationship between the melt viscosities of the components [A] and [B] is as follows: Vicat softening temperature + 30 ° C. or melting point + 30 ° C.
At the temperature of, the melt viscosity of the component [A] may be smaller than the melt viscosity of the component [B].

The melt viscosity of the component [A] is desirably 100 poise or less. More preferably, it is 20 poise or less. If the melt viscosity is higher than 100 poise, a thermoplastic resin composition having high fluidity may not be obtained. In addition, when the molding material of the present invention described below is manufactured, it is difficult to impregnate the reinforcing fiber bundle with the component [A], and the productivity of the molding material may be reduced. On the other hand, the lower limit of the melt viscosity is not particularly limited, but is preferably 0.5 poise or more, and more preferably 1 poise or more. Below the lower limit, it is difficult to impregnate the reinforcing fiber bundle with a certain amount of the component [A], which is not preferable. Further, the melt viscosity of the component [B] is desirably 500 poise or more, preferably 700 poise or more, and more preferably 800 poise or more. If the value is below the lower limit, the mechanical properties of the thermoplastic resin composition may deteriorate, which is not preferable.
On the other hand, the upper limit is not particularly limited,
It is preferably no greater than poise, and more preferably no greater than 7000 poise. Exceeding the upper limit is not preferred because the fluidity of the thermoplastic resin composition may deteriorate. The melt viscosities of the constituents [A] and [B] described here are determined by the Vicat softening temperature of the substance to be measured (the constituents [A] and [B], respectively) + 30 ° C. or the melting point + 30.
Viscosity at temperature in ° C. If the substance is crystalline and has a distinct melting point, the condition of the melting point + 30 ° C. is used, and otherwise, the condition of the softening temperature + 30 ° C. is used. The viscosity was measured using a capillary rheometer according to JIS K71.
Measured according to the 99 test method. The shear rate in the measurement is 10 ³ s ^-1 . The Vicat softening temperature is determined according to JIS
The melting point is measured according to a K7206 test method, and the melting point is measured by a differential scanning calorimeter (hereinafter abbreviated as DSC).

In the thermoplastic resin composition of the present invention, the component [A] preferably contains 0.5 to 40 parts by weight based on 100 parts by weight of the total of the components [A] and [B]. 0.
If the amount is less than 5 parts by weight, the fluidity improving effect may be small. If the amount exceeds 40 parts by weight, the mechanical properties of the resin composition may be greatly reduced. A more desirable amount is 2
The range is from 30 to 30 parts by weight, more preferably from 5 to 15 parts by weight.

The thermoplastic resin composition of the present invention contains a reinforcing fiber, a flame retardant, a weather resistance improver, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a colorant, a compatibilizer, and a conductive agent. A filler or the like can be added.

The degree of mixing of the thermoplastic resin composition of the present invention is not particularly limited. The components may be kneaded so that each component is substantially uniformly dispersed, or, for example, the component [A] is impregnated in the reinforcing fiber, and the component [B] is disposed in contact with the reinforcing fiber. It may be a composition of a separate type. In this case, the component [A] also functions as an auxiliary agent for easily impregnating the component [B] into the reinforcing fiber when molding the thermoplastic resin composition.

Next, the thermoplastic resin used as the component [B] must have a weight average molecular weight of 10,000 or more, more preferably 12,000 or more. If the weight-average molecular weight is less than 10,000, the mechanical properties of the finally obtained composite material molded article will be low. Although the upper limit is not particularly limited, it is 5,000,0.
00 or less, more preferably 1,000,000 or less, and even more preferably 500,000 or less. Exceeding the above upper limit is not preferred because the viscosity of the molding material becomes too high and the fluidity may decrease.

Component [B] has a weight average molecular weight of 10,
Although not particularly limited as long as it is not less than 000, preferred thermoplastic resins in terms of mechanical properties include polyamide, polyester, polycarbonate, polyarylene oxide, polyarylene sulfide, polysulfone, polyimide, aromatic vinyl monomer and vinyl cyanide. It is preferably a copolymer containing at least two kinds selected from monomers and rubbery polymers, a mixture of these two or more kinds, or a copolymer thereof (for example, a block or a graft).

