JP2010150358A - Molding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide reinforcing fiber bundles which are excellent in adhesiveness to a thermoplastic resin, particularly to a polyolefin-based resin and exhibit good handleability. <P>SOLUTION: A molding material comprising the following components (A) to (D) is provided, wherein the component (D) is bonded to a complex comprising the components (A) to (C) and the order of weight average molecular weight Mw is (D)>(B)>(C); (A) 1-75 wt.% of reinforcing fiber bundles, (B) 0.01-10 wt.% of a first propylene-based resin, (C) 0.01-10 wt.% of a second propylene-based resin containing at least a carboxylate bonded to a polymer chain, and (D) 30-98.98 wt.% of a third propylene-based resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a long fiber reinforced thermoplastic resin molding material having an olefin resin as a matrix. More specifically, the present invention relates to a molding material capable of producing a molded product having good dispersion of reinforcing fibers in the molded product and excellent mechanical properties when performing injection molding.

  As a molding material having a continuous reinforcing fiber bundle and a thermoplastic resin as a matrix, a wide variety of forms such as thermoplastic prepreg, yarn, and glass mat (GMT) are known. Such a molding material makes use of the properties of the thermoplastic resin to facilitate molding, does not require a storage load like a thermosetting resin, and the obtained molded product has high toughness and excellent recyclability. There are features. In particular, a molding material processed into a pellet can be applied to a molding method having excellent economic efficiency and productivity such as injection molding and stamping molding, and is useful as an industrial material.

  However, in the process of producing a molding material, impregnating a continuous reinforcing fiber bundle with a thermoplastic resin has a problem in terms of economy and productivity and is not widely used at present. For example, it is well known that the higher the melt viscosity of the resin, the more difficult the impregnation of the reinforcing fiber bundle is. Thermoplastic resins with excellent mechanical properties such as toughness and elongation are high molecular weight polymers, have higher viscosity than thermosetting resins, and require higher processing temperatures, making molding materials easier. In addition, it is unsuitable for manufacturing with good productivity.

  On the other hand, when a low molecular weight, that is, a low viscosity thermoplastic resin is used for the matrix resin due to the ease of impregnation, there is a problem that the mechanical properties of the obtained molded product are significantly lowered. A molding material is disclosed in which a high molecular weight thermoplastic resin is placed in contact with a composite composed of a low molecular weight thermoplastic polymer and continuous reinforcing fibers (for example, Patent Document 1).

  In this molding material, a low molecular weight material is used separately for impregnation into a continuous reinforcing fiber bundle, and a high molecular weight material is used for the matrix resin, thereby achieving both economic efficiency, productivity and mechanical properties. Also, when this molding material is molded by injection molding, it is easily mixed with matrix resin while minimizing breakage of reinforcing fibers at the stage of material plasticization during molding, and molding with excellent fiber dispersibility Product can be manufactured. Therefore, the obtained molded product can increase the fiber length of the reinforcing fiber as compared with the conventional one, and can have both good mechanical properties and excellent appearance quality.

  In recent years, however, fiber-reinforced composite materials have gained a lot of attention, and their applications have been subdivided into various fields, requiring molding materials with excellent moldability, handleability, and mechanical properties of the resulting molded products. In addition, industrially higher economic efficiency and productivity have become necessary. For example, the fiber reinforced composite material has been required to be lightweight and economical, and a lightweight olefin resin, particularly a propylene resin has been used for the matrix resin. Patent Document 2 discloses a long fiber pellet obtained by impregnating carbon fiber treated with a sizing agent having a functional group capable of reacting with an acid group with an acid-modified olefin resin. However, the thermoplastic resin is only an acid-modified olefin resin, and since the viscosity is high, it is very difficult to disperse the carbon fiber bundle in the matrix resin, and there are problems in the mechanical properties and appearance of the molded product.

Under such circumstances, there has been a demand for a long-fiber reinforced thermoplastic resin molding material that exhibits high mechanical properties even when a low-polarity olefin resin is used as a matrix resin and has good dispersibility of reinforcing fibers. It was.
Japanese Patent Laid-Open No. 10-138379 JP 2005-125581 A

  In view of the background of the prior art, the present invention provides excellent dispersion of reinforcing fibers in a molded product when injection molding of a long fiber reinforced thermoplastic resin using a propylene resin as a matrix and excellent mechanical properties. An object of the present invention is to provide a molding material capable of producing a molded product.

  As a result of intensive studies to achieve the above object, the present inventors have found the following molding material that can achieve the above-mentioned problems.

(1) A molding material having the following components (A) to (D), wherein the component (D) is bonded to a composite having the components (A) to (C) A molding material in which the order of the weight average molecular weight Mw is component (D)> component (B)> component (C).
(A) Reinforcing fiber bundle 1 to 75% by weight
(B) First propylene-based resin 0.01 to 10% by weight
(C) Second propylene resin containing at least a carboxylate bonded to a polymer chain 0.01 to 10% by weight
(D) 3rd propylene-type resin 5-98.98 weight%
(2) The component (C) has at least a carboxylate salt at a concentration of 0.05 to 5 mmol equivalent in terms of the group represented by the formula (I) per gram of the resin (1) The molding material as described in 2.
-C (= O) -O -... Formula (I)
(3) One or more types in which 50 to 100% of the carboxylate bonded to the polymer chain of the component (C) is selected from lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and zinc salt The molding material according to either (1) or (2), which is obtained by conversion with two or more metal salts.

  (4) The reinforcing fiber bundle according to (1) or (2), wherein 50 to 100% of the carboxylate bonded to the polymer chain of component (C) is converted with an ammonium salt.

  (5) The molding material in any one of (1)-(4) whose weight average molecular weight Mw of the said component (C) is the range of 1,000-50,000.

  (6) The component (B) has a weight average molecular weight Mw of 30,000 to less than 150,000, 30 to 100% by weight of a propylene resin (B-1), and a weight average molecular weight Mw of 150,000. The molding material according to any one of (1) to (5), comprising a propylene-based resin (B-2) in a range of 500,000 or less and 0 to 70% by weight.

  (7) The molding material according to any one of (1) to (6), wherein the component (B) comprises 50 mol% or more of a structural unit derived from propylene.

  (8) The said component (B) has at least the carboxylate couple | bonded with the polymer chain, and the weight average molecular weight Mw exceeds 50,000 and is 150,000 or less, (1)-(7 ) The molding material according to any one of

  (9) The molding material according to any one of (1) to (8), wherein the component (D) has a group of a carboxylic acid and / or a salt thereof bonded to a polymer chain.

  (10) 5 to 50% by weight of the propylene resin (D-1) having the carboxylic acid and / or salt group bonded to the polymer chain as the component (D), and the carboxylic acid and / or salt thereof. The molding material according to (9), comprising 50 to 95% by weight of a propylene-based resin (D-2) having no group.

(11) The order of millimole equivalents of the group of carboxylic acid and / or salt thereof in terms of group represented by formula (I) per gram of resin is as follows: component (C) ≧ component (B) ≧ component (D The molding material according to any one of (8) to (10).
-C (= O) -O -... Formula (I)
(12) The molding material according to any one of (1) to (11), wherein the reinforcing fiber of the component (A) is a carbon fiber.

