JP6795369B2 - Tape winding molding method, fiber reinforced resin composition for tape winding molding - Google Patents

Description

The present invention relates to a tape winding molding method. Further, the present invention relates to a fiber reinforced resin composition using the same, particularly a carbon fiber reinforced resin composition.

Fiber-reinforced thermoplastic resin molded products, which are made by combining reinforced fibers with thermoplastic resins, have excellent mechanical properties and dimensional stability, so they are used in pipes, pressure vessels, automobiles, aircraft, electrical and electronic equipment, toys, home appliances, etc. It is used in a wide range of fields. Carbon fiber, which is a kind of reinforcing fiber, is a reinforcing fiber that has recently attracted attention because of its light weight, high strength, and high rigidity.

On the other hand, polyolefin-based resins, which are hydrocarbon-based resins, are generally inexpensive, have excellent processability and chemical resistance, do not easily generate harmful gases even when incinerated, and have excellent recyclability. Therefore, it is attracting attention as a matrix resin of fiber reinforced resin. Of these, polypropylene resins, which are inexpensive, have a low specific gravity, have relatively high heat resistance, and have excellent properties such as moldability and chemical resistance, are attracting attention. However, since the polyolefin resin has low polarity, it is inferior in interfacial adhesiveness with reinforcing fibers. For this reason, attempts have been made for some time to improve the interfacial adhesiveness between the fiber and the matrix resin by surface treatment of the reinforcing fiber or application of a sizing agent.

Patent Document 1 describes a fiber treatment agent using a polypropylene resin modified with an unsaturated dicarboxylic acid or a salt thereof, and Patent Document 2 describes a specific acid value as a sizing agent suitable for a polypropylene resin. It is disclosed to impart an acid-modified polypropylene resin having.

Further, Patent Document 3 discloses a carbon fiber containing an ionomer resin. Similarly, Patent Document 4 discloses carbon fibers containing two types of acid-modified polypropylene-based resins. These can improve the interfacial adhesion between carbon fiber and matrix resin by using a resin that has affinity for both carbon fiber and polyolefin resin, including the use as a binder for carbon fiber. I am aiming.

There are few examples of using such a resin composition containing carbon fibers for tape winding molding. Since the tape winding molding method can be applied to a molded body having a relatively complicated shape, it is a method preferably used for forming an external reinforcing layer such as a pipe or a pressure vessel. (See, for example, Patent Document 5)

As a tape winding molding method having a particularly high degree of freedom in shape, a molding method using a laser fusion method can be mentioned.

Japanese Unexamined Patent Publication No. 6-107442 Japanese Unexamined Patent Publication No. 2005-48343 Japanese Unexamined Patent Publication No. 2006-124852 International Publication No. 2006/101269 Japanese Unexamined Patent Publication No. 9-257193

When the present inventors examined tape winding molding using a laser fusion method, it was found that the adhesive strength and surface texture of the fusion surface of the tape may not be sufficient. That is, there was a tendency that the fused surface was easily peeled off and the surface smoothness was deteriorated.

The present inventors presumed that such a phenomenon was caused by the following causes. That is, the heat generated in the vicinity of reinforcing fibers such as carbon fibers that easily absorb the energy of the laser and generate heat is too high, and the polyolefin, which is a matrix resin, is locally deteriorated, which triggers surface roughness. Sometimes. Further, due to the abnormal heat generation, the resin may be squeezed out from the fibers and the surface condition may be extremely deteriorated. The resin in the vicinity of the carbon fibers melts and shrinks to generate cavities, and the carbon fibers are easily peeled off.

That is, it was considered that the phenomenon was caused by a significant decrease in the homogeneity of the composition containing the resin and the fiber.

From the above viewpoint, the present invention has been made to improve the peel strength and surface texture (surface roughness) of the tape winding molded product by controlling the heat generated by the laser of the fiber reinforced resin composition.

As a result of diligent studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by containing a specific dye, and completed the present invention, that is, the present invention has the following configuration. Have.

[1] (I) 20 to 80% by mass of a polymer containing an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or a glass transition temperature of 50 to 300 ° C.
(II) 0.01 to 5% by mass of a dye that absorbs light having a wavelength of 300 to 3000 μm, and (C) 20 to 80% by mass of reinforcing fibers.
A tape winding molding method using a tape containing a fiber-reinforced resin composition containing (however, the total of the component (I) and the component (C) is 100% by mass).

[2] The tape winding molding method according to [1], wherein the component (I) contains a carboxylic acid group and the content of the structural unit thereof is 0.010 to 0.045 % by mass.

[3] (I) 20 to 80% by mass of a polymer containing an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or a glass transition temperature of 50 to 250 ° C.
(II) 0.01 to 5% by mass of a dye that absorbs light having a wavelength of 300 to 3000 μm, and (C) 20 to 80% by mass of reinforcing fibers.
Tape winding molding fiber-reinforced resin composition comprising (however, the total 100 mass% of the (I) and component wherein component (C)).

[4] The resin composition for tape winding molding according to [3], wherein the component (I) contains a carboxylic acid group and the content of the structural unit thereof is 0.010 to 0.045 % by mass.

Since the fiber-reinforced resin composition of the present invention contains a specific pigment, deterioration and deformation of the matrix resin are suppressed even in tape winding molding using the laser fusion method, and as a result, the peel strength and surface of the fusion surface are suppressed. It is possible to provide a tape winding molded product having excellent properties. Therefore, the contribution of the present invention to the industrial development is great.

It is an appearance photograph of the winding molded article of Example 1. It is an external photograph of the winding molded article of Comparative Example 1.

The fiber-reinforced resin composition used in the present invention contains a reinforcing fiber (C) and a structural unit having 2 to 20 carbon atoms, and has a melting point or a glass transition temperature of 50 to 300 ° C., a polymer (I) and a dye (II). It is characterized by including and. More specific preferred examples include the following reinforcing fiber bundles, matrix resin (example of polymer (I)), and dye (II).

The reinforcing fiber bundle of the present invention is a polyolefin containing an olefin unit having 2 to 20 carbon atoms, and is bonded to a polymer chain with a propylene resin (A) having a constituent unit derived from propylene of preferably 50 mol% or more. It is preferable to contain a propylene resin (B) containing at least a carboxylate and a reinforcing fiber (C).

In the propylene resin (A), the component (A-1) having a weight average molecular weight Mw of more than 50,000 is more than 60% by mass, and the component (A-2) having a weight average molecular weight of 100,000 or less is 100% by mass or less. , 0 to 40% by mass (however, the total of the components (A-1) and (A-2) is 100% by mass, and the molecular weight thereof is (A-1)> (A-2). ), The weight average molecular weight of the propylene-based resin (A) is larger than the weight average molecular weight of the propylene-based resin (B). The preferable content of the propylene resin (A-1) is more than 70% by mass and 100% by mass or less. The melting point or glass transition temperature of the propylene resin (A) is 0 to 165 ° C. A resin that does not show a melting point may be used.