Among the thermoplastic resins mentioned above, more preferred are polyamides, polyesters, polycarbonates, polyarylene oxides, aromatic vinyl monomers, vinyl cyanide monomers, and rubbery polymers. Or a mixture of two or more of these, or a copolymer thereof. In particular, in order to obtain a molded product having excellent mechanical properties and a good surface appearance, polyamide, polyester, polycarbonate, aromatic vinyl monomer, vinyl cyanide monomer,
A copolymer containing at least two kinds selected from rubbery polymers as constituent components, a mixture of these two or more kinds or a copolymer thereof (for example, a block, a graft, or the like) is preferable.

Here, the polyamide is a resin having an amide bond in the main chain. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polyhexamethylene sebacamide (nylon 6).
10), polyhexamethylene dodecamide (nylon 61
2) homopolymers such as polydodecaneamide (nylon 12), polyundecaneamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), and polyxylylene adipamide (nylon XD6) or copolymers thereof And the like, and these can be used alone or as a mixture. From the viewpoint of mechanical properties, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyxylylene adipamide (nylon XD6) may be used alone, or a mixture or copolymer thereof may be used. More preferably, another polyamide may be mixed or copolymerized with the polyamide.

Polyester is a resin having a carboxylic acid ester bond in the main chain. Specific examples include homopolymers such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, and polyethylene naphthalate, and copolymers thereof. Further, a polycondensate of a dihydric phenol compound and an aromatic dicarboxylic acid, for example, a polycondensate using bisphenol A as a dihydric phenol compound, terephthalic acid as an aromatic dicarboxylic acid, or isophthalic acid, The liquid crystalline polyester shown can also be used. These can be used alone or as a mixture. Among these, polybutylene terephthalate is preferred from the viewpoint of good moldability.

Polycarbonate is a resin having a carbonate bond in the main chain. Specifically, it is a polymer obtained by a phosgene method of reacting a dihydric phenol compound with phosgene, or a transesterification method of reacting a dihydric phenol compound with a carbonate such as diphenyl carbonate. And those produced using bisphenol A as a dihydric phenol compound. Further, in order to improve the flowability of the polycarbonate and improve the molding processability, at least two kinds selected from aromatic vinyl polymers such as polystyrene, aromatic vinyl monomers, vinyl cyanide monomers, and rubbery polymers. Also, a composition containing a copolymer or the like having a component as a component is often used.

Polyarylene oxide is a resin having a main chain structure in which divalent aromatic groups and oxygen atoms are alternately arranged. A typical example is poly (2,6-dimethyl-1,4-phenylene ether). Also,
In order to improve the moldability of polyarylene oxide,
A composition containing polystyrene or the like is often used.

Polyarylene sulfide is a resin having a main chain structure in which divalent aromatic groups and sulfur atoms are alternately arranged. A typical example is poly (1,4-phenylene thioether). Further, the main chain may have a sulfonyl group or an ether bond in some cases.

Polysulfone is a resin having a sulfonyl group in the main chain. In some cases, the main chain may have an ether bond or the like.

Polyimide is a resin having a dicarboxylic imide structure in the main chain. In some cases, the main chain may have an ether bond, an amide bond, or the like.

There are many types of copolymers containing at least two components selected from aromatic vinyl monomers, vinyl cyanide monomers, and rubbery polymers.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, monochlorostyrene, dichlorostyrene, monobromostyrene,
Dibromostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like are preferable, and styrene and α-methylstyrene are preferable. The vinyl cyanide monomer is, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like, and is preferably acrylonitrile. Examples of the rubbery polymer include, for example, polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers. Diene rubbers such as polymers, random copolymers and block copolymers of ethylene-propylene, ethylene and α-
Copolymer with olefin, ethylene-methacrylate,
Copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-butyl acrylate, acrylic elastic polymer such as acrylate-butadiene copolymer, butyl acrylate-butadiene copolymer, and ethylene such as ethylene-vinyl acetate Copolymer of ethylene and fatty acid vinyl, ethylene-propylene non-conjugated diene terpolymer such as ethylene-propylene-hexadiene, butylene-isoprene copolymer, chlorinated polyethylene and the like, and one or a combination of two or more of these. Used in. Preferred rubbery polymers are diene rubbers, acrylic elastic polymers, ethylene-propylene non-conjugated diene terpolymers, more preferably polybutadiene and styrene-
It is a butadiene copolymer.

Further, a vinyl monomer copolymerizable with these components can be used together. Examples of such a monomer include methacrylates such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, and glycidyl methacrylate, methyl acrylate, ethyl acrylate, acrylates such as butyl acrylate, N-phenylmaleimide,
Maleimide monomers such as N-methylmaleimide; and maleic anhydride.