  (13) The molding material according to (12), wherein a surface oxygen concentration ratio (O / C) measured by X-ray photoelectron spectroscopy (ESCA) of the carbon fiber is 0.05 to 0.5.

  (14) The molding material according to any one of (1) to (13), wherein the reinforcing fiber bundle of the component (A) is composed of 20,000 to 100,000 single fibers.

  (15) The molding material according to any one of (1) to (14), wherein the porosity for the component (A) is 20% or less.

  (16) The components (A) are arranged substantially parallel to the axial direction, and the length of the components (A) is substantially the same as the length of the molding material (1) to (15) The molding material in any one of.

  (17) The molding material according to (16), wherein the composite has a core structure, and the component (D) has a core-sheath structure covering the periphery of the composite.

  (18) The molding material according to any one of (1) to (17), wherein the molding material is in the form of long fiber pellets.

  (19) The molding material according to any one of (1) to (18), wherein the length of the long fiber pellet in the longitudinal direction is 1 to 50 mm.

  The long fiber reinforced thermoplastic resin molding material of the present invention can produce a molded product with good dispersion of the reinforcing fiber in the molded product and excellent mechanical properties during injection molding. Since it is used, a molded product having excellent lightness can be obtained. The molding material of the present invention is extremely useful for various parts and members such as automobiles, electric / electronic devices, and home appliances.

  The present invention includes a reinforcing fiber bundle (A), a first propylene resin (B), a second propylene resin (C) containing at least a carboxylate bonded to a polymer chain, a third propylene resin ( D). First, these components will be described.

  Although not particularly limited as a reinforcing fiber bundle according to the present invention, for example, high strength, high elastic modulus fibers such as carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber can be used, These may be used alone or in combination of two or more. Among these, PAN-based, pitch-based and rayon-based carbon fibers are preferable from the viewpoint of improving the mechanical properties and reducing the weight of the molded product, and from the viewpoint of the balance between the strength and elastic modulus of the molded product obtained. More preferred are fibers. For the purpose of imparting conductivity, reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be used.

  Further, as the carbon fiber, the surface oxygen concentration ratio [O / C], which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy, is 0.05-0. 5 is preferable, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3. When the surface oxygen concentration ratio is 0.05 or more, the functional group amount on the surface of the carbon fiber can be secured, and a stronger adhesion to the thermoplastic resin can be obtained. Moreover, although there is no restriction | limiting in particular in the upper limit of surface oxygen concentration ratio, Generally it can be illustrated to 0.5 or less from the balance of the handleability of carbon fiber, and productivity.

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

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

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

  The average fiber diameter of the reinforcing fibers is not particularly limited, but is preferably in the range of 1 to 20 μm and in the range of 3 to 15 μm from the viewpoint of mechanical properties and surface appearance of the obtained molded product. More preferred. There is no restriction | limiting in particular in the number of single yarns of a reinforced fiber bundle, It can use within the range of 100-350,000, It is preferable to use within the range of 1,000-250,000 especially. Further, from the viewpoint of productivity of reinforcing fibers, those having a large number of single yarns are preferable, and it is preferable to use them within a range of 20,000 to 100,000. The effect of the present invention, that the dispersion of the reinforcing fibers in the molded product at the time of injection molding is good, can exhibit an excellent effect even on a reinforcing fiber bundle having a larger number of single yarns, and productivity. Both molded product characteristics can be achieved.

  The reinforcing fiber bundle (A) used in the molding material of the present invention means that the reinforcing fiber bundle in which single fibers are arranged in one direction is in a continuous state in the length direction. It is not necessary for all of the single fibers to be continuous over the entire length, and some of the single fibers may be divided in the middle. Examples of such continuous reinforcing fiber bundles include unidirectional fiber bundles, bi-directional fiber bundles, and multidirectional fiber bundles, but from the viewpoint of productivity in the process of manufacturing a molding material, unidirectional The fiber bundle can be used more preferably.

  Examples of the first propylene-based resin (B) of the present invention include a propylene homopolymer or a copolymer of propylene and at least one α-olefin, conjugated diene, non-conjugated diene, and the like.

  Examples of the monomer repeating unit constituting the α-olefin include ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 2-12 carbon atoms excluding propylene such as 1-hexene, 4,4 dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene and 1-dodecene Examples of the monomer repeating unit constituting the α-olefin, conjugated diene, and non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the like. One type or two or more types can be selected.

  Examples of the skeleton structure of the first propylene-based resin (B) include a propylene homopolymer, one or two or more random or block copolymers of propylene and the other monomers, or other heat. Examples thereof include a copolymer with a plastic monomer. For example, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, and the like are preferable.

  In particular, in order to increase the affinity with the third propylene-based resin (D), the first propylene-based resin (B) preferably has 50 mol% or more of structural units derived from propylene. Furthermore, in order to reduce the crystallinity of the first propylene-based resin (B), increase the affinity with the second propylene-based resin (C), and increase the strength of the resulting molded product, the first propylene-based resin (B) preferably has 50 to 99 mol% of structural units derived from propylene, more preferably 55 to 98 mol%, and still more preferably 60 to 97 mol%. Identification of the monomer repeating unit in the propylene-based resin can be performed using a general polymer compound analysis technique such as IR, NMR, mass spectrometry, and elemental analysis.

  The second propylene resin (C) is a propylene resin containing at least a carboxylate bonded to a polymer chain. This is because it is effective to contain a carboxylate in order to enhance the interaction with the reinforcing fiber.

  Examples of the raw material for the second propylene resin (C) include polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, and propylene represented by ethylene / propylene / 1-butene copolymer. α-Olefin alone or a copolymer with two or more types, a neutralized or non-neutralized monomer having a carboxylic acid group, and / or saponified or not saponified A monomer having a carboxylic acid ester can be obtained by graft polymerization. The monomer repeating unit and the skeleton structure of the copolymer of propylene and α-olefin alone or in combination of two or more types can be selected in the same manner as the first propylene resin (B).

  Here, as a monomer having a neutralized or non-neutralized carboxylic acid group, and a monomer having a saponified or unsaponified carboxylic acid ester group, for example, ethylene System unsaturated carboxylic acids and anhydrides thereof, and esters thereof, and compounds having unsaturated vinyl groups other than olefins.

Ethylenically unsaturated carboxylic acids, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Examples of the anhydrides, nadic ^TM Examples thereof include (endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride and the like.

  As monomers having unsaturated vinyl groups other than olefins, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert -Butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (Meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylic acid such as nyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Esters, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc. Hydroxyl group-containing vinyls, epoxy group-containing vinyls such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, vinyl isocyanate, isopropenyl Isocyanate group-containing vinyls such as cyanate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, diacetoneacrylamide Amides such as maleic acid amide, vinyl esters such as vinyl acetate and vinyl propionate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl) Aminoalkyl (meta) such as (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate Acrylates, styrene sulfonic acid, sodium styrene sulfonate, unsaturated sulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) And unsaturated phosphates such as acid phosphates.

  These monomers can be used alone or in combination of two or more. Of these, acid anhydrides are preferable, and maleic anhydride is more preferable.