Further, the propylene-based resin (B) is 3 to 50 parts by mass, more preferably 5 to 45 parts by mass, and further preferably 10 to 40 parts by mass with respect to 100 parts by mass of the propylene-based resin (A). The total content of the propylene resin (A) and the propylene resin (B) is preferably 60 to 5% by mass, more preferably 55 to 3% by mass, and further preferably 50 to 3% by mass in the entire reinforcing fiber bundle. It is characterized by being.

First, the components constituting the reinforcing fiber bundle according to the present invention will be described. As the reinforcing fibers constituting the reinforcing fiber bundle (C), for example, high-strength, high-elasticity fibers such as carbon fibers, glass fibers, aramid fibers, alumina fibers, silicon carbide fibers, boron fibers, and metal fibers can be used. These may be used alone or in combination of two or more. Of these, carbon fibers are preferable, and more specifically, carbon fibers such as PAN-based, pitch-based, and rayon-based are preferable from the viewpoint of improving mechanical properties and reducing the weight of the molded product, and the strength and elasticity of the obtained molded product are preferable. From the viewpoint of the balance with the rate, PAN-based carbon fibers are more preferable. Further, when imparting conductivity, reinforcing fibers containing a metal such as nickel, copper or ytterbium can also be used. In this case, the metal preferably contains a form that covers the reinforcing fibers.

Further, as the carbon fiber, the surface oxygen concentration ratio [O / C], which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy, is 0.05 to 0. It is preferably 5, more preferably 0.08 to 0.4, still more preferably 0.1 to 0.3. When the surface oxygen concentration ratio is 0.05 or more, the amount of functional groups on the surface of the carbon fiber can be secured, and stronger adhesion with the thermoplastic resin can be obtained. The upper limit of the surface oxygen concentration ratio is not particularly limited, but is generally preferably 0.5 or less from the viewpoint of the balance between the handleability and productivity of carbon fibers.

The surface oxygen concentration ratio of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface were removed with a solvent was cut into 20 mm, spread on a copper sample support and arranged, and then A1Kα1 and 2 were used as the X-ray source. Keep the inside of the sample chamber at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a correction value of the peak due to charging at the time of measurement. C _1s peak area is K. E. It is obtained by drawing a straight baseline in the range of 1191 to 1205 eV. O _1s peak area is K. E. It is obtained by drawing a straight baseline in the range of 947 to 959 eV.

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

The means for controlling the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited, but for example, methods such as electrolytic oxidation treatment, chemical solution oxidation treatment, and vapor phase oxidation treatment. Of these, electrolytic oxidation treatment is preferable.

The average fiber diameter of the reinforcing fiber (C) is not particularly limited, but is preferably in the range of 1 to 20 μm, preferably in the range of 3 to 15 μm, from the viewpoint of the mechanical properties and surface appearance of the obtained molded product. More preferably. The number of single threads of the reinforcing fiber bundle is not particularly limited, and those in the range of 100 to 350,000 can usually be used. It is preferably used in the range of 1,000 to 250,000, more preferably 5,000 to 220,000. Since the propylene-based resin (A) and the propylene-based resin (B), which will be described later, are used in the present invention, it is expected to show an excellent effect even on a fiber bundle (large tow) having 40,000 or more fibers.

Next, it is preferable that the propylene-based resin (A) used in combination with the reinforcing fiber (C) of the present invention contains olefin units having 2 to 20 carbon atoms and the constituent unit derived from propylene is 50 mol% or more. ), It is characterized by containing a component (A-1) having a weight average molecular weight of more than 50,000. The preferred weight average molecular weight range is 70,000 or more, more preferably 100,000 or more. On the other hand, although the upper limit of the weight average molecular weight is not particularly specified, it is preferably 700,000, more preferably 500,000, still more preferably 45, from the viewpoint of melt fluidity during molding and the appearance of the composition molded product described later. 10,000, especially preferably 400,000. The total of the propylene-based resin component (A-1) and the polypropylene-based resin component (A-2) described later is 100% by mass, and the propylene-based resin component (A-1) exceeds 60% by mass and 100% by mass or less. Is included in the ratio of. It is preferably 70 to 100% by mass, more preferably 73 to 100% by mass.

The polypropylene-based resin (A) of the present invention is characterized by containing a component (A-2) having a weight average molecular weight of 100,000 or less, if necessary. The preferred weight average molecular weight range is 50,000 or less, more preferably 40,000 or less. On the other hand, the lower limit of the weight average molecular weight is preferably 10,000, more preferably 15,000, still more preferably 20,000, particularly preferably 20,000, in consideration of the strength and handleability (stickiness, etc.) of the reinforcing fiber bundle described later. Is 25,000. The polypropylene resin component (A-2) is contained in a proportion of 0 to 40% by mass (however, the total of the above component (A-1) and the component (A-2) is 100% by mass. ). It is preferably 0 to 30% by mass, more preferably 0 to 27% by mass.

In the present invention, the difference between the weight average molecular weight of the propylene resin (A-1) and the weight average molecular weight of the propylene resin (A-2) is preferably 20,000 to 300,000. It is more preferably 30,000 to 200,000, still more preferably 35,000 to 200,000.

A reinforcing fiber bundle containing a specific amount of polypropylene resin when a relatively large amount of a component having a high weight average molecular weight is contained has a fluffy shape, for example, its impact, etc., even when the above-mentioned propylene-based resin is used in a relatively small amount. There is a tendency that shape changes such as collapse, peeling, and breakage due to environmental factors, and shape changes such as fine powder due to them are unlikely to occur.

The propylene-based resin (A) is a resin having a structural unit derived from propylene, and is usually a polymer of propylene. A so-called copolymer containing at least one olefin or polyene-derived structural unit selected from α-olefins, conjugated dienes, non-conjugated dienes and the like is preferable.

Specifically, as the α-olefin, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 4 , 4Dimethyl-1-hexene, 1-nonene, 1-octene, 1-hexene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- Examples thereof include α-olefins having 2 to 20 carbon atoms excluding propylene such as eikosen. Among these, 1-butene, ethylene, 4-methyl-1-pentene and 1-hexene can be mentioned as preferable examples, and 1-butene and 4-methyl-1-pentene are particularly preferable.

Examples of the conjugated diene and the non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the like, and one or more of these components can be selected.

The propylene-based resin (A) is preferably a random or block copolymer of propylene and the olefin or polyene compound. Other thermoplastic polymers can be used as long as the object of the present application is not impaired. For example, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer and the like are preferable.