Examples of such a copolymer include an acrylonitrile-styrene copolymer (AS resin) and an acrylonitrile-styrene-polybutadiene copolymer (ABS).
Resin), a copolymer (AAS resin) composed of an acrylonitrile-styrene-acrylic elastic polymer, and the like, and these can be preferably used.

The component [B] includes a flame retardant, a weather resistance improver, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a lubricant according to the required characteristics of the molded article to be obtained. , A colorant, a compatibilizer, a conductive filler, and the like.

In the present invention, component [A] needs to have a lower melt viscosity than component [B]. Although not particularly limited, the viscosity of the component [B] is preferably at least 5 times, more preferably at least 25 times, and at least 40 times the viscosity of the component [A]. Is particularly preferred. If the value is below the lower limit, the mechanical properties may be undesirably reduced. On the other hand, the upper limit is not particularly limited, but is preferably 10,000 times or less. Exceeding the upper limit is not preferable because mixing of the component [A] and the component [B] during molding may become difficult. The constituent element [A] or [B] may be cross-linked or polymerized by a cross-linking agent or a curing agent at the time of molding, or may be degraded by heat or other physical or chemical action at the time of processing or the like. In some cases, the molding material or molded article of the present invention may not have such a melt viscosity ratio. In such a case, it is only necessary that the melt viscosities of the constituent elements [A] and [B] estimated from the molecular weight before modification have the above melt viscosity ratio.

Next, the molding material of the present invention will be described.

The molding material of the present invention comprises the above-mentioned thermoplastic resin composition of the present invention and reinforcing fibers.

Preferred as a molding material is a reinforcing fiber bundle in which reinforcing fibers are continuous, and the reinforcing fibers and the constituent element [A] are used.
Is a molding material that is configured by disposing the component [B] in contact with the composite made of In the molding material of the present invention, the reinforcing fiber is a continuous fiber bundle, for example, in a pellet, the reinforcing fiber is cut in the middle of the pellet, the reinforcing fiber significantly shorter than the entire length of the pellet substantially. It is not included. In particular, although the amount of the reinforcing fiber shorter than the entire length of the pellet is not specified, 70% by weight or more of the total pellet has a carbon fiber content of 50% or less of the entire length of the pellet. % Or less (preferably 20% by weight or less). The total length of the pellet is the length of the pellet in the reinforcing fiber orientation direction. It is considered that by forming the component [A] into a continuous reinforcing fiber bundle, it is possible to impart high mechanical properties to a molded article as a reinforcing fiber of a composite material. The constituent element [B] is a matrix resin having a relatively high viscosity and high mechanical properties such as toughness. It is considered that the constituent element [B] has a role of impregnating the reinforcing fibers after molding, bonding to the reinforcing fibers, and holding the reinforcing fibers firmly. The component [A] is a relatively low-viscosity thermoplastic polymer, forms a composite with the reinforcing fibers, and at the time of molding, the matrix resin (component [B]) is used to form the reinforcing fiber bundle (component [C]). ) Is considered to have a role as a so-called impregnation aid / dispersion aid, which helps to impregnate and also helps the reinforcing fibers to disperse in the matrix.

The reinforcing fiber and the component [A] form a complex with the two. The form of this composite is as shown in FIG. 1, and the component [C] (1) which is a continuous fiber bundle
The component [A] (2) is filled between each single fiber. That is, the reinforcing fibers are dispersed like an island in the sea of the component [A]. Specifically, the composite is formed by heat-melting the component [A] and impregnating the reinforcing fibers.

FIGS. 2 to 7 schematically show examples of the cross-sectional shape of the molding material of the present invention. The cross-sectional shape of the molding material is a composite (3) composed of reinforcing fibers and component [A].
However, as long as the component [B] (4) is disposed so as to be in contact with the composite, the component is not limited to the one shown in the drawings. Preferably, as shown in FIGS. It is preferable that [B] is arranged so as to cover the periphery or, as shown in FIGS. 6 and 7, the complex and the component [B] are arranged in layers. When arranging a plurality of composites as shown in FIG. 4 so that the component [B] covers them, the number of composites is preferably about 2 to 6.

