JP2018059030A - Tape winding molding method, fiber reinforced resin composition for tape winding molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced resin composition and a molding method which are suitable for tape winding molding using a laser welding method, and more specifically, a fiber-reinforced resin composition which can provide a molded body that hardly causes interfacial peeling and is excellent also in surface properties and a molding method using the same.SOLUTION: There are provided a fiber-reinforced thermoplastic resin composition containing a structural unit containing a specific amount of a carboxylic acid group; and a tape winding molded body using the same. It is considered that due to the above constitution, deterioration and thermal degradation of a resin composition by a laser beam can be suppressed.SELECTED DRAWING: None

Description

  The present invention relates to a tape winding molding method. Moreover, it is related with the fiber reinforced resin composition using it, especially a carbon fiber reinforced resin composition.

  Fiber reinforced thermoplastic resin molded products in which reinforced fibers are combined with thermoplastic resins are excellent in mechanical properties and dimensional stability, so pipes, pressure vessels, automobiles, aircraft, electrical / electronic equipment, toys, home appliances, etc. Used in a wide range of fields. Carbon fiber, which is a kind of reinforcing fiber, has recently been attracting attention because of its light weight, high strength, and high rigidity.

  On the other hand, polyolefin resin, which is a hydrocarbon resin, is generally inexpensive, has excellent processability and chemical resistance, does not generate harmful gas even when incinerated, and has excellent recyclability. Therefore, it is attracting attention as a matrix resin for fiber reinforced resin. Of these, polypropylene resins are attracting attention because they are inexpensive, have a low specific gravity, have relatively high heat resistance, and have excellent properties such as moldability and chemical resistance. However, since polyolefin resin has low polarity, it is inferior in interfacial adhesion with reinforcing fibers. For this reason, attempts have been made to improve the interfacial adhesion between the fibers and the matrix resin by surface treatment of reinforcing fibers 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. Patent Document 2 discloses a specific acid value as a sizing agent suitable for a polypropylene resin. It is disclosed to provide an acid-modified polypropylene resin having:

  Patent Document 3 discloses a carbon fiber containing an ionomer resin. Similarly, Patent Document 4 discloses a carbon fiber containing two types of acid-modified polypropylene resins. These are to 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 of carbon fiber as a binder. It is aimed.

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

  In particular, as a tape winding molding method having a high degree of freedom in shape, a molding method using a laser fusion method can be exemplified.

JP-A-6-107442 JP 2005-48343 A JP 2006-124852 A International Publication No. 2006/101269 JP-A-9-257193

  When the present inventors examined tape winding molding using the laser fusion method, it was found that the adhesive strength and surface properties of the fusion surface of the tape may not be sufficient. That is, the fusion surface tends to peel off and the surface smoothness may be deteriorated.

  The present inventors have determined that such a phenomenon may be caused by the following causes. In other words, heat generation near the reinforcing fiber such as carbon fiber that easily absorbs laser energy and generates heat is too high, and the matrix resin polyolefin deteriorates locally, which triggers surface roughness. Sometimes. In addition, due to the abnormal heat generation, the resin may be squeezed out of the fiber, and the surface state may be extremely deteriorated. The resin in the vicinity of the carbon fiber melts and shrinks to generate a cavity, and peeling around the carbon fiber easily occurs.

In other words, it was thought that this was a phenomenon caused by a marked decrease in homogeneity as a composition containing resin and fiber.

  In view of the above, the present invention has been made with an object of improving the peel strength and surface properties (surface roughness) of a tape winding molded article by controlling the heat generation of the fiber-reinforced resin composition by laser.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by controlling the content of the modified polyolefin within a relatively high range, and thus the present invention has been completed. The configuration is as follows.

[1] (I) 20 to 80% by mass of a polymer having a carboxylic acid group having an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or glass transition temperature of 50 to 300 ° C., and (C) a reinforcing fiber 20-80% by mass
A fiber reinforced resin composition containing a carboxylic acid group and having a carboxylic acid group content of 0.025 to 0.1% by mass (provided that the component (I) and the component (C Tape winding molding method using a tape containing a total component of 100).

[2] (II) 0.01 to 5% by mass of a dye that absorbs light having a wavelength of 300 to 3000 μm (provided that the total of the component (I) and the component (C) is 100% by mass) The tape winding molding method according to [1].