In the present invention, from the viewpoints of both increasing the affinity with the propylene-based resin (D) described later (generally referred to as a matrix resin) and enhancing the affinity with the propylene-based resin (B) described later. The propylene-based resin (A) contains a constituent unit derived from propylene, preferably 50 mol% or more, 100 mol% or less, more preferably 50 to 99 mol%, still more preferably 55 to 98 mol%, and particularly preferably 60. Contains ~ 97 mol%.

The identification of the monomer repeating unit in the propylene resin is mainly determined by the ¹³ C NMR method. Mass spectrometry and elemental analysis may also be used. In addition, there is also a method of performing IR analysis of a plurality of types of copolymers having different compositions whose compositions have been determined by the NMR method, and creating a calibration curve from information such as absorption of a specific wave number and sample thickness to determine the composition. Can be adopted. This IR method is preferably used for process analysis and the like.

Further, in the present invention, the shore A hardness of the propylene resin (A) is preferably 60 to 90, or the shore D hardness is preferably 45 to 65. A more preferred range of shore A hardness is 65-88, more preferably 70-85. A more preferred range of shore D hardness is 48-63. More preferably, it is 50 to 60.

When the propylene resin (A) is in such a hardness range, it has good followability to the reinforcing fibers, so that partial cracking is unlikely to occur, and it is easy to form a reinforcing fiber bundle having a stable shape. There is. Further, when the composition is combined with the propylene-based resin (D) described later, it tends to be advantageous in increasing its strength. It is presumed that this is because the propylene-based resin (A) and the propylene-based resin (D) have a good molecular chain entangled structure.

The propylene-based resin (A) may be modified with a compound containing a carboxylic acid group, a carboxylic acid ester group, or the like, or may be an unmodified product. When the propylene resin (A) is a modified product, the modified amount is preferably less than 2.0 mmol equivalent in terms of the group represented by −C (= O) −O−. It is more preferably 1.0 mmol or less, still more preferably 0.5 mmol or less. When the propylene resin (A) is a modified product, it is preferable that the component (A-2) is mainly a modified product.

On the other hand, depending on the intended use, it may be preferable that the propylene resin (A) is substantially unmodified. Here, substantially undenatured means that the substance is not denatured at all, but the amount of denatured is −C (= O) −O−, which is a range that does not impair the above-mentioned purpose even if denatured. It is preferably less than 0.05 mmol equivalent in terms of the group represented. It is more preferably 0.01 mmol or less, still more preferably 0.001 mmol or less, and particularly preferably 0.0001 mmol or less.

The propylene-based resin (B) of the present invention is a propylene-based resin containing at least a carboxylate bonded to a polymer chain. This is because it is effective to include the carboxylate in enhancing the interaction with the reinforcing fibers.

The raw materials of the propylene resin (B) are propylene and α-olefin represented by polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, and ethylene / propylene / 1-butene copolymer. First of all, a copolymer of the above alone or with two or more kinds of the above is mentioned. Then, a monomer having a neutralized or unneutralized carboxylic acid group and / or a monomer having a saponified or unsaken carboxylic acid ester can be mentioned. In such a polymer, radical graft polymerization of a propylene-based polymer and a monomer having a carboxylic acid structure is a typical method for producing a propylene-based resin (B). The olefin used in the propylene-based polymer can be selected in the same manner as the propylene-based resin (A).

If a special catalyst is used, propylene can be directly polymerized with the above-mentioned monomer having a carboxylic acid ester, or if the polymer contains a large amount of ethylene, an olefin (such as ethylene and propylene) and a carboxylic acid structure can be obtained. There is also a possibility that the propylene-based resin (B) can be obtained by mainly high-pressure radical polymerization with the monomer having.

Here, examples of the monomer having a carboxylic acid group that is neutralized or not neutralized and the monomer having a carboxylic acid ester group that is sanitized or not sanitized include ethylene. Examples thereof include system-unsaturated carboxylic acids and anhydrides thereof, and examples thereof include esters thereof and compounds having an unsaturated vinyl group other than olefins.

Examples of the ethylene-based unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid, and examples of the anhydride thereof include nadic acid ^TM. (Endosys-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride and the like can be exemplified.

Examples of monomers having an unsaturated vinyl group other than olefins include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 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 (Meta) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobolonyl (meth) ) Acrylate, (meth) acrylic acid esters such as dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl acrylate, 2- Hydroxyl-containing vinyls such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, glycidyl (meth) ) Epoxy group-containing vinyls such as acrylate and methylglycidyl (meth) acrylate, isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and the like. Aromatic vinyls, acrylamide, methacrylicamide, N-methylolmethacrylicamide, N-methylolacrylamide, diacetoneacrylamide, maleic acid amide and other amides, vinyl acetate, vinyl propionate and other vinyl esters, N, N-dimethyl Aminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) Aminoalkyl (meth) acrylates, N, N-dihydroxyethylaminoethyl (meth) acrylates and the like ) Aliases, styrene sulfonic acid, sodium styrene sulfonic acid, unsaturated sulfonic acids such as 2-acrylamide-2-methylpropane sulfonic acid, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) ) Unsaturated phosphoric acids such as acid phosphate and the like can be mentioned.

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

The propylene-based resin (B) can be obtained by various methods as described above, but more specifically, an ethylene-based unsaturated carboxylic acid having a propylene-based resin and an unsaturated vinyl group in an organic solvent, or A method of reacting a monomer having an unsaturated vinyl group other than olefin with a monomer having an unsaturated vinyl group in the presence of a polymerization initiator and then removing the solvent, or a melt obtained by heating and melting a propylene resin has an unsaturated vinyl group. A method of reacting the carboxylic acid and the polymerization initiator under stirring, or a mixture of a propylene resin, a carboxylic acid having an unsaturated vinyl group and a polymerization initiator was supplied to an extruder and reacted while being heated and kneaded. After that, a method of converting into a carboxylate by a method such as neutralization or saponification can be mentioned.

Here, as the polymerization initiator, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexin-3, Various peroxide compounds such as 1,4-bis (tert-butylperoxyisopropyl) benzene can be mentioned. Further, an azo compound such as azobisisobutyronitrile may be used. These can be used alone or in combination of two or more.

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

It is known that the content of the carboxylic acid group of the propylene resin (B) obtained as described above can be determined by NMR or IR measurement described later. Further, for example, as another method, it can be evaluated by the acid value. The preferred range of the acid value of the propylene resin (B) of the present invention is 10 mg-KOH / g to 100 mg-KOH / g, more preferably 20 mg-KOH / g to 80 mg-KOH / g, and even more preferably. It is 25 mg-KOH / g to 70 mg-KOH / g, and particularly preferably 25 mg-KOH / g to 65 mg-KOH / g.