  Although the raw material of said 2nd propylene-type resin (C) can be obtained by various methods, For example, other than ethylene-type unsaturated carboxylic acid and olefin which have propylene-type resin and unsaturated vinyl group in the organic solvent A method of removing a solvent after reacting with a monomer having an unsaturated vinyl group in the presence of a polymerization initiator, a carboxylic acid having an unsaturated vinyl group in a melt obtained by heating and melting a propylene-based resin, and Examples include a method in which a polymerization initiator is reacted under stirring, a method in which a mixture of a propylene resin, a carboxylic acid having an unsaturated vinyl group, and a polymerization initiator is supplied to an extruder and reacted while heating and kneading. be able to.

  Here, as the polymerization initiator, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene and the like can be mentioned. These can be used alone or in admixture of two or more.

  Organic solvents include aromatic hydrocarbons such as xylene, toluene and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane, decane, isooctane and isodecane, cycloaliphatic such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane. Organic solvents such as hydrocarbon solvents, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ester solvents such as 3 methoxybutyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone A solvent can be used, and a mixture of two or more of these may be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferably used.

  The second propylene-based resin (C) can be obtained by neutralizing or saponifying the raw material of the second propylene-based resin (C) obtained as described above. In the case of neutralization or saponification, it is easy and preferable to treat the raw material of the second propylene resin (C) as an aqueous dispersion.

  Examples of the basic substance used for neutralization or saponification of the aqueous dispersion of the raw material of the second propylene resin (C) include alkali metals such as sodium, potassium, lithium, calcium, magnesium and zinc and / or alkaline earth. Metals and / or other metals, inorganic amines such as hydroxylamine and ammonium hydroxide, ammonia, (tri) methylamine, (tri) ethanolamine, (tri) ethylamine, dimethylethanolamine, organic amines such as morpholine, Sodium oxide, sodium peroxide, alkali metal and / or alkaline earth metal oxides and / or other metals, hydroxides, hydrides, sodium carbonate and other alkali metals and / or alkaline earth metals and / or others Mention of weak acid salts of metalsAs the carboxylate group or carboxylic acid ester group neutralized or saponified with a basic substance, an alkali metal carboxylate such as sodium carboxylate or potassium carboxylate or ammonium carboxylate is preferred.

  In addition, the degree of neutralization or saponification, that is, the conversion rate of the carboxylic acid group contained in the raw material of the second propylene-based resin (C) to the above metal salt, ammonium salt, or the like depends on the stability of the aqueous dispersion From the viewpoint of adhesiveness, it is usually 50 to 100%, preferably 70 to 100%, more preferably 85 to 100%. Therefore, it is desirable that all of the carboxylic acid groups in the second propylene-based resin (C) are neutralized or saponified by the basic substance, but some carboxylic acid groups are not neutralized or saponified. It may remain. As a method for analyzing the salt component of the acid group as described above, a method for detecting a metal species forming a salt by ICP emission analysis, an acid group using IR, NMR, mass spectrometry, elemental analysis, etc. And a method for identifying the structure of the salt.

  Here, the conversion ratio of the carboxylic acid group to the neutralized salt was determined by dissolving the propylene resin in heated toluene and titrating with a 0.1 N potassium hydroxide-ethanol standard solution to lower the acid value of the propylene resin. It calculates | requires from a formula and calculates by comparing with the total mole number of the original carboxylic acid group.

Acid value = (5.611 × A × F) / B (mgKOH / g)
A: 0.1 N potassium hydroxide-ethanol standard solution usage (ml)
F: Factor of 0.1 N potassium hydroxide-ethanol standard solution B: Sample collection amount (g).

  The acid value calculated above is converted into the number of moles of carboxylic acid groups that are not neutralized using the following formula.

Number of moles of unneutralized carboxylic acid group = acid value × 1000/56 (mol / g).
The conversion ratio of the carboxylic acid group to the neutralized salt is calculated by calculating the total number of moles (mol / g) of the carboxylic acid group by separately determining the carbonyl carbon of the carboxylic acid group using IR, NMR and elemental analysis. Use the following formula to calculate.

Conversion rate% = (1-r) × 100 (%)
r: Number of moles of unneutralized carboxylic acid groups / total number of moles of carboxylic acid groups.

  Further, from the viewpoint of enhancing the interaction with the reinforcing fiber, the content of the carboxylate bonded to the polymer chain of the second propylene resin (C) is −C (g per second propylene resin. The total amount is preferably 0.05 to 5 mmol equivalent in terms of a group represented by = O) -O-. More preferably, it is 0.1-4 mmol equivalent, More preferably, it is 0.3-3 mmol equivalent. As a method for analyzing the content of the carboxylate as described above, a method of quantitatively detecting a metal species forming a salt by ICP emission analysis, or a method using IR, NMR, elemental analysis, etc. A method for quantifying the carbonyl carbon of the acid salt is mentioned.

  In the molding material of the present invention, the third propylene-based resin (D) adheres to the composite composed of the reinforcing fiber bundle (A), the first propylene-based resin (B), and the second propylene-based resin (C). The molding material is such that the order of the weight average molecular weights of the components (B), (C), and (D) is (D)> (B)> (C).

  The reinforcing fiber bundle (A), the first propylene-based resin (B), and the second propylene-based resin (C) form a composite with these three components. The form of this composite is as shown in FIG. 1, and a mixture of the first propylene resin (B) and the second propylene resin (C) between the single fibers of the reinforcing fiber bundle (A). Is satisfied. That is, the reinforcing fibers (A) are dispersed like islands in the sea of the mixture of the first propylene resin (B) and the second propylene resin (C).

  In the molding material of the present invention, the mixture of the first propylene-based resin (B) and the second propylene-based resin (C) is a composite in which the reinforcing fiber bundle (A) is satisfactorily impregnated. For example, when the molding material of the present invention is injection-molded, the first propylene-based resin (B) and the second propylene-based resin (D) are melt-kneaded in a cylinder of an injection molding machine. The mixture of the two propylene resins (C) diffuses into the third propylene resin (D) and helps the reinforcing fiber bundle (A) to be dispersed in the third propylene resin (D). The third propylene-based resin (D) serves as a so-called impregnation aid / dispersion aid that assists the substitution and impregnation of the reinforcing fiber bundle (A). In achieving this role, if the order of the weight average molecular weight of the components (B), (C), (D) is (D)> (B)> (C), the components (B), (C) Can easily diffuse into the component (D).

  From the viewpoint of acting as an impregnation aid / dispersion aid and the entanglement of molecular chains with the first propylene resin (B), the interaction with the first propylene resin (B) is achieved. From the viewpoint of increasing, the weight average molecular weight Mw of the second propylene resin (C) is preferably 1,000 to 50,000. More preferably, it is 2,000-40,000, More preferably, it is 5,000-30,000. The weight average molecular weight is measured using gel permeation chromatography (GPC).