[3] (I) 20 to 80% by mass of a polymer having a carboxylic acid group having an olefin-derived unit having 2 to 20 carbon atoms and a melting point and / or glass transition temperature of 50 to 300 ° C., and (C) a reinforcing fiber 20-80% by mass
A fiber-reinforced resin composition for tape winding molding in which the content of the structural unit having a carboxylic acid group is 0.025 to 0.1% by mass (provided that the component (I) above) And the total of the component (C) is 100% by mass).

[4] (II) 0.01 to 5% by mass of a dye that absorbs light having a wavelength of 300 to 3000 μm (provided that the total of the component (I) and the component (C) is 100% by mass) The resin composition for tape winding molding as set forth in [3].

  Since the fiber-reinforced resin composition of the present invention contains a modified polyolefin having a specific content, it suppresses deterioration and deformation of the matrix resin even in tape winding molding using a laser fusion method, and as a result, A tape winding molded article having excellent peel strength and surface properties can be provided. Therefore, the contribution of the present invention to industrial development is great.

  The fiber reinforced resin composition used in the present invention includes a reinforcing fiber (C) and a structural unit having 2 to 20 carbon atoms, a melting point or glass transition temperature of 50 to 300 ° C., and a specific range of carboxylic acid groups. And a polymer (I) having a structural unit content. The fiber reinforced resin composition preferably contains a dye (II). Specific preferred examples include the following reinforcing fiber bundles, matrix resins (examples 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 the structural unit derived from propylene is preferably bonded to a propylene-based resin (A) having a content of 50 mol% or more and a polymer chain. It is preferable to include a propylene-based resin (B) containing at least a carboxylate and a reinforcing fiber (C).

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

  The propylene resin (B) is 3 to 50 parts by mass, more preferably 5 to 45 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the propylene resin (A). The total content of (A) and the propylene-based 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 fiber constituting the reinforcing fiber bundle (C), 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 them, 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. From the viewpoint of balance with the rate, PAN-based carbon fibers are more preferable. Moreover, when providing electroconductivity, the reinforcing fiber containing metals, such as nickel, copper, and ytterbium, can also be used. In this case, the metal preferably includes a form that covers the reinforcing fiber.

  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 is a preferable example to set it as 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 (C) 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 the mechanical properties and surface appearance of the obtained molded product. More preferably. There is no restriction | limiting in particular in the number of single yarns of a reinforced fiber bundle, Usually, the thing in the range of 100-350,000 can be used. It is preferably used in the range of 1,000 to 250,000, more preferably 5,000 to 220,000. In this invention, since the propylene-type resin (A) mentioned later and propylene-type resin (B) are used, it is anticipated that the effect excellent also in the fiber bundle (large tow) of 40,000 or more fibers is anticipated.

  Next, the propylene-based resin (A) used in combination with the reinforcing fiber (C) of the present invention (containing olefin units having 2 to 20 carbon atoms, and the structural unit derived from propylene is preferably 50 mol% or more. ), The component (A-1) having a weight average molecular weight exceeding 50,000 is included. A preferred weight average molecular weight range is 70,000 or more, more preferably 100,000 or more. On the other hand, the upper limit value of the weight average molecular weight is not particularly specified, but is preferably 700,000, more preferably 500,000, and still more preferably 45 from the viewpoint of melt fluidity at the time of molding and the appearance of the composition molded body described later. 10,000, particularly preferably 400,000. The total of the propylene-based resin component (A-1) and the later-described polypropylene-based resin component (A-2) is 100% by mass, and the propylene-based resin component (A-1) exceeds 60% by mass and is 100% by mass or less. Included in the ratio. Preferably it is 70-100 mass%, More preferably, it is 73-100 mass%.

  The polypropylene 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 as required. The range of a preferable weight average molecular weight 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 in consideration of the strength and handleability (such as stickiness) of the reinforcing fiber bundle described later. Is 25,000. Moreover, a polypropylene resin component (A-2) is contained in the ratio of 0-40. (However, the total of the component (A-1) and the component (A-2) is 100% by mass.) The content is preferably 0-30% by mass, more preferably 0-27% 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. More preferably, it is 30,000-200,000, More preferably, it is 35,000-200,000.