The method of obtaining the propylene-based resin (B) obtained as described above through a neutralization or saponification step makes it easy to treat the raw material of the propylene-based resin (B) as an aqueous dispersion. This is a practically preferable method.

Examples of the basic substance used for neutralizing or saponifying the aqueous dispersion of the raw material of the propylene resin (B) 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, Of sodium peroxide, alkali metals and / or oxides of alkaline earth metals and / or other metals, hydroxides, hydrides, alkali metals such as sodium carbonate and / or alkaline earth metals and / or other metals Weak salts can be mentioned. As the carboxylic acid salt group or the carboxylic acid ester group neutralized or saponified by the basic substance, an alkali metal carboxylic acid salt such as sodium carboxylate or potassium carboxylate or ammonium carboxylate is preferable.

Further, the degree of neutralization or saponification, that is, the conversion rate of the carboxylic acid group of the raw material of the propylene resin (B) to the above metal salt, ammonium salt, etc., determines the stability of the aqueous dispersion and the adhesion to the fiber. From the viewpoint of sex, it is usually 50 to 100%, preferably 70 to 100%, and more preferably 85 to 100%. Therefore, it is desirable that all the carboxylic acid groups in the propylene resin (B) are neutralized or saponified by the basic substance, but some carboxylic acid groups remain without being neutralized or saponified. You may. As a method for analyzing the salt component of an acid group as described above, a method of detecting a metal species forming a salt by ICP emission spectrometry, an acid group using IR, NMR, mass spectrometry, elemental analysis, or the like is used. There is a method of identifying the structure of the salt of.

Here, the conversion rate of the carboxylic acid group to a neutralized salt is determined by dissolving the propylene-based resin in heated toluene and titrating with a potassium hydroxide-ethanol standard solution of 0.1N to lower the acid value of the propylene-based resin. Examples thereof include a method of obtaining from the formula and calculating by comparing with the total number of moles of the original carboxylic acid group.
Acid value = (5.611 x A x F) / B (mgKOH / g)
A: 0.1 Standard potassium hydroxide-ethanol standard solution usage amount (ml)
F: Factor of 0.1 standard potassium hydroxide-ethanol standard solution B: Sample amount (g).

The acid value calculated above is converted into the number of moles of unneutralized carboxylic acid groups using the following formula.
Number of moles of unneutralized carboxylic acid group = acid value x 1000/56 (molar / g).

The conversion rate of a carboxylic acid group to a neutralized salt is the total number of moles (molar / g) of the carboxylic acid group calculated by separately quantifying the carbonyl carbon of the carboxylic acid group using IR, NMR, element analysis, etc. Calculate using the following formula.
Conversion rate% = (1-r) x 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 (C), the content of the carboxylic acid salt bonded to the polymer chain of the propylene-based resin (B) is −C (1 g) per 1 g of the propylene-based resin (B). = O) It is preferable that the total amount is 0.05 to 5 mmol equivalent in terms of the group represented by −O−. It is more preferably 0.1 to 4 mmol equivalent, still more preferably 0.3 to 3 mmol equivalent. As a method for analyzing the content of the carboxylic acid salt as described above, a method of quantitatively detecting a metal species forming a salt by ICP luminescence analysis, a method of quantitatively detecting a metal species forming a salt, or carboxylic acid using IR, NMR, elemental analysis, or the like. Examples thereof include a method for quantifying the carbonyl carbon of the acid salt. The following method can be exemplified as a more specific method for measuring the content of the carboxylic acid skeleton. The content of the carboxylic acid skeleton can be specified by a conventional method by the ¹³ C NMR method in the sample under the condition of 100 MHz or more and the high temperature solution condition of 120 ° C. or more. In addition, after measuring a plurality of samples having different carbonyl skeleton contents by the above ¹³ CNMR to specify the carboxylic acid skeleton content, IR measurement of the same sample is performed to obtain characteristic absorption of carbonyl and the like and sample thickness. A method of specifying the introduction rate of the carboxylic acid skeleton by IR measurement is also known by creating a calibration curve between the ratio to other typical absorption and the content of the carboxylic acid skeleton.

Further, the relationship of the weight average molecular weight Mw between the propylene-based resin (A) and the propylene-based resin (B) of the present invention is preferably larger than the weight average molecular weight Mw of the propylene-based resin (A). In this case, in the present invention, the difference between the weight average molecular weight of the propylene resin (A) and the weight average molecular weight of the propylene resin (B) is preferably 10,000 to 380,000. It is more preferably 120,000 to 380,000 and even more preferably 130,000 to 380,000.

By making the weight average molecular weight Mw of the propylene resin (B) smaller than the weight average molecular weight Mw of the propylene resin (A), the propylene resin (B) can easily move during molding, and the reinforcing fiber and the propylene resin ( It is expected that the interaction with B) will be stronger.

The weight average molecular weight Mw of the propylene-based resin (B) is 1,000 to 1, considering the viewpoint of the above interaction and compatibility with the propylene-based resin (A), preferably the propylene-based resin (A-2). It is preferably 100,000. It is more preferably 2,000 to 80,000, still more preferably 5,000 to 50,000, and particularly preferably 5,000 to 30,000.

The weight average molecular weight in the present invention is determined by gel permeation chromatography (GPC).

The melt flow rate (ASTM1238 standard, 230 ° C., 2.16 kg load) of the propylene resin (B) is preferably 3 to 500 g / 10 minutes. The preferred lower limit is 5 g / 10 min, more preferably 7 g / 10 min, and the preferred upper limit is 400 g / 10 min, even more preferably 350 g / 10 min.

Further, as a preferable melt flow rate range, the measured value under the ATM1238 standard, 190 ° C., and 2.16 kg load may be in the same numerical range as the above.

The propylene-based resin (A) and the propylene-based resin (B) of the present invention can be used in various forms. For example, a method in which the propylene-based resin is melted as it is or in combination with a heat-resistant stabilizer and brought into contact with the reinforcing fiber (C), or the propylene-based resin (A) and the propylene-based resin (B) are reinforced in an emulsion or suspension state. A method of contacting with the fiber (C) can be mentioned. After the contact step, heat treatment or the like may be performed.

In the present invention, the propylene-based resin (A) and the propylene-based resin (B) are preferably used in an emulsion state from the viewpoint of efficient contact with the reinforcing fiber (C).