  In addition, the first propylene-based resin (B) has a weight average molecular weight Mw from the viewpoint of serving as an impregnation aid / dispersion aid and an affinity with the third propylene-based resin (D). 30 to 100% by weight of a propylene resin (B-1) having a weight average molecular weight Mw of 150,000 or more and 500,000 or less (B-2) Is preferably 0 to 70% by weight. The weight average molecular weight Mw of the propylene-based resin (B-1) is preferably 35,000 or more and 140,000 or less. The weight average molecular weight Mw of the propylene-based resin (B-2) is preferably 150,000 or more and 450,000 or less. As for the upper limit, if the weight average molecular weight Mw becomes too large, it may be difficult to play a role as an impregnation aid / dispersion aid, and is preferably within the above-mentioned range. The blending amount is more preferably 35 to 100% by weight of the propylene resin (B-1) and 0 to 65% by weight of the propylene resin (B-2).

  Examples of the third propylene-based resin (D) of the present invention include a propylene homopolymer or a copolymer of propylene and at least one α-olefin, conjugated diene, non-conjugated diene, or the like.

  Examples of the monomer repeating unit constituting the α-olefin include ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 2-12 carbon atoms excluding propylene such as 1-hexene, 4,4 dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene and 1-dodecene Examples of the monomer repeating unit constituting the α-olefin, conjugated diene, and non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the like. One type or two or more types can be selected.

  As the skeleton structure of the third propylene-based resin (D), a homopolymer of propylene, one or two or more random or block copolymers of propylene and the other monomers, or other heat Examples thereof include a copolymer with a plastic monomer. For example, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, and the like are preferable.

  The third propylene-based resin (D) may contain an impact resistance improver such as an elastomer or a rubber component and other fillers and additives as long as the object of the present invention is not impaired. Examples of these include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers. , Release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents.

  Here, as described above, it is important that the order of the weight average molecular weight of the third propylene-based resin (D) is (D)> (B)> (C). In other words, the third propylene-based resin (D) plays a role as a matrix resin in the molded product obtained by molding the molding material of the present invention, so that the strength of the resin itself is required, so that the weight average molecular weight is determined from the component (B). , (C) is important.

  The third propylene resin (D) is preferably a modified propylene resin from the viewpoint of improving the mechanical properties of the obtained molded product. An acid-modified propylene resin is preferred, and a propylene resin having a carboxylic acid and / or salt group bonded to the polymer chain. The acid-modified propylene-based resin can be obtained by various methods, for example, the same method as the raw material of the second propylene-based resin (B) and the production example of the second propylene-based resin.

  When the third propylene-based resin (D) is a propylene-based resin having a carboxylic acid and / or a salt thereof bonded to the polymer chain, the mechanical properties of the resin are kept high; In view of raw material costs, it is preferable to use a mixture with an unmodified propylene resin. Specifically, 5 to 50% by weight of propylene resin (D-1) having a carboxylic acid and / or salt group bonded to a polymer chain, and a propylene resin having no carboxylic acid and / or salt group thereof It is preferable to have 50 to 95 weight% of resin (D-2). More preferably, the component (D-1) is 5 to 45% by weight, the component (D-2) is 55 to 95% by weight, more preferably the component (D-1) is 5 to 35% by weight, and the component (D-2). ) Is 65 to 95% by weight.

  When the third propylene-based resin (D) is an acid-modified propylene-based resin, it is preferable that the first propylene-based resin (B) is also modified in order to increase the affinity. Specifically, the first propylene resin (B) has at least a carboxylate bonded to a polymer chain. Further, as described above, the weight average molecular weight Mw of the first propylene-based resin (B) needs to be larger than the weight average molecular weight Mw of the second propylene-based resin (C). The propylene-based resin (B) preferably has a weight average molecular weight Mw of more than 50,000 and not more than 150,000. More preferably, it is 60,000-130,000. As a manufacturing method of 1st propylene-type resin (B) containing at least the carboxylate couple | bonded with the said polymer chain, it can manufacture similarly to the above-mentioned 2nd propylene-type resin (C).

  When the first to third propylene resins are propylene resins containing at least a carboxylic acid bonded to a polymer chain and / or a salt thereof, the content of the carboxylic acid and / or the salt is 1 g of resin. The total amount in terms of groups represented by —C (═O) —O—, that is, the order of millimolar equivalents of —C (═O) —O— per gram of resin is component (C) ≧ component (B) ≧ It is preferable that it is a component (D). This is because the first and second propylene resins composited with the reinforcing fibers are preferably more acid-modified from the viewpoint of adhesion to the reinforcing fibers, and in particular, the second propylene resins having a small weight average molecular weight. (C) is preferably present in the vicinity of the reinforcing fiber, so that the amount of acid modification is the largest in order to improve the adhesion to the reinforcing fiber and the dispersibility of the reinforcing fiber. The amount of acid modification of the third propylene-based resin (A) is preferably smaller than the first and second propylene-based resins considering the interaction with the reinforcing fiber from the viewpoint of resin cost.

  The molding material of the present invention is composed of a reinforcing fiber bundle (A), a first propylene-based resin (B), a second propylene-based resin (C), and a third propylene-based resin (D). Is 100% by weight.

  Among these, the reinforcing fiber bundle (A) is 1 to 75% by weight, preferably 5 to 65% by weight, and more preferably 10 to 50% by weight. If the reinforcing fiber bundle (A) is less than 1% by weight, the resulting molded article may have insufficient mechanical properties, and if it exceeds 75% by weight, fluidity may be reduced during injection molding.

  The first propylene-based resin (B) is 0.01 to 10% by weight, preferably 0.5 to 9% by weight, and more preferably 1 to 8% by weight. Furthermore, the second propylene-based resin (C) is 0.01 to 10% by weight, preferably 0.5 to 9% by weight, and more preferably 1 to 8% by weight. When the first propylene-based resin (B) and the second propylene-based resin (C) are less than 0.1% by weight, the moldability of the molding material, that is, the dispersion of the reinforcing fibers during molding may be insufficient. If it exceeds 10% by weight, the mechanical properties of the thermoplastic resin as the matrix resin may be lowered. Further, the third propylene-based resin (D) is 5 to 98.98% by weight, preferably 25 to 94% by weight, more preferably 50 to 88% by weight. The effect can be achieved.

  In the molding material of the present invention, the third propylene-based resin (D) adheres to the composite composed of the reinforcing fiber bundle (A), the first propylene-based resin (B), and the second propylene-based resin (C). The molding material is arranged and configured as described above. As a preferred embodiment of the molding material, as shown in FIG. 2, the reinforcing fiber bundle (A) is arranged substantially parallel to the axial direction of the molding material, and the length of the reinforcing fiber bundle (A) is the same as that of the molding material. The length is substantially the same as the length.

  Here, “arranged substantially in parallel” means that the long axis of the reinforcing fiber bundle and the long axis of the molding material are oriented in the same direction. The angle deviation is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. In addition, “substantially the same length” means that, for example, in a pellet-shaped molding material, a reinforcing fiber bundle is cut in the middle of the pellet, or a reinforcing fiber bundle substantially shorter than the entire length of the pellet is substantially included. It is not done. In particular, the amount of reinforcing fiber bundle shorter than the total length of the pellet is not specified, but when the content of reinforcing fiber having a length of 50% or less of the total length of the pellet is 30% by weight or less, the pellet It is evaluated that the reinforcing fiber bundle significantly shorter than the full length is not substantially contained. Furthermore, the content of reinforcing fibers having a length of 50% or less of the total length of the pellet is preferably 20% by weight or less. In addition, a pellet full length is the length of the reinforcing fiber orientation direction in a pellet. Since the reinforcing fiber bundle (A) has a length equivalent to that of the molding material, the reinforcing fiber length in the molded product can be increased, so that excellent mechanical properties can be obtained.