  Reinforcing fiber bundles containing a specific amount of polypropylene resin when a relatively high amount of components having a high weight average molecular weight are contained, even when the propylene-based resin is used in a relatively small amount, such as fluffing shape, for example, its impact There is a tendency that shape changes such as disintegration, peeling, and folding due to environmental factors, and shape changes such as fine powder resulting from them do not easily occur.

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

  Specific examples of the α-olefin include 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-heptene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- Mention may be made of α-olefins having 2 to 20 carbon atoms excluding propylene such as eicosene. Among these, 1-butene, ethylene, 4-methyl-1-pentene, and 1-hexene can be given as preferable examples, and 1-butene and 4-methyl-1-pentene are particularly preferable.

  Examples of the conjugated diene and 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 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 purpose of the present application is not impaired. For example, an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / propylene / 1-butene copolymer, and the like are preferable.

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

Identification of the monomer repeating unit in the propylene-based resin is mainly determined by ¹³ C NMR method. Mass spectrometry and elemental analysis may be used. There is also a method of determining the composition by performing IR analysis of a plurality of types of copolymers having different compositions determined by the NMR method, and creating a calibration curve from information such as absorption of a specific wave number and specimen thickness. Can be adopted. This IR method is preferably used for process analysis and the like.

  Moreover, in this invention, it is preferable that the Shore A hardness of propylene-type resin (A) is 60-90, or Shore D hardness is 45-65. A more preferable range of Shore A hardness is 65 to 88, and more preferably 70 to 85. A more preferable range of Shore D hardness is 48 to 63. More preferably, it is 50-60.

  When the propylene resin (A) is in such a hardness range, the followability to the reinforcing fibers is good, so that partial cracks are hardly generated, and it is easy to form a reinforcing fiber bundle having a stable shape. There is. Moreover, when it is set as the composition combined with the propylene-type resin (D) mentioned later, there exists an advantageous tendency when raising the intensity | strength. It is presumed that this is because the propylene resin (A) and the propylene resin (D) have a good molecular chain entanglement structure.

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

  On the other hand, depending on the application to be used, it may be preferable that the propylene-based resin (A) is substantially unmodified. Here, “substantially unmodified” means that it is desirably not modified at all, but the amount of modification is —C (═O) —O— which does not impair the purpose even if modified. It is preferably less than 0.05 mmol equivalent in terms of the group represented. More preferably, it is 0.01 mmol equivalent or less, More preferably, it is 0.001 mmol or less, Most preferably, it is 0.0001 mmol equivalent or less.

  The propylene resin (B) of the present invention 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 of the propylene-based resin (B) include polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, and propylene / α-olefin represented by ethylene / propylene / 1-butene copolymer. First of all, a copolymer of singly or in combination of two or more thereof is mentioned. Mention may then be made of monomers that have neutralized or non-neutralized carboxylic acid groups and / or monomers that have saponified or unsaponified carboxylic acid esters. 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 the propylene-based resin (B). The olefin used for the propylene polymer can be selected based on the same idea as the propylene resin (A).

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

  Here, as the monomer having a neutralized or non-neutralized carboxylic acid group, and the 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.

  The propylene resin (B) can be obtained by various methods as described above. More specifically, an ethylenically unsaturated carboxylic acid having an unsaturated vinyl group and a propylene resin in an organic solvent can be used. A method of removing a solvent after reacting with a monomer having an unsaturated vinyl group other than olefin in the presence of a polymerization initiator, or a melt obtained by heating and melting a propylene resin has an unsaturated vinyl group. A method of reacting a carboxylic acid and a polymerization initiator under stirring, or a mixture of a propylene-based resin, a carboxylic acid having an unsaturated vinyl group, and a polymerization initiator is supplied to an extruder and reacted while heating and kneading. Thereafter, a method of forming 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) hexyne-3, Examples include various peroxide compounds such as 1,4-bis (tert-butylperoxyisopropyl) benzene. An azo compound such as azobisisobutyronitrile may be used. These can be used alone or in combination 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 groups such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane. Organics 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.