As described above, the ratio of the propylene-based resin (A) to the propylene-based resin (B) is 3 to 50 parts by mass for the propylene-based resin (B) with respect to 100 parts by mass of the propylene-based resin (A). Within this range, it is possible to achieve both the strength and shape-related properties mainly derived from the propylene resin (A) and the affinity with the reinforcing fibers at a high level. Preferably, the propylene-based resin (B) is 5 to 45 parts by mass with respect to 100 parts by mass of the propylene-based resin (A), and more preferably the propylene-based resin (B) is contained with respect to 100 parts by mass of the propylene-based resin (A). The amount of the propylene-based resin (B) is 7 to 40 parts by mass with respect to 5 to 45 parts by mass, more preferably 100 parts by mass of the propylene-based resin (A). If the amount of the propylene-based resin (B) is less than 3 parts by mass, the affinity with the reinforcing fibers is lowered, and the adhesive properties may be inferior. Further, if the amount of the propylene resin (B) is more than 50 parts by mass, the strength of the mixture itself may decrease or the fluff may increase, and it may not be possible to maintain strong adhesive properties.

By setting the molecular weight and content of the various propylene resins used in the reinforcing fiber bundle of the present invention within the above ranges, the propylene resins (A) and (B) effectively interact with the reinforcing fibers and the matrix resin. In addition, the compatibility with the propylene resins (A) and (B) is relatively high, and it is expected that the adhesiveness will be improved.

In addition to the propylene-based resin (A) and the propylene-based resin (B), other components may be used in combination with the reinforcing fiber bundle of the present invention as long as the effects of the present invention are not impaired. For example, when the propylene resin is applied to the reinforcing fiber bundle in the form of an emulsion, a surfactant or the like that stabilizes the emulsion may be added separately. Such other components are preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, based on the total of the propylene-based resin (A) and the propylene-based resin (B). is there.

The above-mentioned propylene-based resin (A) and propylene-based resin (B) are contained in a relatively small amount of 0.3 to 5% by mass of the entire reinforcing fiber bundle. When the content of the propylene-based resin (A) and the propylene-based resin (B) is less than 0.3% by mass, a large number of exposed reinforcing fibers may be present. In such a case, the strength of the obtained product may be lowered, or the handleability of the reinforcing fiber bundle may be insufficient. The handleability referred to here includes, for example, the hardness and ease of handling of the fiber bundle when the fiber bundle is wound around the bobbin. Further, when the fiber bundle is cut and used as a chopped fiber bundle, it means the focusing property of the chopped fiber bundle. On the other hand, if the content is more than 5% by mass, the mechanical properties of the molded product may be extremely deteriorated, or the fiber bundle may become extremely hard and may not be wound on the bobbin. The total content of the propylene-based resin (A) and the propylene-based resin (B) in the entire reinforcing fiber bundle is preferably 0.4 from the viewpoint of the balance between the adhesiveness and the handleability of the reinforcing fiber bundle. It is mass%. On the other hand, the preferable upper limit value is 4% by mass, and more preferably 3% by mass.

The method for adhering the mixture of the propylene-based resin to the reinforcing fiber bundle is not particularly limited, but from the viewpoint of easily adhering the mixture between the single fibers uniformly, the propylene-based resin (A) and the propylene-based resin (B) are used. A method in which an emulsion of the mixture of the above is applied to the reinforcing fiber bundle and then dried is preferable. As a method of applying the emulsion to the reinforcing fiber bundle, a method of applying the emulsion by an existing method such as a roller dipping method, a roller transfer method, or a spray method can be used.

The molding resin composition using the reinforcing fiber bundle of the present invention and the matrix resin for molding a molded product are preferably propylene-based polymerization (D) described later. In addition, polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin (PPS resin), modified polyphenylene ether resin (modified PPE resin), polyacetal resin (POM resin), liquid crystal polyester, polyarylate, polymethylmethacrylate. Acrylic resin such as resin (PMMA), vinyl chloride, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone, polyethersulfone, polyketone, polyetherketone, polyetheretherketone (PEEK), Polyetherketones such as polyethylene, polypropylene, polybutene and poly-4-methyl-1-pentene, thermoplastic resins such as modified polyolefins, phenol resins and phenoxy resins, as well as ethylene / propylene copolymers and ethylene / 1-butene copolymers. Ethylene / propylene / diene copolymer, ethylene / carbon monoxide / diene copolymer, ethylene / ethyl (meth) acrylate copolymer, glycidyl ethylene / (meth) acrylate, ethylene / vinyl acetate / (meth) acrylic A glycidyl acid copolymer may be used, or one or more of these may be used in combination. Among these, a polyolefin-based resin having a particularly low polarity is preferable, and an ethylene-based polymer or a propylene-based polymer is preferable from the viewpoint of cost and lightness of the molded product, and the propylene-based resin (D) described later is more preferable. preferable. That is, a propylene-based resin composition containing a reinforcing fiber bundle is preferably used as a molding material or a molded product.

The propylene-based resin (D) may be an unmodified propylene-based resin, or may contain a propylene-based resin containing a carboxylic acid structure or a carboxylate structure by a method such as modification. Is preferably the latter aspect containing the modified propylene resin. The preferred weight ratio is the unmodified / modified ratio of 80/21 to 99/1, preferably 89/11 to 99/1, and more preferably 89/11 to 93/7. More preferably, it is 90/10 to 95/5. The composition of the propylene-based resin is a general propylene containing a structural unit derived from the monomer (olefin, carboxylic acid ester compound, etc.) described in the description of the propylene-based resin (A) and the propylene-based resin (B). Resin is a preferred embodiment. For example, it is a propylene polymer called homopolypropylene, random polypropylene, block polypropylene, or modified polypropylene.

The weight average molecular weight of the propylene-based resin (D) of the present invention preferably has the following relationship with the propylene-based resin (A) and the propylene-based resin (B).
Propene resin (A) ＞ Propene resin (D) ＞ Propene resin (B)
The weight average molecular weight of the propylene resin (D) is preferably in the range of 50,000 to 350,000, more preferably 100,000 to 330,000, and further preferably 150,000 to 320,000. is there. The difference in molecular weight between the propylene-based resin (A) and the propylene-based resin (D) is preferably 10,000 to 400,000, more preferably 20,000 to 200,000, and further preferably 20,000 to 100,000. Is.

The molding material (propylene-based resin composition containing a reinforcing fiber bundle) of the present invention contains 25 to 75 parts by mass, preferably 30 to 68 parts by mass, and more preferably 35 to 65 parts by mass of the reinforcing fiber bundle. I'm out. On the other hand, the propylene-based resin (D) contains 75 to 25 parts by mass, preferably 70 to 32 parts by mass, and more preferably 65 to 35 parts by mass. However, the above ratio is a value when the total of the reinforcing fiber bundle and the propylene resin (D) is 100 parts by mass.
The propylene-based resin (D) is preferably in a form of being mainly adhered around a reinforcing fiber bundle containing a reinforcing fiber, a propylene-based resin (A), and a propylene-based resin (B).