  3 to 6 schematically show examples of the shape of the cross section in the axial center direction of the molding material of the present invention, and FIGS. 7 to 10 show examples of the shape of the cross section in the orthogonal direction of the molding material of the present invention. This is a schematic representation.

  The cross-sectional shape of the molding material is such that the third propylene-based resin (D) is added to the composite composed of the reinforcing fiber bundle (A), the first propylene-based resin (B), and the second propylene-based resin (C). If it is arranged so as to adhere, it is not limited to the one shown in the figure, but as shown in FIGS. 3 to 5 which are preferably cross sections in the axial center direction, the composite serves as a core material and a third propylene resin (D) The structure arrange | positioned between layers is preferable.

  Moreover, as FIG. 7-9 which is an orthogonal cross section shows, the structure arrange | positioned at the core sheath structure which the 3rd propylene-type resin (D) coat | covers the circumference | surroundings with respect to a composite_body | complex is a core. preferable. When arranging a plurality of composites as shown in FIG. 11 so as to be covered with the third propylene-based resin (D), the number of composites is preferably about 2 to 6.

  The boundary between the composite and the third propylene-based resin (D) is bonded, and the third propylene-based resin (D) partially enters the composite near the boundary, and the first propylene in the composite It may be in a state in which it is compatible with the propylene-based resin (B) and the second propylene-based resin (C), or in a state in which the reinforcing fibers are impregnated.

  The axial direction of the molding material may be continuous while maintaining substantially the same cross-sectional shape. Depending on the molding method, such a continuous molding material may be cut into a certain length.

  The molding material of the present invention is obtained by, for example, combining a reinforcing fiber bundle (A) with a first propylene resin (B) and a second propylene resin (C) by a technique such as injection molding or press molding. The final molded product can be produced by kneading the propylene resin (D) 3. From the viewpoint of the handling property of the molding material, it is important that the composite and the third propylene resin (D) are not separated until the molding is performed and the shape as described above is maintained. In the composite and the third propylene-based resin (D), the shape (size, aspect ratio), specific gravity, and weight are completely different, so classification is performed at the time of transporting and handling the material until molding, and at the time of transferring the material in the molding process. There are cases where the mechanical properties of the molded product vary, the fluidity is lowered and the mold is clogged, or blocking occurs in the molding process.

  Therefore, as illustrated in FIGS. 7 to 9, a composite composed of a reinforcing fiber bundle (A) that is a reinforcing fiber, a first propylene resin (B), and a second propylene resin (C). The third propylene-based resin (D) is disposed so as to cover the periphery of the composite, that is, the reinforcing fiber bundle (A) as the reinforcing fiber and the first propylene-based resin (B) and The composite made of the second propylene-based resin (C) preferably has a core structure, and the third propylene-based resin (D) preferably has a core-sheath structure covering the periphery of the composite. With such an arrangement, the composite can make the third propylene-based resin (D) stronger. The third propylene-based resin (D) is disposed so as to cover the periphery of the composite composed of the reinforcing fiber bundle (A), the first propylene resin (B), and the second propylene-based resin (C). Whether the composite and the third propylene-based resin (D) are arranged in layers, which is advantageous depends on the ease of manufacture and the ease of handling of the material. More preferably, the system resin (D) is disposed so as to cover the periphery of the composite.

  As described above, the reinforcing fiber bundle (A) is completely impregnated with the first propylene resin (B), the second propylene resin (C), and a part of the third propylene resin (D). Although it is desirable, it is practically difficult. From the reinforcing fiber and the first propylene resin (B), the second propylene resin (C), and a part of the third propylene resin (D). There are some voids in the composite. In particular, when the reinforcing fiber content is high, the number of voids increases. However, even when a certain amount of voids are present, the effect of promoting impregnation and fiber dispersion of the present invention is exhibited. However, if the porosity exceeds 20%, the effect of promoting impregnation and fiber dispersion is remarkably reduced, so the porosity is preferably in the range of 0 to 20%. A more preferable range of the porosity is 15% or less. The porosity is measured by ASTM D2734 (1997) test method for the portion of the composite, or in the cross section of the molding material, the reinforcing fiber bundle (A), the first propylene resin (B), and the second propylene resin The voids present in the composite part formed by the resin (C) and a part of the third propylene resin (D) are observed, and the following formula is used from the total area of the composite part and the total area of the void part. Can be calculated.

Porosity (%) = total area of void part / (total area of composite part + total area of void part) × 100
The molding material of the present invention is preferably used after being cut to a length in the range of 1 to 50 mm. By adjusting to the above length, the fluidity and handleability during molding can be sufficiently enhanced. A particularly preferred embodiment of the molding material cut to an appropriate length in this way can be exemplified by long fiber pellets for injection molding.

  Further, 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 products include liquefied natural gas tanks. It is also possible to produce a unidirectional thermoplastic prepreg by heating and fusing a plurality of molding materials of the present invention in one direction. Such a prepreg can be applied to fields where lightness, high strength, elastic modulus, and impact resistance are required, such as automobile members.

  The molding material 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. As a molded article, it is suitable for automobile parts such as various modules such as an instrument panel, a door beam, an under cover, a lamp housing, a pedal housing, a radiator support, a spare tire cover, and a front end. Furthermore, home and office electrical product parts such as telephones, facsimiles, VTRs, copiers, televisions, microwave ovens, audio equipment, toiletries, laser discs, refrigerators, and air conditioners are also included. Further, since the molding material of the present invention is excellent in moldability, 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 casing used for a notebook computer, a mobile phone, a digital still camera, a PDA, a plasma display, or a member that supports a keyboard inside a personal computer. Examples include members for electric and electronic devices represented by a keyboard support. In such a member for an electric / electronic device, when carbon fiber having conductivity is used as the reinforcing fiber, electromagnetic shielding properties are imparted, which is more preferable.

  The molding material described above can be used as an injection molding pellet. In injection molding, when plasticizing a pellet-shaped molding material, temperature, pressure, and kneading are applied. According to the present invention, the first propylene resin (B) and the second propylene resin are used at that time. Resin (C) exhibits a great effect as a dispersion / impregnation aid. In this case, a normal in-line screw type injection molding machine can be used, such as using a screw with a low compression ratio or setting a low back pressure during material plasticization. Even when the kneading effect by is weak, the reinforcing fiber is well dispersed in the matrix resin, and a molded product in which the fiber is impregnated with the resin can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(1) Weight average molecular weight measurement of propylene-based resin The first propylene-based resin (B), the second propylene-based resin (C) and the third propylene-based resin (D) are subjected to gel permeation chromatography (GPC). Measured. A GPC column packed with polystyrene cross-linked gel was used. Measurement was performed at 150 ° C. using 1,2,4-trichlorobenzene as a solvent. The molecular weight was calculated in terms of standard polystyrene.