  It is known that the content of the carboxylic acid group of the propylene-based resin (B) obtained as described above can be determined by NMR or IR measurement described later. Further, for example, as another method, evaluation can be performed by an acid value. The preferable range of the acid value of the propylene-based 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, still 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 propylene-based resin (B) obtained as described above can be easily treated by neutralizing or saponifying 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 neutralization or saponification of the aqueous dispersion of the raw material of the propylene-based resin (B) include alkali metals such as sodium, potassium, lithium, calcium, magnesium, 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, morpholine and other organic amines, sodium oxide, Of 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 other metals Mention may be made of weak acid salts. As 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 of the raw material of the propylene-based resin (B) to the metal salt, ammonium salt, or the like is the stability of the aqueous dispersion and the adhesion to the fiber. From the viewpoint of property, it is usually 50 to 100%, preferably 70 to 100%, more preferably 85 to 100%. Accordingly, it is desirable that all of the carboxylic acid groups in the propylene-based resin (B) are neutralized or saponified by the basic substance, but some carboxylic acid groups remain without being neutralized or saponified. May be. 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. The method of calculating | requiring from a formula and calculating in comparison with the total mole number of the original carboxylic acid group etc. are mentioned.
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 (C), the content of the carboxylate bonded to the polymer chain of the propylene resin (B) is -C (g per propylene resin (B). 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. The following method can be illustrated 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 ¹³ C NMR method under a high temperature solution condition of 120 ° C. or higher under a condition of 100 MHz or higher. Further, after measuring a plurality of samples having different carbonyl skeleton content by ¹³ CNMR to identify the carboxylic acid skeleton content, IR measurement of the same sample is performed, and characteristic absorption such as carbonyl and sample thickness and A method for identifying the introduction rate of the carboxylic acid skeleton by IR measurement by creating a calibration curve between the ratio of the other typical absorption and the content of the carboxylic acid skeleton is also known.

  Moreover, it is preferable that the weight average molecular weight Mw of propylene-type resin (A) is larger in the relationship of the weight average molecular weight Mw of propylene-type resin (A) and propylene-type resin (B) of this invention. 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. More preferably, it is 120,000-380,000, More preferably, it is 130,000-380,000.

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

The weight average molecular weight Mw of the propylene-based resin (B) is 1,000 to 1,000 in view of the above interaction and the compatibility with the propylene-based resin (A), preferably the propylene-based resin (A-2). Preferably it is 100,000. More preferably, it is 2,000-80,000, More preferably, it is 5,000-50,000, Most preferably, it is 5,000-30,000.

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

The melt flow rate (ASTM 1238 standard, 230 ° C., 2.16 kg load) of the propylene-based resin (B) is preferably 3 to 500 g / 10 min. A preferred lower limit is 5 g / 10 minutes, more preferably 7 g / 10 minutes, and a preferred upper limit is 400 g / 10 minutes, more preferably 350 g / 10 minutes.
In addition, as a preferable melt flow rate range, there are cases where the measured value at ASTM 1238 standard, 190 ° C., 2.16 kg load is the same numerical range as described above.

The propylene resin (A) and the propylene resin (B) of the present invention can be used in various forms. For example, a method in which a propylene resin is melted as it is or in combination with a heat stabilizer and brought into contact with a reinforcing fiber (C), or a propylene resin (A) and a propylene resin (B) are reinforced in an emulsion or suspension state. The method of making it contact with a fiber (C) is mentioned. A heat treatment or the like may be performed after the contact step.
In this invention, it is preferable to use a propylene-type resin (A) and a propylene-type resin (B) in an emulsion state from a viewpoint made to contact with a reinforced fiber (C) efficiently.

  As above-mentioned, the ratio of propylene-type resin (A) and propylene-type resin (B) is 3-50 mass parts of propylene-type resin (B) with respect to 100 mass parts of propylene-type resin (A). If it is in this range, it becomes possible to make compatible the characteristic mainly related to the strength and shape derived from the propylene-based resin (A) and the affinity with the reinforcing fiber at a high level. Preferably, the propylene resin (B) is 5 to 45 parts by mass with respect to 100 parts by mass of the propylene resin (A), more preferably the propylene resin (B) with respect to 100 parts by mass of the propylene resin (A). The propylene resin (B) is 10 to 40 parts by mass with respect to 5 to 45 parts by mass, more preferably 100 parts by mass of the propylene resin (A). When the amount of the propylene-based resin (B) is less than 3 parts by mass, the affinity with the reinforcing fiber is lowered and the adhesive properties may be inferior. Moreover, when there are more propylene-type resin (B) than 50 mass parts, the intensity | strength of mixture itself may fall or a fluff may increase, and there exists a possibility that a firm adhesive characteristic cannot be maintained.