It is desirable that the boundary between the composite and the component [B] is bonded. The component [B] partially enters the composite near the boundary and is in a state of being compatible with the component [A] or impregnating the reinforcing fibers. You may.

The molding material may be continuous as long as it keeps substantially the same cross-sectional shape in the longitudinal direction. Depending on the molding method, such a continuous molding material may be cut to a certain length.

The molding material of the present invention can be made into a final molded product by mixing the constituents [A], [B] and [C] by a technique such as injection molding or press molding. From the viewpoint of handleability of the molding material, it is important that the respective components do not separate until the molding is performed, and maintain the shape as described above. Since the constituent element [A] has a low molecular weight, it is usually a relatively fragile solid or liquid at room temperature and often a liquid. For this reason, the high-molecular-weight component [B] is arranged so as to protect the composite, and the material is transported until molding, shock during handling,
It is desirable to prevent the component [B] from being crushed and scattered due to abrasion or the like.

Therefore, as shown in FIGS. 2 to 5, a composite composed of the constituent element [C] and the constituent element [A], which is a reinforcing fiber, moves the constituent element [B] around the composite. It is preferable that the composite and the component [B] are arranged so as to cover or are arranged in layers as illustrated in FIGS. With such an arrangement, the high-molecular-weight component [B] wraps the fragile component [A] or is disposed on a surface that is easily rubbed, so that the shape is maintained as a molding material. Cheap. Further, whether the component [B] is arranged so as to cover the periphery of the composite or the composite and the component [B] are arranged in a layer, which is more advantageous, is easy to manufacture. From the viewpoint of ease of handling of the material, the component [B] is more preferably arranged so as to cover the periphery of the composite.

It is desirable that the reinforcing fibers be completely impregnated with the component [A]. Theoretically speaking, the state in which the reinforcing fibers (component [C]) are arranged in a hexagonal shape and are in the closest packing state, and the component [A] is impregnated in the gaps between the fibers, is the most component [ A] is small, and assuming that the fibers have the same diameter in a perfect circular cross section, the volume content of the reinforcing fibers is 90.7% (= π / (2 ×
3 ^1/2 )). In fact, achieving such a volume content without voids is technically difficult. However,
Even when a certain amount of voids are present, or even when the volume content rate is so high that an unimpregnated portion is calculated, the effect of promoting impregnation and fiber dispersion can be obtained. In consideration of this, the volume content of the reinforcing fibers in the composite is preferably 40% or more in order to prevent the mechanical properties of the formed composite material from being deteriorated. On the other hand, if the volume content exceeds 95%, the portion between the single fibers that cannot be filled with the component [A] increases, and as a result, the effect of accelerating the impregnation decreases rapidly. The content is preferably 95% or less. A more preferred volume content is 80% or less.

As described above, it is desirable that the reinforcing fiber is completely impregnated with the constituent element [A], but it is difficult in practice, and the composite made of the reinforcing fiber and the constituent element [A] is difficult. There are some voids. In particular, when the content of the reinforcing fibers is large, the number of voids increases. However, even when a certain amount of voids are present, the effect of the present invention for promoting impregnation and fiber dispersion is exhibited. However, if the void ratio exceeds 40%, the effect of promoting impregnation and fiber dispersion is significantly reduced, and therefore the void ratio is preferably in the range of 0 to 40%. A more desirable range of the void fraction is 20% or less. The void fraction is determined by dividing the part of the composite into ASTM D2734.
Measure by the test method.

The reinforcing fiber bundle used as the reinforcing fiber is not particularly limited. High-strength, high-modulus fibers such as carbon fibers, glass fibers, polyaramid fibers, alumina fibers, silicon carbide fibers, boron fibers, and metal fibers can be used. These may be used in combination of two or more. Among these, carbon fibers are preferable because of their excellent effect of improving mechanical properties. In addition, since carbon fibers have conductivity, molded articles exhibit excellent electromagnetic wave shielding properties, and are particularly preferable for housing applications such as personal computers and mobile phones.