(2) Structural analysis of propylene-based resin For each of the first, second and third propylene-based resins, organic compound elemental analysis, inductively coupled plasma (ICP) emission analysis, IR (infrared absorption) spectrum analysis, 1H-NMR Measurement and 13C-NMR measurement were carried out, and the content ratio of the monomer structure was evaluated from the amount of element contained in the propylene-based resin, identification of the functional group structure, each assigned proton, and the peak intensity of carbon.

  The organic compound elemental analysis was performed using an organic elemental analyzer 2400II (manufactured by PerkinElmer). ICP emission analysis was performed using ICPS-7510 (manufactured by Shimadzu Corporation). IR spectrum analysis was performed using IR-Prestige-21 (manufactured by Shimadzu Corporation). 1H-NMR measurement and 13C-NMR measurement were performed using a JEOL JNM-GX400 spectrometer (manufactured by JEOL Ltd.).

(3) Composite porosity The porosity (%) of the composite was calculated based on the ASTM D2734 (1997) test method.

  The composite porosity was determined according to the following criteria, and A to C were set as acceptable.

A: 0 to less than 5% B: 5% to less than 20% C: 20% to less than 40% D: 40% or more.

(4) Fiber dispersibility of molded product obtained by using molding material A molded product of 100 mm × 100 mm × 2 mm was molded, and the number of undispersed CF bundles present on the front and back surfaces was counted visually. The evaluation was performed on 50 molded products, the fiber dispersibility was determined for the total number based on the following criteria, and A to C were set as acceptable.

A: 1 or less undispersed CF bundle B: 1 or more and less than 5 undispersed CF bundles C: 5 or more and less than 10 undispersed CF bundles D: 10 or more undispersed CF bundles

(5) Bending test of molded product obtained using molding material In accordance with ASTM D790 (1997), a support span is set to 100 mm using a three-point bending test jig (indenter 10 mm, fulcrum 10 mm), and crosshead Bending strength and flexural modulus were measured under the test conditions of a speed of 5.3 mm / min. As a testing machine, “Instron” (registered trademark) universal testing machine 4201 type (manufactured by Instron) was used.

  Judgment of bending strength was performed according to the following criteria, and A to C were set as acceptable.

A: 150 MPa or more B: 130 MPa or more and less than 150 MPa C: 100 MPa or more and less than 130 MPa D: Less than 100 MPa.

(6) Izod Impact Test of Molded Product Obtained Using Molding Material An Izod impact test with a mold notch was performed according to ASTM D256 (1993). The Izod impact strength (J / m) was measured when the thickness of the used test piece was 3.2 mm and the moisture content of the test piece was 0.1% by weight or less.

  Judgment of the Izod impact test was performed according to the following criteria, and A to C were set as acceptable.

A: 250 J / m or more B: 200 J / m or more and less than 250 J / m C: 150 J / m or more and less than 200 J / m D: Less than 150 J / m.

Reference Example 1 Carbon fiber 1
Spinning, firing treatment, and surface oxidation treatment were carried out from a copolymer containing polyacrylonitrile as a main component to obtain continuous carbon fibers having a total number of 24,000 single yarns. The characteristics of this continuous carbon fiber were as follows.

Single fiber diameter: 7μm
Mass per unit length: 1.6 g / m
Specific gravity: 1.8
Surface oxygen concentration ratio [O / C]: 0.06
Tensile strength: 4600 MPa
Tensile modulus: 220 GPa.

Here, the surface oxygen concentration ratio was determined according to the following procedure by X-ray photoelectron spectroscopy using the carbon fiber after the surface oxidation treatment. First, the carbon fiber bundle was cut to 20 mm, spread and arranged on a copper sample support, and then A1Kα1 and 2 were used as X-ray sources, and the inside of the sample chamber was kept at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s was adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. It was obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. As a linear base line in the range of 947 to 959 eV. The atomic ratio was calculated from the ratio of the O _1s peak area to the C _1s peak area using the sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, Kokusai Denki Co., Ltd. model ES-200 was used, and the sensitivity correction value was set to 1.74.

Reference Example 2 Carbon fiber 2
Spinning, firing treatment, and surface oxidation treatment were carried out from a copolymer containing polyacrylonitrile as a main component to obtain continuous carbon fibers having a total number of 24,000 single yarns. The characteristics of this continuous carbon fiber were as follows.

Single fiber diameter: 7μm
Mass per unit length: 1.6 g / m
Specific gravity: 1.8
Surface oxygen concentration ratio [O / C]: 0.12
Tensile strength: 4600 MPa
Tensile modulus: 220 GPa.

Reference Example 3. Preparation of Propylene Resin Mixture PP (1) As the first propylene resin (B), propylene / butene / ethylene copolymer (B-1) (constituent unit derived from propylene (hereinafter also referred to as “C3”). ) = 66 mol%, Mw = 90,000) 91 parts by weight, as a raw material for the second propylene-based resin (C), maleic anhydride-modified propylene / ethylene copolymer (C3 = 98 mol%, Mw = 25, 000, acid content = 0.81 mmol equivalent) 9 parts by weight, 3 parts by weight of potassium oleate were mixed as a surfactant. This mixture was supplied at a rate of 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40), and from the supply port provided in the vent portion of the extruder, A 20% aqueous potassium hydroxide solution was continuously supplied at a rate of 90 g / hour and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder mouth, and further poured into warm water at 80 ° C. to obtain an emulsion. The obtained emulsion had a solid content concentration of 45%.

  The maleic anhydride-modified propylene / ethylene copolymer (C3 = 98 mol%, Mw = 25,000, acid content = 0.81 mmol equivalent) is 96 parts by weight of propylene / ethylene copolymer, maleic anhydride. It was obtained by mixing 4 parts by weight and 0.4 part by weight of Perhexi 25B (manufactured by NOF Corporation) as a polymerization initiator and performing modification at a heating temperature of 160 ° C. for 2 hours.

Reference Example 4 Preparation of Propylene Resin Mixture PP (2) As a raw material for the second propylene resin (C), maleic anhydride-modified propylene / ethylene polymer (C3 = 98 mol%, Mw = 5,000, acid content = An emulsion was prepared in the same manner as in Reference Example 3 except that 0.81 mmol equivalent) was used. The emulsion had a solids concentration of 45% by weight.

Reference Example 5 Preparation of Propylene Resin Mixture PP (3) As a raw material for the second propylene resin (C), maleic anhydride-modified propylene / ethylene polymer (C3 = 95 mol%, Mw = 25,000, acid content = An emulsion was prepared in the same manner as in Reference Example 3 except that 0.1 mmol equivalent) was used. The emulsion had a solids concentration of 45% by weight.

Reference Example 6 Preparation of Propylene Resin Mixture PP (4) An emulsion was prepared in the same manner as in Reference Example 3 except that the amount of 20% aqueous potassium hydroxide solution was changed from 90 g / hour to 43 g / hour. The emulsion had a solids concentration of 45% by weight.

Reference Example 7 Preparation of Propylene Resin Mixture PP (5) Emulsion in the same manner as in Reference Example 3 except that the 20% aqueous potassium hydroxide solution was changed to 20% aqueous ammonia and the supply rate was changed from 90 g / hour to 150 g / hour. Was made. The emulsion had a solids concentration of 45% by weight.