  By setting the molecular weight and content of 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. It is expected that the compatibility with the propylene-based resins (A) and (B) is relatively high and the adhesiveness is improved.

  In addition to the propylene-based resin (A) and the propylene-based resin (B), other components may be used in 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-based resin is applied to the reinforcing fiber bundle in the form of an emulsion, a surfactant or the like for stabilizing the emulsion may be added separately. Such other components are preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less with respect to the total of the propylene-based resin (A) and the propylene-based resin (B). is there.

  The above-described 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 propylene-based resin (A) and the propylene-based resin (B) contained are less than 0.3% by mass, there may be many exposed portions of the reinforcing fibers. In such a case, the strength of the resulting product may be reduced, or the handling of the reinforcing fiber bundle may be insufficient. Examples of the handleability herein include the hardness and ease of handling of the fiber bundle when the fiber bundle is wound around a bobbin. Moreover, when cutting a fiber bundle and using it as a chopped fiber bundle, it means the convergence of a 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 be 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 because of the balance between adhesiveness and handleability of the reinforcing fiber bundle. % By mass. On the other hand, the preferable upper limit is 4% by mass, and more preferably 3% by mass.

  The method for adhering the mixture of propylene resins to the reinforcing fiber bundle is not particularly limited, but from the viewpoint of easily adhering uniformly between single fibers, the propylene resin (A) and the propylene resin (B) A method of drying after applying an emulsion of the above mixture to the reinforcing fiber bundle is preferred. As a method for applying the emulsion to the reinforcing fiber bundle, 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 when molding a molded product are preferably propylene-based polymerization (D) described later. Others, 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, polymethyl methacrylate Acrylic resin such as resin (PMMA), vinyl chloride, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone, polyethersulfone, polyketone, polyetherketone, polyetheretherketone (PEEK), Polyolefins such as polyethylene, polypropylene, polybutene, poly-4-methyl-1-pentene, thermoplastic resins such as modified polyolefin, phenolic resin, phenoxy resin, and more Tylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / diene copolymer, ethylene / carbon monoxide / diene copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / A glycidyl (meth) acrylate, an ethylene / vinyl acetate / glycidyl (meth) acrylate copolymer may be used, or one or more of these may be used in combination. Among these, polyolefin resins having a low polarity are particularly preferable. Among them, ethylene polymers and propylene polymers are preferable from the viewpoint of cost and lightness of molded products, and propylene resins (D) described later are more preferable. preferable. That is, the reinforcing fiber bundle-containing propylene resin composition is preferably used for a molding material or a molded product.

  The propylene-based resin (D) may be an unmodified propylene-based resin or may include a propylene-based resin including a carboxylic acid structure or a carboxylate structure by a method such as modification. Is an embodiment containing the latter modified propylene resin. The preferred weight ratio is 80/21 to 93/7, preferably 82/18 to 92/8, more preferably 83/17 to 92/8, in an unmodified / modified product ratio. More preferably, it is 83 / 17-91 / 9. The composition of the propylene resin is a general propylene containing a structural unit derived from a monomer (such as an olefin or a carboxylic acid ester compound) described in the description of the propylene resin (A) or the propylene resin (B). Resin is a preferred embodiment. For example, propylene polymers called homopolypropylene, random polypropylene, block polypropylene, and modified polypropylene.

The weight average molecular weight of the propylene resin (D) of the present invention is preferably in the following relationship with the propylene resin (A) and the propylene resin (B).
Propylene resin (A)> Propylene resin (D)> Propylene resin (B)

  Specifically, the weight average molecular weight of the propylene-based 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 still more preferably 20,000 to 100,000. It is.

The molding material (reinforcing fiber bundle-containing propylene resin composition) of the present invention is 25 to 75 parts by mass of the reinforcing fiber bundle, preferably 30 to 68 parts by mass, and more preferably 35 to 65 parts by mass. It is out. On the other hand, propylene-type resin (D) contains 75-25 mass parts, Preferably it is 70-32 mass parts, More preferably, 65-35 mass parts is contained. However, said ratio is a value when the sum total of the said reinforcing fiber bundle and propylene-type resin (D) is 100 mass parts.
It is preferable that the propylene-based resin (D) is in an aspect in which the propylene-based resin (D) is bonded around the reinforcing fiber bundle mainly including the reinforcing fiber, the propylene-based resin (A), and the propylene-based resin (B).