More preferably, the surface functional group content (O / C), which is the ratio of the number of oxygen (O) to the number of carbon (C) atoms on the fiber surface measured by X-ray photoelectron spectroscopy, is from 0.05 to 0.05. 0.
Continuous carbon fibers in the range of 4 are suitable. O / C
Is smaller than 0.05 means that the surface of the carbon fiber has very few functional groups that contribute to the adhesion to the matrix resin. If the adhesion between the carbon fiber and the matrix resin is inferior, high mechanical properties cannot be expected from the molded product. On the other hand, when O / C is larger than 0.4, it means that the carbon fiber surface is subjected to an oxidizing treatment or the like more than necessary, and the crystal structure of carbon is destroyed and a fragile layer is formed on the fiber surface. are doing. In this case as well, when the O / C is too low,
Since the fracture is likely to occur near the fiber surface layer, high mechanical properties cannot be expected in the molded product. Further, by setting the O / C within the above range, not only the adhesion at the fiber / matrix interface but also the affinity at the time of impregnating the component [A], the dispersibility at the time of fiber molding, and the like are preferable. Bring effect.

The surface functional group content (O / C) can be determined by X-ray photoelectron spectroscopy according to the following procedure. First, carbon fiber (bundle) from which the sizing agent etc. has been removed with a solvent
Was cut and spread on a copper sample support, and the photoelectron escape angle was set to 90 °, and MgKα1 was used as an X-ray source.
2 and the sample chamber is kept at 1 × 10 ⁻⁸ Torr. Fit main peak of the kinetic energy value of C _1S a (K. E.) to 969eV as a correction of the peak due to measurement during charging. The C _1S peak area is K. E. FIG. 958-9
It is determined by drawing a straight base line in the range of 72 eV. The O _1S peak area is K. E. FIG. As 714-7
It is determined by drawing a straight base line within a range of 26 eV. Here, the surface functional group content (O / C) refers to the above O _1S
From the ratio of the peak area to the _C1S peak area, the ratio is calculated as the atomic number ratio using a sensitivity correction value unique to the apparatus.

The molding material of the present invention is preferably 1 to 50
Cut into lengths in the range of mm for use. By adjusting the length to the above-mentioned length, fluidity of the molding material is generated, and shapeability at the time of molding is greatly increased. The shorter the cutting length, the more the moldability such as shapeability and fluidity increases, but if the cutting length is less than 1 mm, the reinforcing fiber length becomes shorter as a result, and the fiber reinforcing effect rapidly decreases. When the cutting length exceeds 50 mm, the reinforcing effect is increased, but the formability is greatly reduced. A more desirable range of the cutting length is 3 to 12 mm. The molding material cut to an appropriate length in this manner can be preferably used as pellets for injection molding.

The molding material of the present invention can be used depending on the molding method even if it is continuous or long. For example, as a thermoplastic yarn prepreg, it can be wound around a mandrel while heating to obtain a roll-shaped molded product. Examples of such molded articles include liquefied natural gas tanks and the like. It is also possible to produce a one-way thermoplastic prepreg by heating and fusing a plurality of the molding materials of the present invention in one direction. Such a prepreg can be applied to a field where high strength, elastic modulus and impact resistance are required, for example, an aircraft primary structural material.

As a method for producing the molding material of the present invention, a method described in JP-A-10-138378 can be preferably used. That is, a composite is formed by impregnating the reinforcing fiber with the component [A] that has been heated and melted so that the viscosity becomes 100 poise or less, and then the melted component [B] having a viscosity of 500 poise or more is added to the composite. After arranging so as to be in contact with the composite, a method of cooling the whole to room temperature can be used.

The molding material and the thermoplastic resin composition of the present invention can be processed into a final product by a known molding method. Examples of the molding method include press molding, transfer molding, injection molding, and combinations thereof. Examples of molded articles include automobile parts such as cylinder head covers, bearing retainers, intake manifolds, pedals, etc., tools such as monkeys and wrenches, and small articles such as gears. Further, since the molding material of the present invention is excellent in fluidity, a thin molded product having a thickness of 0.5 to 2 mm can be obtained relatively easily. Such thin-wall molding is required, for example, in a housing such as used in a personal computer or a mobile phone, or a keyboard support which is a member for supporting a keyboard inside the personal computer. For electrical and electronic equipment. In such a member for electric / electronic devices, it is more desirable to use an electrically conductive carbon fiber as the reinforcing fiber because electromagnetic wave shielding properties are imparted.

The above-mentioned molding material and thermoplastic resin composition can be used as pellets for injection molding. In injection molding, temperature, pressure, and kneading are added when plasticizing a pellet-shaped molding material. According to the present invention, the component [A] has a great effect as a dispersing / impregnating aid according to the present invention. Demonstrate. In this case, a normal in-line screw type injection molding machine can be used, for example, using a screw having a low compression ratio or setting a low back pressure at the time of plasticizing the material, and kneading with the screw. Even when the effect is weak, the reinforcing fibers are well dispersed in the matrix resin, and a molded article with good resin impregnation into the fibers can be obtained.