Reference Example 8 Preparation of Propylene Resin Mixture PP (6) As a raw material for the second propylene resin (C), maleic anhydride-modified propylene / ethylene polymer (C3 = 95 mol%, Mw = 40,000, acid content = An emulsion was prepared in the same manner as in Reference Example 3 except that 0.81 mmol equivalent) was used. The emulsion had a solids concentration of 45% by weight.

Reference Example 9 Preparation of Propylene Resin Mixture PP (7) As the first propylene resin (B), propylene / butene / ethylene copolymer (B-1) (C3 = 66 mol%, Mw = 90,000) 45. The same as Reference Example 3 except that a mixed resin of 5 parts by weight and 45.5 parts by weight of propylene / butene copolymer (B-2) (C3 = 81 mol%, Mw = 300,000) was used. An emulsion was prepared. The emulsion had a solids concentration of 45% by weight.

Reference Example 10 Preparation of Propylene Resin Mixture PP (8) As the first propylene resin (B), maleic anhydride-modified propylene / butene / ethylene copolymer (B-3) (C3 = 66 mol%, Mw = 70, 000, acid content: 0.81 mmol equivalent), and an emulsion was prepared in the same manner as in Reference Example 3. The emulsion had a solids concentration of 45% by weight.

Reference Example 11 Preparation of Propylene Resin Mixture PP (9) Unmodified polypropylene resin (weight average molecular weight 100,000) was pulverized to obtain polypropylene resin powder having an average particle size of 10 μm. The powder was put into n-hexane and stirred to prepare a suspension of unmodified polypropylene resin. The solid concentration was 45%.

Reference Example 12. Preparation of Propylene Resin Mixture PP (10) Maleic anhydride-modified propylene / ethylene copolymer (B-4) used as a raw material for the second propylene resin (C) as the first propylene resin (B) ) (C3 = 98 mol%, Mw = 25,000, acid content = 0.81 mmol equivalent) was used to prepare an emulsion in the same manner as in Reference Example 3. The emulsion had a solids concentration of 45% by weight.

Reference Example 13 Preparation of Propylene Resin Mixture PP (11) As a raw material for the second propylene resin (C), maleic anhydride-modified propylene / ethylene polymer (C3 = 95 mol%, Mw = 200,000, acid content = An emulsion was prepared in the same manner as in Reference Example 3 except that 0.81 mmol equivalent) was used. The emulsion had a solids concentration of 45% by weight.

Reference Example 14 Preparation of Propylene Resin Mixture PP (12) As the first propylene resin (B), propylene / butene / ethylene copolymer (B-1) (constituent unit derived from propylene (hereinafter also referred to as “C3”). ) = 66 mol%, Mw = 90,000) 50 parts by weight, as a raw material for the second propylene-based resin (C), maleic anhydride-modified propylene / ethylene copolymer (C3 = 98 mol%, Mw = 25, 000, acid content = 0.81 mmol equivalent) and 50 parts by weight were used to prepare an emulsion in the same manner as in Reference Example 3. The emulsion had a solids concentration of 45% by weight.

Reference Example 15. Synthesis of acid-modified propylene resin used for third propylene-based resin (D) 99.6 parts by weight of propylene polymer, 0.4 parts by weight of maleic anhydride, and perhexi 25B (manufactured by NOF Corporation) as a polymerization initiator 0.4 parts by weight was mixed and modified at a heating temperature of 160 ° C. for 2 hours to obtain an acid-modified polypropylene resin (Mw = 400,000, acid content = 0.08 mmol equivalent).

Example 1.
After the emulsion of the propylene-based resin mixture PP (1) prepared in Reference Example 3 was adjusted to a solid content concentration of 27% by weight and adhered by the roller impregnation method to the continuous carbon fiber bundle obtained in Reference Example 1 Then, it was dried online at 210 ° C. for 2 minutes, and the water was removed to obtain a composite of the carbon fiber bundle and the first and second propylene resins. The properties of the obtained composite are shown in Table 1. The adhesion amount of the propylene resin mixture PP (1) was 20% by weight.

  Next, polypropylene resin (Prime Polypro J105G resin manufactured by Prime Polymer Co., Ltd.) was melted at 200 ° C. with a single screw extruder and extruded into a crosshead die attached to the tip of the extruder, and at the same time, the continuous reinforcement obtained. A strand made of the fiber bundle (A) and the first and second propylene-based resins is also continuously fed into the crosshead die, whereby the melted component (D) is converted into component (A), component (B) and The composite of component (C) was coated. At this time, the amount of the component (D) was adjusted so that the content of the reinforcing fiber was 20% by weight.

  The strand obtained by the method described above was cooled and then cut into a length of 7 mm with a cutter to obtain a core-sheath columnar pellet (long fiber pellet).

  The obtained long fiber pellets showed no fuzz due to transportation and showed good handleability. The obtained molding material was dried under vacuum at 80 ° C. for 5 hours or more. The obtained molding material was molded using a mold for each test piece using a J150EII-P type injection molding machine manufactured by Nippon Steel Works. The conditions were as follows: cylinder temperature: 210 ° C., mold temperature: 60 ° C., and cooling time 30 seconds. After the molding, the test piece was dried at 80 ° C. for 12 hours under vacuum, and the dried test piece was stored in a desiccator at room temperature for 3 hours. The characteristic evaluation results are collectively shown in Table 1.

Example 2
For the third propylene resin (D), a resin comprising 50% by weight of polypropylene resin (Prime Polypro J105G resin manufactured by Prime Polymer Co., Ltd.) and 50% by weight of the acid-modified propylene resin prepared in Reference Example 15 is used. Except for the above, long fiber pellets were obtained in the same manner as in Example 1 and evaluated for molding. The characteristic evaluation results are collectively shown in Table 1.

Example 3 FIG.
Except that the solid content concentration of the propylene-based resin mixture PP (1) emulsion was 10 wt%, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 4
A long fiber pellet was obtained in the same manner as in Example 2 except that the solid content concentration of the emulsion of the propylene-based resin mixture PP (1) was 45% by weight, and molding evaluation was performed. The characteristic evaluation results are collectively shown in Table 1.

Embodiment 5 FIG.
A long fiber pellet was obtained and evaluated for molding in the same manner as in Example 2 except that the solid content concentration of 35% of the emulsion of the propylene resin mixture PP (12) prepared in Reference Example 14 was used. The characteristic evaluation results are collectively shown in Table 1.

Example 6
A long fiber pellet was obtained in the same manner as in Example 2 except that the solid content concentration of 27% by weight of the emulsion of the propylene-based resin mixture PP (2) prepared in Reference Example 4 was used, and molding evaluation was performed. The characteristic evaluation results are collectively shown in Table 1.

Example 7
Before the polypropylene fiber is coated on the carbon fiber bundle using an extruder, the carbon fiber bundle is impregnated with “Clearon” K110 (terpene-based hydrogenated resin) manufactured by Yashara Chemical Co. so as to be 15% by weight. Except that the resin was coated, long fiber pellets were obtained in the same manner as in Example 2 and evaluated for molding. The characteristic evaluation results are collectively shown in Table 1.