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

  The propylene 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-described resins (particularly unmodified resins) include, for example, International Publication No. 2004/088775 Pamphlet, International Publication No. 2006/057361 Pamphlet, International Publication No. 2006/123759 Pamphlet, and Japanese Patent Application Laid-Open No. 2007-2007. 308667 gazette, International publication 2005/103141 pamphlet, patent 4675629 gazette, international publication 2014/050817 pamphlet, JP, 2013-237861, A, etc. 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. Preferably, it is 75 / 25-30 / 70, More preferably, it is 70 / 30-35 / 65, More preferably, it is 65 / 35-40 / 60, Most preferably, it is 60 / 40-40-60. If the fiber content is too high, tape peeling may easily occur in the tape winding molded body described later. On the other hand, if the resin content is too high, the strength of the tape winding molded body described later may be reduced.

  The melting point or glass transition temperature of the resin is 50 to 300 ° C. A preferred lower limit is 70 ° C, more preferably 80 ° C. On the other hand, a preferable upper limit is 280 ° C, more preferably 270 ° C, and further preferably 260 ° C. Further, the above definition is preferably a melting point, and a more preferable upper limit of the melting point is 250 ° C., more preferably 240 ° C.

  The resin contains a carboxylic acid group. The total content of the reinforcing fiber (C) and the polymer (I) of the fiber reinforced resin composition is 100% by mass, and the content of the structural unit containing the carboxylic acid group is 0.025 to 0.10% by mass. A preferred lower limit is 0.027 mass%, more preferably 0.030 mass%. On the other hand, the preferable upper limit is 0.09% by mass, more preferably 0.08% by mass, and particularly preferably 0.07% 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 body described later. In particular, peeling between the reinforcing fibers and the resin tends to occur. If the content rate of the structural unit containing the carboxylic acid group is within the above range, the tape peeling does not tend to occur unless the reinforcing fiber itself is broken. In addition, as a structural unit containing the said carboxylic acid group, the structural unit derived from the carboxylic acid group contained in the said propylene-type resin (A), propylene-type resin (B), propylene-type resin (D), and carboxylate, for example The structural unit derived from can be mentioned.

  When the carboxylic acid group is contained in the resin, the content can be grasped by the acid value. A preferable acid value is 0.34 to 1.15 mg-KOH / g, more preferably 0.35 to 1.05 mg-KOH / g, and still more preferably 0.36 to 0.08 mg-KOH / g.

  The content rate of the structural unit containing the carboxylic acid group is, for example, the carboxylic acid group content rate of the propylene resin (B) or the propylene resin (D) itself forming the reinforcing fiber bundle, or the propylene resin (B ) And the content of the propylene-based resin (D) can be controlled within the range specified in the present application.

Moreover, the preferable melt flow rate (ASTM 1238 standard, 230 degreeC, 2.16kg load) of resin used for the fiber reinforced resin composition of this invention is 1-500g / 10min, More preferably, it is 3-300g / 10min. More preferably, it is 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 even more preferably 150,000 to 350,000.

  The fiber reinforced resin composition of the present invention having the structural unit containing the carboxylic acid group is preferable for forming a molded article that has a good appearance and is difficult to peel even when tape winding molding is performed by laser. This may be because the resin containing a carboxylic acid group has the property of being relatively difficult to be deteriorated by light. In addition, even if the polymer main chain is cleaved, the intermolecular interaction of the carboxylic acid groups The present inventors believe that this may be due to the effect of pseudo-crosslinking to keep the apparent molecular weight high.

  Moreover, the manufacturing method of an emulsion can also use a well-known method, for example, international publication 2007/125924 pamphlet, international publication 2008/096682 pamphlet, Unexamined-Japanese-Patent No. 2008-144146 etc. can be illustrated.

  In addition, as a method for specifying the easiness of unraveling the fiber bundle, which is considered to be the cause of the above-described fuzzing, the method described in Japanese Patent No. 5584977 and the evaluation method of convergence property described in Japanese Patent Laid-Open No. 2015-165055 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 scissors. The obtained short fiber is evaluated by the following visual judgment.
○: Short fibers are almost in the same state as before cutting.
X: The short fibers are largely dispersed or cracked.

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

A preferable 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 combined with a thermoplastic resin.