[0066]

The present invention will be described in more detail with reference to the following examples.

(1) Measurement of Vicat Softening Temperature The Vicat softening temperature was measured according to the method A and the air heating method described in JIS K7206.

(2) Melting point measurement According to JIS K7121, DSC system TA300
Using 0 (manufactured by Mettler) at a heating rate of 10 ° C./min, the melting peak temperature was taken as the melting point.

(3) Viscosity measurement In accordance with JIS K7199, a capillary rheometer (Capillograph 1B, manufactured by Toyo Seiki Seisaku-sho, Ltd.) is used.
Viscosity at a shear rate of 10 ³ s ⁻¹ was measured at a temperature of 0 ° C. and at a temperature of Vicat softening point + 30 ° C. for those not showing a clear melting point.

(4) Measurement of Surface Roughness of Molded Product Using a surface roughness meter (Form Talysurf Series 2, manufactured by Taylor Hobson), a thickness of 1 mm and an outer shape of 150 mm ×
A cross-sectional curve over a length of 12.5 mm was obtained from the center point of a 150 mm thin-walled flat product in the direction opposite to the fan gate, and this length was used as an evaluation length according to JIS B06.
01 and a roughness curve was obtained. From the roughness curve, an arithmetic average roughness (Ra) at a cutoff value of 2.5 mm and a maximum height (Ry) at a reference length of 2.5 mm were determined.

(5) Measurement of Izod impact strength Test specimen thickness 3.2 mm according to ASTM D256
A (1/8 inch) notched Izod impact strength test specimen was injection molded. The test piece was used for the test after drying to a moisture content of 0.1% or less.

Example 1 A phenol novolak resin (Shaunol BRG-55) was placed on a roll heated to 130 ° C. using a kiss coater.
8. A liquid film was formed by heating and melting a registered trademark (manufactured by Showa Polymer Co., Ltd., Vicat softening temperature: 95 ° C.). A continuous carbon fiber bundle (tensile strength 4900MP) on this roll
a, tensile elastic modulus 230 GPa, elongation 2.1%, number of filaments 12,000, fineness 800 g / 1000 m, density 1.8 g / cm ³ ), while passing through them, keeping constant per unit length of carbon fiber bundle An amount of phenol novolak resin was deposited.

The carbon fiber to which the phenol novolak resin was adhered was heated to 180 ° C., rotated freely by a bearing, and arranged in ten straight lines with a diameter of 50 mm.
, And passed alternately over and under the roll. By this operation, the polymer was impregnated into the inside of the fiber bundle to form a continuous composite composed of carbon fibers and a phenol novolak resin. At this stage, the amount of the polymer relative to the entire composite is 1
It was 5% by weight. BRG-558 at 125 ° C
The melt viscosity at a shear rate of 10 ³ s ^-1 was 40 poise.

This continuous composite was passed through a coating die for covering electric wires installed at the tip of a single-screw extruder having a diameter of 40 mm, and nylon 6 resin (Amilan) melted at 240 ° C. from the extruder into the die. CM1017, registered trademark, “Amilan” CM1017 manufactured by Toray Industries, Inc., weight average molecular weight 18,600,
(Melting point: 210 ° C.), and nylon 6 resin was continuously disposed so as to cover the periphery of the composite. The melt viscosity of this nylon 6 resin at 240 ° C. at a shear rate of 10 ³ s ⁻¹ was 2030 poise.

The molding material obtained by coating the composite with nylon 6 was cooled to near normal temperature, and then cut to a length of 7 mm with a strand cutter to produce injection molding pellets. The production of the molding material up to this point was performed in a continuous process, and the take-up speed of the carbon fiber bundle was 30 m / min.

Using these pellets, a mold clamping force of 980 k
150mm x 150m outer shape by N injection molding machine
m, a thin flat molded product having a thickness of 1 mm was molded using a mold having a fan gate. In addition, a test piece for measuring Izod impact strength with a notch was molded by the same injection molding machine. During molding, the cylinder temperature was set at 250 ° C. near the nozzle, and the mold temperature was 70 ° C.

The composition ratio of the molded product was carbon fiber: phenol novolak resin: nylon 6 resin = 35: 6: 59.