Example 8 FIG.
Except for using the propylene resin mixture PP (3) emulsion prepared in Reference Example 5, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 9
Except that the emulsion of the propylene resin mixture PP (4) prepared in Reference Example 6 was used, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 10
Except that the emulsion of the propylene-based resin mixture PP (5) prepared in Reference Example 7 was used, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 11
Except that the emulsion of the propylene-based resin mixture PP (6) prepared in Reference Example 8 was used, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 12 FIG.
Except that the emulsion of the propylene resin mixture PP (7) prepared in Reference Example 9 was used, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 13
Except for using the propylene resin mixture PP (8) emulsion prepared in Reference Example 10, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Example 14
Except that the continuous carbon fiber obtained in Reference Example 2 was used, long fiber pellets were obtained in the same manner as in Example 2, and molding evaluation was performed. The characteristic evaluation results are collectively shown in Table 1.

Example 15.
Before the emulsion of the propylene resin mixture PP (1) was applied by the roller impregnation method, the carbon fiber bundle was twisted 5 times per 10 cm and the same as in Example 2 except that the emulsion was impregnated. Thus, long fiber pellets were obtained and evaluated for molding. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 1
The continuous carbon fiber bundle obtained in Reference Example 1 was subjected to the evaluation as it was without adhering the mixture of propylene resin. Carbon fiber fuzzed during the production of long fiber pellets, making it impossible to proceed with the process.

Comparative Example 2
The same procedure as in Example 2 was performed except that the emulsion of the propylene resin mixture PP (1) was attached by the roller impregnation method and then the emulsion of the same concentration was again attached to the carbon fiber bundle by the roller impregnation method. Long fiber pellets were obtained and evaluated for molding. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 3
Except that the suspension of the propylene resin mixture PP (9) prepared in Reference Example 11 was used, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 4
Except having used the emulsion of the propylene-based resin mixture PP (10) prepared in Reference Example 12, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

Comparative Example 5
Except that the emulsion of the propylene resin mixture PP (11) prepared in Reference Example 13 was used, long fiber pellets were obtained and evaluated for molding in the same manner as in Example 2. The characteristic evaluation results are collectively shown in Table 1.

  As described above, in Examples 1 to 15, the molding material (long fiber pellet) was excellent in handleability, and a molded product having excellent mechanical properties could be obtained by using the molding material.

  On the other hand, in Comparative Example 1, nothing was adhered to the carbon fiber bundle, and it was impossible to produce a molding material (long fiber pellet). In Comparative Examples 2 to 5, a molding material that can achieve both fiber dispersibility and mechanical properties was not obtained.

  The reinforcing fiber bundle of the present invention has excellent handleability, exhibits excellent adhesion when a polyolefin resin, particularly polypropylene resin, is used as a matrix resin, and obtains a fiber reinforced thermoplastic resin molded article having high mechanical properties. Can be developed for various applications. It is particularly suitable for automobile parts, electrical / electronic parts, household / office electrical product parts.

It is the schematic which shows an example of the form of the composite_body | complex which consists of a reinforced fiber bundle (A) and a polyarylene sulfide (B). It is the schematic which shows an example of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the axial direction cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention. It is the schematic which shows an example of the shape of the orthogonal cross section of the preferable aspect of the molding material of this invention.

Explanation of symbols

1 Reinforcing fiber bundle (A)
2 Second propylene resin (B) and third propylene resin (C)
3 Composite made of reinforcing fiber bundle (A), second propylene resin (B) and third propylene resin (C) 4 Third propylene resin (D)

Claims (19)

A molding material comprising the following components (A) to (D), wherein the component (D) is adhered to a composite comprising the components (A) to (C), and the weight Molding material in which the order of the average molecular weight Mw is component (D)> component (B)> component (C).
(A) Reinforcing fiber bundle 1 to 75% by weight
(B) First propylene-based resin 0.01 to 10% by weight
(C) Second propylene resin containing at least a carboxylate bonded to a polymer chain 0.01 to 10% by weight
(D) 3rd propylene-type resin 5-98.98 weight% 2. The component (C) according to claim 1, wherein the component (C) has at least a carboxylate salt at a concentration of 0.05 to 5 mmol equivalent in terms of a group represented by the formula (I) per gram of resin. Molding material.
-C (= O) -O -... Formula (I) One or two or more of 50 to 100% of the carboxylate bonded to the polymer chain of component (C) is selected from lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and zinc salt The molding material according to claim 1, which is obtained by conversion with a metal salt of The reinforcing fiber bundle according to claim 1 or 2, wherein 50 to 100% of the carboxylate bonded to the polymer chain of component (C) is converted with an ammonium salt. The molding material in any one of Claims 1-4 whose weight average molecular weight Mw of the said component (C) is the range of 1,000-50,000. The component (B) has a weight average molecular weight Mw in the range of 30,000 to less than 150,000, 30 to 100% by weight of the propylene resin (B-1), and a weight average molecular weight Mw of 150,000 to 500, The molding material in any one of Claims 1-5 which has 0 to 70 weight% of propylene-type resin (B-2) which is the range of 000 or less. The molding material in any one of Claims 1-6 in which the said component (B) has 50 mol% or more of structural units derived from propylene. The said component (B) has at least the carboxylate couple | bonded with the polymer chain, and the weight average molecular weight Mw exceeds 50,000 and is 150,000 or less in any one of Claims 1-7. The molding material as described. The molding material in any one of Claims 1-8 in which the said component (D) has the group of the carboxylic acid and / or its salt couple | bonded with the polymer chain. The component (D) has 5 to 50% by weight of a propylene resin (D-1) having a carboxylic acid and / or salt group bonded to a polymer chain, and a carboxylic acid and / or salt group. The molding material of Claim 9 which has 50 to 95 weight% of propylene-type resin (D-2) which does not carry out. The order of millimole equivalent of the group of carboxylic acid and / or salt thereof in terms of group represented by formula (I) per gram of resin is component (C) ≧ component (B) ≧ component (D). The molding material in any one of Claims 8-10.
-C (= O) -O -... Formula (I) The molding material according to any one of claims 1 to 11, wherein the reinforcing fiber of the component (A) is a carbon fiber. The molding material of Claim 12 whose surface oxygen concentration ratio (O / C) measured by the X ray photoelectron spectroscopy (ESCA) of the said carbon fiber is 0.05-0.5. The molding material according to any one of claims 1 to 13, wherein the reinforcing fiber bundle of the component (A) is composed of 20,000 to 100,000 single fibers. The molding material in any one of Claims 1-14 whose porosity with respect to a component (A) is 20% or less in the said molding material. The component (A) is arranged substantially parallel to the axial direction, and the length of the component (A) is substantially the same as the length of the molding material. Molding material. The molding material according to claim 16, wherein the composite has a core structure, and the component (D) has a core-sheath structure covering the periphery of the composite. The molding material in any one of Claims 1-17 whose form of the said molding material is a long fiber pellet. The molding material in any one of Claims 1-18 whose length of the longitudinal direction of the said long fiber pellet is 1-50 mm.

Images