  The fiber-reinforced resin composition of the present invention preferably contains a dye (II) that absorbs light having a wavelength of 300 to 3000 μm. As such a dye, a known substance can be used without limitation. Preferred examples include carbon-based dyes. More preferably, it is carbon black.

  When such a pigment | dye (II) is used, it is contained in the ratio of 0.01-5 mass% of the whole fiber reinforced thermoplastic resin of this invention. A preferred lower limit is 0.1% by mass, more preferably 0.2% by mass. On the other hand, the preferable upper limit is 3% by mass, more preferably 2% by mass.

  By including the dye (II) in the fiber reinforced resin composition of the present invention, it is expected that local heat generation by a laser, which will be described later, is suppressed and the entire resin composition is easily heated more uniformly. Thereby, deterioration and deformation of the matrix resin, more specifically, fiber surface protrusion, surface smoothness, and deterioration in appearance can be suppressed.

  As a molding method using the reinforcing fiber bundle of the present invention, for example, after opening the fiber bundle, the unidirectional carbon fiber reinforced thermoplastic resin is brought into contact with the molten matrix resin (D). The method of obtaining a molded object (unidirectional material) can be mentioned. This unidirectional material can be used as it is, or a laminate can be prepared by stacking and integrating a plurality of the unidirectional materials. Moreover, it can also cut | disconnect suitably and can also be made into a tape shape.

The tape winding molded body of the present invention is obtained by processing the above-mentioned fiber reinforced resin composition into a tape shape by a known method and using this as a mandrel while melting the tape surface by a tape winding method using a known laser fusing method. It is obtained by fusing while making contact. As an example of the tape winding molding method, for example, a method 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 tape winding molding used in the present invention, for example, a robot as disclosed on September 8, 2016 on the AFPT (Germany) website (http://www.afpt.de/welcome/). In an apparatus in which a laser irradiation unit is attached as a light source to an arm, a method of molding using the thermoplastic resin can be given as an example. Others include “Development of a hybrid tail rotor drive shaft by the use of thermoplastic Automated fiber placement” presented at 17 ^th -Europian conference on Composite Materials, 1-8 (2016), and “Selective reinforcement of steel with CF”. / PA6 composites in a laser tape placement process: effect of surface preparation and laser angle on interfacial bond strength ”.

  However, when performing fusion by laser, it is preferable that the light source and mandrel are appropriately moved to efficiently melt and fuse them. When taking such a method, the moving speed is 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) or the pigment (II). Moreover, it is preferable that the output of a laser is 50W-5kW. If this output is too strong, the resin may be deteriorated or deformed. On the other hand, if it is too weak, the resin may not melt.

  The tape winding molded body using the fiber reinforced thermoplastic resin composition tape formed into the tape shape by the method as described above can be developed for various uses. For example, it is a suitable example to use the external reinforcement part of various containers, such as a pipe and a pressure vessel. That is, it can be suitably used for containers 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-based resin to reinforcing fiber bundle About 5 g of the reinforcing fiber bundle to which the propylene-based resin adhered was taken and 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 adhesion amount was calculated by the following equation using W ₁ (g) and W ₂ (g).
Adhesion amount = [(W ₁ −W ₂ ) / W ₂ ] × 100 (mass%).

(2) Weight average molecular weight measurement of propylene-based resin The molecular weight was determined by the GPC method under the following conditions.
Liquid chromatograph: PL-GPC220 high-temperature gel permeation chromatograph manufactured by Polymer Laboratories (with built-in differential refractometer)
Column: Tosoh Corporation TSKgel GMH _HR- H (S) -HT × 2 and GMH _HR- H (S) × 1 were connected in series.
Mobile phase medium: 1,2,4-trichlorobenzene (containing 0.025% stabilizer)
Flow rate: 1.0 ml / min Measurement temperature: 150 ° C
Method for preparing calibration curve: A standard polystyrene sample was used.
Sample concentration: 0.15% (w / v)
Sample solution volume: 500 μl
Standard sample for 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 performed, and the content ratio of the monomer structure was evaluated from the content of the propylene-based resin, the 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). ¹ H-NMR measurement and ¹³ C-NMR measurement were performed using a JEOL JNM-GX400 spectrometer (manufactured by JEOL Ltd.).

(4) Measurement of carboxylate content of propylene-based resin Carboxylate content and non-neutralized carboxylic acid content by performing the following operations on the first and second propylene-based resins Was measured.