In the visual observation, the surface of the flat molded product was smooth and glossy, and there was no problem in the dispersibility of the fibers in the molded product.
Microscopic observation of the cross section of the molded product revealed no voids.

The arithmetic average roughness (Ra) of the molded product is 3.3
μm.

The maximum height (Ry) is 18.4 μm
Met.

The notched Izod impact strength of the molded product was 220 J / m.

Example 2 In place of the phenol novolak resin of Example 1, a phenol novolak resin (Phenolite TD2090, registered trademark,
Vicat softening temperature 12 manufactured by Dainippon Ink and Chemicals, Inc.
0 ° C.) and the roll temperature was changed to 180 ° C.
In the same manner as in Example 1, injection molding pellets were produced.
Further, the shear rate of TD2090 at 150 ° C. was 10 ³ s ^−1.
Was 70 poise.

Using the pellets, a thin plate molded product and a test piece for measuring the Izod impact strength with a notch were formed in the same manner as in Example 1.

The composition ratio of the molded article was carbon fiber: phenol novolak resin: nylon 6 resin = 35: 6: 59.

In the visual observation, the surface of the flat molded product was smooth and glossy, and there was no problem in the dispersibility of the fibers in the molded product.
Microscopic observation of the cross section of the molded product revealed no voids.

The arithmetic average roughness (Ra) of the molded product is 2.6.
μm.

The maximum height (Ry) is 14.4 μm
Met.

The notched Izod impact strength of the molded product was 245 J / m.

Example 3 Instead of the phenol novolak resin of Example 1, a cresol novolak resin (Shaunol CRG-951, registered trademark, manufactured by Showa Polymer Co., Ltd., Vicat softening temperature 105 ° C.)
A pellet for injection molding was produced in the same manner as in Example 1 except that を was used. The CRG-951 at 135 ° C.
The melt viscosity at a shear rate of 10 ³ s ^-1 was 16 poise.

Using the pellets, a thin plate molded product and a test piece for measuring the Izod impact strength with a notch were formed in the same manner as in Example 1.

The composition ratio of the molded article was carbon fiber: cresol novolak resin: nylon 6 resin = 35: 6: 59.

In the visual observation, the surface of the flat molded product was smooth and glossy, and there was no problem in the dispersibility of the fibers in the molded product.
Microscopic observation of the cross section of the molded product revealed no voids.

The arithmetic average roughness (Ra) of the molded product is 3.7
μm.

The maximum height (Ry) is 16.6 μm
Met.

The notched Izod impact strength of the molded product was 240 J / m.

Example 4 Example 1 was repeated except that a phenol aralkyl resin (Mirex XLC-LL, registered trademark, manufactured by Mitsui Chemicals, Inc., Vicat softening temperature: 82 ° C.) was used in place of the phenol novolak resin of Example 1. In the same manner as in the above, injection molding pellets were produced. The shear rate of XLC-LL at 112 ° C was 1
The melt viscosity at 0 ³ s ^-1 was 15 poise.

Using the pellets, a thin plate molded product and a notched Izod impact strength test specimen were molded in the same manner as in Example 1.

The composition ratio of the molded article was carbon fiber: phenol aralkyl resin: nylon 6 resin = 35: 6: 59.

In the visual observation, the surface of the flat molded product was smooth and glossy, and there was no problem in the dispersibility of the fibers in the molded product.
Microscopic observation of the cross section of the molded product revealed no voids.

The arithmetic average roughness (Ra) of the molded product is 2.2
μm.

The maximum height (Ry) is 10.2 μm
Met.

The notched Izod impact strength of the molded product was 255 J / m.

Comparative Example 1 This comparative example corresponds to Example 1 of JP-A-10-138379.

In place of the phenol novolak resin of Example 1, a terpene phenol polymer (YP90L, trade name,
Except for using Showa Polymer Co., Ltd., Vicat softening temperature of 100 ° C.), injection molding pellets were prepared in the same manner as in Example 1. The melt viscosity of YP90L at 130 ° C. at a shear rate of 10 ³ s ⁻¹ was 11 poise.

Using the pellets, a thin plate molded product and a notched Izod impact strength test specimen were molded in the same manner as in Example 1.

The composition ratio of the molded article was carbon fiber: terpene phenol polymer: nylon 6 resin = 35: 6: 59.