The propylene-based resin (D) of the present invention preferably contains an unmodified propylene-based resin and an acid-modified propylene-based resin. In particular, since it contains a relatively large amount of modified propylene-based resin, the structure between the reinforcing fiber and the resin tends to be difficult to change even if the laser fusion method described later is used. It is presumed that this is because the modified resin of the propylene resin (D) is stored even if the modified olefin polymer (A-2) in the vicinity of the reinforcing fibers is destroyed.

The propylene-based resin used in the present invention can be produced by a known method, and the stereoregularity of the resin (polymer) may be isotactic, syndiotactic, or atactic. .. The stereoregularity is preferably isotactic or syndiotactic.

Specific methods for producing the above resins (particularly unmodified resins) include, for example, International Publication No. 2004/0877775 Pamphlet, International Publication No. 2006/057361 Pamphlet, International Publication No. 2006/123759 Pamphlet, Japanese Patent Application Laid-Open No. 2007- 308667, Pamphlet 2005/103141, Japanese Patent No. 4675629, Pamphlet 2014/050817, Japanese Patent Application Laid-Open No. 2013-237861 and the like can be mentioned.

The weight ratio of the reinforcing fiber (C) and the polymer (I) of the fiber-reinforced resin composition used in the present invention is 80/20 to 20/80. It is preferably 75/25 to 30/70, more preferably 70/30 to 35/65, still more preferably 65/35 to 40/60, and particularly preferably 60/40 to 40 to 60. If the fiber content is too high, tape peeling may easily occur in the tape winding molded product described later. On the other hand, if the resin content is too high, the strength of the tape winding molded product described later may decrease.

The melting point or glass transition temperature of the resin is 50 to 300 ° C. The preferred lower limit is 70 ° C, more preferably 80 ° C. On the other hand, the preferred upper limit is 280 ° C, more preferably 270 ° C, and even more preferably 260 ° C. Further, the above specification preferably has a melting point, and further, the upper limit of the preferable melting point is 250 ° C., more preferably 240 ° C.
The resin preferably contains a carboxylic acid group. Assuming that the total of the reinforcing fibers (C) and the polymer (I) of the fiber-reinforced resin composition is 100% by mass, the content of the structural unit containing the carboxylic acid group is 0.010 to 0.045% by mass. It is preferably 0.012 to 0.040% by mass, more preferably 0.015 to 0.035% by mass. If the content of the structural unit containing the carboxylic acid group is too low, tape peeling may easily occur in the tape winding molded product described later. The structural unit containing the carboxylic acid group includes, for example, a structural unit derived from the carboxylic acid group contained in the propylene-based resin (A), the propylene-based resin (B), and the propylene-based resin (D) or a carboxylic acid salt. The structural unit of origin can be mentioned.

When the resin contains a carboxylic acid group, it is also possible to grasp the content rate by the acid value. The preferred acid value is 0.1 to 0.55 mg-KOH / g, more preferably 0.12 to 0.45 mg-KOH / g, and even more preferably 0.13 to 0.40 mg-KOH / g.

The preferred melt flow rate (ASTM1238 standard, 230 ° C., 2.16 kg load) of the resin used in the fiber-reinforced resin composition of the present invention is 1 to 500 g / 10 minutes, more preferably 3 to 300 g / 10 minutes. , More preferably 5 to 100 g / 10 minutes.
Specifically, the weight average molecular weight of the resin is preferably in the range of 50,000 to 400,000, more preferably 100,000 to 370,000, and further preferably 150,000 to 350,000.

Further, a known method can be used as the method for producing the emulsion, and examples thereof include International Publication No. 2007/125924 Pamphlet, International Publication No. 2008/09662 Pamphlet, and JP-A-2008-144146.

As a method for identifying the ease of unraveling of the fiber bundle, which is considered to be the cause of the above-mentioned fluffing, the method described in Japanese Patent No. 5584977 and the method for evaluating the focusing property described in Japanese Patent Application Laid-Open No. 2015-165555 are known. ing. In the embodiment of the present application, the former is evaluated. Specifically, the latter method is as follows.

The reinforcing fiber bundle is cut into short fibers of about 5 mm using stainless steel scissors. The obtained short fibers are evaluated by the following visual judgment.

◯: The short fibers are kept in almost the same state as before cutting.
X: Short fibers are widely scattered or cracked.

In order to exhibit stronger adhesiveness, the single fiber forming the reinforcing fiber bundle of the present invention is coated with a mixture containing propylene-based resin (A) and propylene-based resin (B) in 60% or more of the surface of the single fiber. It is preferable that it is. The uncoated portion cannot exhibit adhesiveness and may become a starting point of peeling, resulting in a decrease in overall adhesiveness. It is more preferably 70% or more covered, and further preferably 80% or more covered. For the coating state, a scanning electron microscope (SEM) or a method of tracing the metal element of the carboxylate by elemental analysis of the fiber surface can be used.

The preferred shape of the reinforcing fiber bundle in the present invention is a unidirectional carbon fiber reinforced thermoplastic resin molded body in which continuous fibers are aligned in one direction and composited with a thermoplastic resin.

The fiber-reinforced resin composition of the present invention is characterized by containing a dye (II) that absorbs light having a wavelength of 300 to 3000 μm. As such a dye, a known one can be used without limitation. A carbon-based dye can be mentioned as a preferable example. More preferably, it is carbon black.

Such dye (II) is 0.01 to 5% by mass of the total fiber-reinforced thermoplastic resin of the present invention. The preferred lower limit is 0.1% by mass, more preferably 0.2% by mass. On the other hand, the preferable upper limit value is 3% by mass, more preferably 2% by mass.
When the fiber-reinforced resin composition of the present invention contains the above-mentioned dye (II), it is expected that local heat generation by a laser, which will be described later, can be suppressed and the entire resin composition can be heated more uniformly. As a result, deterioration and deformation of the matrix resin, more specifically, surface protrusion of fibers, surface smoothness, and deterioration of appearance can be suppressed.

As a molding method using the reinforcing fiber bundle of the present invention, for example, a unidirectional carbon fiber reinforced thermoplastic resin is obtained by aligning the opened fiber bundles and then bringing them into contact with the molten matrix resin (D). A method of obtaining a molded product (unidirectional material) can be mentioned. This unidirectional material can be used as it is, or a laminated body can be created by laminating a plurality of materials and integrating them, and the laminated body can be used. Further, it can be appropriately cut into a tape shape.

In the tape winding molded product of the present invention, the fiber-reinforced resin composition is processed into a tape shape by a known method, and this is processed into a mandrel while melting the tape surface by a tape winding method using a known laser fusion method in combination. It is obtained by fusion while making contact. As an example of the tape winding molding method, for example, a method of using a photocurable resin as a matrix resin is disclosed in Japanese Patent Application Laid-Open No. 2005-206847 (for example, FIG. 8). In the case of the tape winding molding used in the present invention, for example, a robot as disclosed on the homepage (http://www.afpt.de/welcome/) of AFPT (Germany) as of September 8, 2016. In an apparatus in which a laser irradiation unit is attached to the arm as a light source, a method of molding using the above-mentioned thermoplastic resin can be given as an example. Others ^{include, 17 th -Europian conference on Composite Materials} , 1 ~ presented at 8 (2016), the "Development of a hybrid tail rotor drive shaft by the use of thermoplastic Automated fiber placement" and, "Selective reinforcement of steel with CF The devices and methods disclosed in "/ PA6 composites in a laser tape placement process: effect of surface preparation and laser angle on interfacial bond strength" can be exemplified.

However, when fusion is performed by a laser, it is preferable to move the light source and the mandrel appropriately to efficiently melt and fuse. When such a method is adopted, the moving speed thereof is preferably 10 to 100 m / min, preferably 30 to 90 m / min, as the scanning speed of the fiber-reinforced thermoplastic resin composition tape.

The wavelength of the laser is preferably 300 to 3000 μm. This wavelength preferably includes the absorption wavelength region of the reinforcing fiber (C) and the dye (II). Further, the output of the laser is preferably 50 W to 5 kW. If this output is too strong, it may cause deterioration or deformation of the resin. On the other hand, if it is too weak, the resin may not melt.

As for the resin composition of the present invention, a tape winding molded product using a fiber-reinforced thermoplastic resin composition tape formed into a tape shape by the method as described above can be developed for various uses. For example, it is a preferable example to use an external reinforcing portion of various containers such as a pipe and a pressure vessel. That is, it can be suitably used for a container having various laminated structures.

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

(1) Measurement of Adhesion Amount of Propylene Resin to Reinforced Fiber Bundle About 5 g of the propylene resin-based reinforcing fiber bundle was taken, dried at 120 ° C. for 3 hours, and its weight W ₁ (g) was measured. Next, the reinforcing fiber bundle was heated at 450 ° C. for 15 minutes in a nitrogen atmosphere, cooled to room temperature, and its weight W ₂ (g) was measured. The amount of adhesion was calculated by the following formula using W ₁ (g) and W ₂ (g).
Adhesion amount = [(W ₁ − W ₂ ) / W ₂ ] × 100 (mass%).

(2) Measurement of Weight Average Molecular Weight of Propylene Resin The molecular weight was determined by the GPC method under the following conditions.
Liquid chromatograph: PL-GPC220 type high performance gel permeation chromatograph manufactured by Polymer Laboratories (built-in differential refractometer)
Column: TSKgel GMH _HR- H (S) -HT x 2 and GMH _HR- H (S) x 1 manufactured by Tosoh Corporation were connected in series.
Mobile phase medium: 1,2,4-trichlorobenzene (containing 0.025% stabilizer)
Flow velocity: 1.0 ml / min Measurement temperature: 150 ° C
Method for preparing a calibration curve: A standard polystyrene sample was used.
Sample concentration: 0.15% (w / v)
Sample solution volume: 500 μl
Standard sample for preparing calibration curve: Monodisperse polystyrene manufactured by Tosoh Corporation Molecular weight calibration method: Standard calibration method (polystyrene conversion)

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

Elemental analysis of organic compounds was carried out 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). ^{1 1} H-NMR measurement and ¹³ C-NMR measurement were carried out using a JEOL JNM-GX400 spectrometer (manufactured by JEOL Ltd.).

(4) Measurement of Carboxylate Content of propylene Resin The Carboxylate Content and Unneutralized Carboxylic Acid Content of each of the first and second propylene resins are performed by performing the following operations. Was measured.

0.5 g of the propylene resin was heated to reflux in 200 ml of toluene to dissolve it. This solution was titrated with 0.1N potassium hydroxide-ethanol standard solution, and the acid value was calculated from the following formula. Phenolphthalein was used as an indicator.
Acid value = (5.611 x A x F) / B (mgKOH / g)
A: 0.1 Standard potassium hydroxide-ethanol standard solution usage amount (ml)
F: Factor of 0.1 standard potassium hydroxide-ethanol standard solution (1.02)
B: Sample collection amount (0.50 g).

The acid value calculated above was converted to the number of moles of unneutralized carboxylic acid groups using the following formula.
Number of moles of unneutralized carboxylic acid group = acid value x 1000/56 (molar / g)

The total number of moles (molar / g) of the carboxylic acid group calculated by quantifying the carbonyl carbon of the carboxylic acid group separately using IR, NMR, element analysis, etc. for the conversion rate of the carboxylic acid group to the neutralized salt. It was calculated by the following formula using.
Conversion rate% = (1-r) x 100 (%)
r: Number of moles of unneutralized carboxylic acid groups / total number of moles of carboxylic acid groups.

(5) Measurement of the number of scraped fluff The determination was made in the same manner as in the method described in Examples of Japanese Patent No. 5584977.
The number of scraped fluff was 0 to 5 / m as a pass, and if it exceeded that, it was rejected.

(6) Appearance Evaluation of Winding Mold The appearance of the winding molded body was visually evaluated. The evaluation items are resin squeezing, fiber ejection, surface low slipperiness, and surface gloss.

(7) Method for Measuring Melting Point The melting point (Tm) of the polymer in the present invention was measured by a differential scanning calorimeter (DSC) with a DSC220C apparatus manufactured by Seiko Instruments. 7-12 mg of sample was sealed in an aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The sample was held at 200 ° C. for 5 minutes to completely melt all crystals and then cooled to −50 ° C. at 10 ° C./min. After standing at −50 ° C. for 5 minutes, the sample was heated a second time to 200 ° C. at 10 ° C./min. In this second heating test, the peak temperature was adopted as the melting point (Tm-II).

The materials used in the examples are shown below as reference examples.

<Reinforcing fiber (C)>
A carbon fiber bundle (manufactured by Mitsubishi Rayon Co., Ltd., product name: Pyrofil TR50S12L, number of filaments 12000, strand strength 5000 MPa, strand elastic modulus 242 GPa) is immersed in acetone, ultrasonically applied for 10 minutes, and then the carbon fiber bundle is formed. It was pulled up, washed with acetone three more times, and dried at room temperature for 8 hours to remove the adhering sizing agent before use.