In the visual observation, the surface of the flat molded product was smooth and glossy, but the gloss was inferior to those of Examples 1-4. There was no problem in the dispersibility of the fibers in the molded product, and the cross section of the molded product was observed under a microscope, but no void was confirmed.

The arithmetic average roughness (Ra) of the molded product is 7.7.
μm, which was larger than Examples 1-4.

The maximum height (Ry) is 22.4 μm
And larger than Examples 1 to 4.

From these results, it is understood that the surface smoothness of Comparative Example 1 is inferior to Examples 1 to 4.

The notched Izod impact strength of the molded product was 206 J / m, which was lower than Examples 1-4.

[0112]

The thermoplastic resin composition according to the present invention has excellent fluidity.

Further, the molding material according to the present invention is easy to produce, has good dispersion of the reinforcing fiber bundle in the molded article when molded by injection molding or the like, has excellent mechanical properties, and is particularly suitable for personal use. A molded article having an excellent surface appearance required for a housing such as a computer or a mobile phone can be obtained. Moreover, a molded article having excellent quality can be provided from these.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a cross section of an example of a form of a composite in a molding material according to the present invention.

FIG. 2 is an explanatory view showing a cross section of an example of a form of a molding material according to the present invention.

FIG. 3 is an explanatory view showing a cross section of another example of the form of the molding material according to the present invention.

FIG. 4 is an explanatory view showing a cross section of another example of the form of the molding material according to the present invention.

FIG. 5 is an explanatory view showing a cross section of another example of the form of the molding material according to the present invention.

FIG. 6 is an explanatory view showing a cross section of another example of the form of the molding material according to the present invention.

FIG. 7 is an explanatory view showing a cross section of another example of the form of the molding material according to the present invention.

[Explanation of symbols]

 1: Single fiber of reinforcing fiber 2: Component [A] 3: Composite composed of reinforcing fiber and component [A] 4: Component [B]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F072 AB10 AB21 AD14 AD37 AD42 AD44 AD45 AD46 AD52 AK15 4J002 BN14X BN15X CC04W CC05W CE00W CF00X CG00X CH07X CL00X CM04X CN01X CN03X DA016 FA046

Claims (10)

[Claims] 1. A thermoplastic resin composition comprising at least the following components [A] and [B]. [A] represented by the following structural formula (1), and a constituent element [B]
Thermoplastic polymer having lower melt viscosity than (Wherein, Ar is a group selected from the following formulas (2) and (3), R is an alkylene group or a group selected from the following formulas (4) to (7), and T ₁ and T ₂ are each independently Represents any one of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, and an aralkyl group, and n represents an integer of 0 or more. Embedded image (In the formula, T _{3 to} T ₁₀ each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, and an aralkyl group.) Embedded image Embedded image Embedded image (In the formula, T _{11 to} T ₃₁ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an aralkyl group.) [B] Thermoplastic resin having a weight average molecular weight of 10,000 or more 2. The thermoplastic resin composition according to claim 1, wherein [A] is contained in an amount of 0.5 to 40 parts by weight based on 100 parts by weight of the total of components [A] and [B]. 3. The constituent element [B] is selected from polyamide, polyester, polycarbonate, polyarylene oxide, polyarylene sulfide, polysulfone, polyimide, aromatic vinyl monomer, vinyl cyanide monomer, and rubbery polymer. 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a copolymer containing at least two kinds of constituent components, a mixture of two or more kinds thereof, or a copolymer thereof. 4. 4. A molding material comprising the thermoplastic resin composition according to claim 1 and reinforced fibers. 5. The molding according to claim 4, wherein the reinforcing fiber is a continuous reinforcing fiber bundle, and the component [B] is arranged so as to be in contact with a composite composed of the reinforcing fiber and the component [A]. material. 6. The molding material according to claim 5, wherein the component [B] is arranged so as to cover the periphery of the composite. 7. The molding material according to claim 4, wherein the reinforcing fibers are continuous carbon fibers. 8. The molding material according to claim 4, wherein the molding material is cut to a length in a range of 1 to 50 mm. 9. A pellet for injection molding, comprising the thermoplastic resin composition according to any one of claims 1 to 3 or the molding material according to any one of claims 4 to 8. 10. The thermoplastic resin composition according to any one of claims 1 to 3, the molding material according to any one of claims 4 to 8, and the pellet for injection molding according to claim 9. A molded product characterized by being molded.