(Production Example 1-Emulsion production method)
As the propylene resin (A), a weight average molecular weight of 120,000 measured by GPC, 100 parts by mass of a propylene / butene / ethylene copolymer having no melting point, and maleic anhydride modification as a raw material of the propylene resin (B). As a propylene-based polymer (weight average molecular weight Mw = 27,000, acid value: 45 mg-KOH / g, maleic anhydride content: 4% by mass, melting point: 140 ° C.), 10 parts by mass, as a surfactant (C) 3 parts by mass of potassium oleate was mixed. This mixture is supplied from the hopper of a twin-screw screw extruder (manufactured by Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40) at a speed of 3000 g / hour, and is supplied from a 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 extruded continuously at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a static mixer with a jacket installed at the mouth of the extruder, 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 resin contains 96 parts by mass of a propylene / butene copolymer, 4 parts by mass of maleic anhydride, and 0.4 parts by mass of perhexy 25B (manufactured by Nippon Oil & Fats Co., Ltd.) as a polymerization initiator. It was obtained by mixing and modifying at a heating temperature of 160 ° C. for 2 hours.

<Example 1>
The emulsion produced in Production Example 1 was adhered to the Mitsubishi Rayon reinforcing fiber by using a roller impregnation method. Then, it was dried online at 130 ° C. for 2 minutes to remove the low boiling point component, and the reinforcing fiber bundle of the present invention was obtained. The amount of the emulsion adhered was 0.87%. The fluffiness of the carbon fiber bundle was acceptable.

Next, 57 parts of this reinforcing fiber, a commercially available unmodified propylene resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro J106MG, melting point: 160 ° C.) and maleic anhydride are grafted as a matrix resin (D) in an amount of 0.5% by mass. Masterbatch containing carbon black (PEONY manufactured by DIC Co., Ltd.) containing modified polypropylene (melt flow rate measured at 190 ° C., load 2.16 kg, 9.1 g / 10 minutes, melting point 155 ° C., according to ASTM D1238). A resin composition containing 43 parts of BLACK BMB-16117 (carbon black content 40%) was prepared, and a sheet having an average thickness of 150 μm was prepared by a conventional method. The weight ratio of the J106MG to the modified polypropylene was 90/10 (the weight average molecular weight was equivalent to 300,000), and the carbon black content was adjusted to be 1% by mass of the entire resin composition. (The melting point of the resin is 160 ° C., the content of maleic anhydride structural units with respect to the entire resin composition: 0.023% by mass) (fibrous volume fraction Vf0.4). This is cut into a tape with a width of 12 mm with a slitter, and the robot is equipped with an AFPT "STWH INB" type take-up head that controls a diode laser with an output of 3 kW and a wavelength of 960 to 70 nm in a closed loop. Then, a pipe was formed by winding it around a mandrel having an inner diameter of φ95 mm. For winding, + 20 ° and −20 ° were alternately laminated to obtain a two-layer winding pipe.

The appearance of the wound molded product was that the resin was not squeezed out, the fibers did not pop out, the surface low slipperiness was good, and the surface gloss was also good.

The tape of the winding molded body was forcibly peeled off using a wedge-shaped jig having a thickness of 1.4 mm and a tip angle of 30 °, and the peeled surface was observed with an electron microscope manufactured by JEOL Ltd. There was no peeling of the resin part. (Peeling of the interface between the reinforcing fiber and the resin was observed.)

<Example 2>
A winding pipe was obtained in the same manner as in Example 1 except that the content of carbon black was 0.6% by mass.

The appearance of the wound molded product was that the resin was not squeezed out, the fibers did not pop out, the surface low slipperiness was good, and the surface gloss was also good.

The appearance of the wound molded product was that the resin was not squeezed out, the fibers did not pop out, the surface low slipperiness was good, and the surface gloss was also good.

The tape of the winding molded body was forcibly peeled off using a wedge-shaped jig having a thickness of 1.4 mm and a tip angle of 30 °, and the peeled surface was observed with an electron microscope manufactured by JEOL Ltd. There was no peeling of the resin part. (Peeling of the interface between the reinforcing fiber and the resin was observed.)

<Example 3>
A winding pipe was obtained in the same manner as in Example 1 except that the content of carbon black was 0.2% by mass.

The appearance of the wound molded product was that the resin was not squeezed out, the fibers did not pop out, the surface low slipperiness was good, and the surface gloss was also good.

The tape of the winding molded body was forcibly peeled off using a wedge-shaped jig having a thickness of 1.4 mm and a tip angle of 30 °, and the peeled surface was observed with an electron microscope manufactured by JEOL Ltd. There was no peeling of the resin part. (Peeling of the interface between the reinforcing fiber and the resin was observed.)

<Comparative example 1>
A winding pipe was obtained in the same manner as in Example 1 except that carbon black was not added. The appearance of the wound molded product was such that the resin was squeezed out and the fibers were squeezed out, and the surface low slipperiness and surface gloss were not sufficient (a level inferior to that of the examples).
The tape of the winding molded body was forcibly peeled off using a wedge-shaped jig having a thickness of 1.4 mm and a tip angle of 30 °, and the peeled surface was observed with an electron microscope manufactured by JEOL Ltd. Peeling of the resin part was observed.

Note that FIG. 1 is an external photograph of the winding molded article of Example 1, and FIG. 2 is an external photograph of the winding molded article of Comparative Example 1.

As can be seen from the above Examples and Comparative Examples, the tape winding molded product of the present invention has an excellent appearance and surface texture.

Since the tape winding molded product of the present invention has excellent surface properties, it can be expected to have excellent handleability and high mechanical properties. Therefore, it can be used for various purposes such as pipes and pressure vessels. It is particularly suitable for automobile parts, electrical / electronic parts, and household / office electrical product parts.

Claims (4)

(I) 20 to 80% by mass of a polymer containing an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or a glass transition temperature of 50 to 300 ° C.
(II) 0.01 to 5% by mass of a dye that absorbs light having a wavelength of 300 to 3000 μm, and (C) 20 to 80% by mass of reinforcing fibers.
A tape winding molding method using a tape containing a fiber-reinforced resin composition containing (however, the total of the component (I) and the component (C) is 100% by mass). The tape winding molding method according to claim 1, wherein the component (I) contains a carboxylic acid group, and the content of the structural unit thereof is 0.010 to 0.045 % by mass. (I) 20 to 80% by mass of a polymer containing an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or a glass transition temperature of 50 to 250 ° C.
(II) 0.01 to 5% by mass of a dye that absorbs light having a wavelength of 300 to 3000 μm, and (C) 20 to 80% by mass of reinforcing fibers.
Tape winding molding fiber-reinforced resin composition comprising (however, the total 100 mass% of the (I) and component wherein component (C)). The fiber-reinforced resin composition for tape winding molding according to claim 3, wherein the component (I) contains a carboxylic acid group and the content of the structural unit thereof is 0.010 to 0.045 % by mass.