Propylene resin 0.5 g was heated to reflux in 200 ml of toluene and dissolved. This solution was titrated with a 0.1 N 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 × 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 (1.02)
B: Sampling amount (0.50 g).

The acid value calculated above was converted into the number of moles of carboxylic acid groups not neutralized using the following formula.
Number of moles of unneutralized carboxylic acid group = acid value × 1000/56 (mol / g)

The total number of moles of carboxylic acid groups (mol / g) calculated by quantifying the carbonyl carbon of the carboxylic acid group separately using IR, NMR, elemental analysis, etc., as the conversion rate of the carboxylic acid group into a neutralized salt And calculated by the following formula.
Conversion rate% = (1-r) × 100 (%)
r: Number of moles of unneutralized carboxylic acid groups / total number of moles of carboxylic acid groups.
(5) Measurement of number of fuzzed fluffs Determined in the same manner as the method described in Example of Japanese Patent No. 5584977.
When the number of fluffs was 0 to 5 / m, it was acceptable, and when it exceeded that, it was rejected.

(6) Appearance evaluation of winding molded body The appearance of the winding molded body was visually evaluated. The evaluation items are resin squeezing, fiber pop-out, low surface slipperiness, and surface gloss.
(7) Measuring method of melting | fusing point Melting | fusing point (Tm) of the polymer in this invention was measured with the differential scanning calorimeter (DSC) with the DSC220C apparatus by Seiko Instruments Inc. Samples 7-12 mg were 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 5 minutes at −50 ° C., 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 as reference examples below.

<Reinforcing fiber (C)>
A carbon fiber bundle (manufactured by Mitsubishi Rayon Co., Ltd., product name: Pyrofil TR50S12L, 12,000 filaments, strand strength 5000 MPa, strand elastic modulus 242 GPa) is immersed in acetone and subjected to ultrasonic waves for 10 minutes, The sizing agent adhering to it was removed and used by further washing with acetone three times and drying at room temperature for 8 hours.

(Production Example 1-Method for producing emulsion)
As propylene resin (A), weight average molecular weight measured by GPC is 120,000, 100 parts by mass of propylene / butene / ethylene copolymer having no melting point, and raw material of propylene resin (B) modified with maleic anhydride 10 parts by mass of a propylene polymer (weight average molecular weight Mw = 20,000, acid value: 45 mg-KOH / g, maleic anhydride content: 4% by mass, melting point: 140 ° C.), surfactant (C), 3 parts by mass of potassium oleate was mixed. 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-based resin comprises 96 parts by weight of a propylene / butene copolymer, 4 parts by weight of maleic anhydride, and 0.4 parts by weight of Perhex 25B (manufactured by NOF Corporation) 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 using a roller impregnation method. Subsequently, the low-boiling component was removed by online drying at 130 ° C. for 2 minutes to obtain a reinforcing fiber bundle of the present invention. The adhesion amount of the emulsion was 0.87%. The fuzziness of the carbon fiber bundle was acceptable.

  Subsequently, 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 0.5% by mass of maleic anhydride as matrix resin (D) A master batch (PEONY manufactured by DIC Corporation) containing modified polypropylene (according to ASTM D1238, melt flow rate of 9.1 g / 10 min, melting point of 155 ° C. measured at 190 ° C. under a load of 2.16 kg) and carbon black BLACK BMB-16117: carbon black content 40%) 43 parts of a resin composition was prepared, and a sheet having an average thickness of 150 μm was prepared by a conventional method. The weight ratio between the J106MG and the modified polypropylene was 85/15 (weight average molecular weight corresponding to 320,000), and the carbon black content was adjusted to 1% by mass of the entire resin composition. (The melting point of the resin is 160 ° C. and the maleic anhydride content is 0.034% by mass with respect to the entire resin composition) (fiber volume fraction Vf0.4). This is cut into a 12mm wide tape using a slitter, and a robot equipped with a "STWH INB" type take-up head manufactured by AFPT that performs closed-loop control of a diode laser with an output of 3 kW and a wavelength of 960 to 1070 nm is used. A pipe was then wound around a mandrel having an inner diameter of φ95 mm. Winding was alternately laminated at + 20 ° and −20 ° to obtain two layers of winding pipes.

  The appearance of the wound molded body was that the resin was not squeezed out, the fibers did not jump out, the surface slipperiness was good, and the surface gloss was good.

  The tape of the winding molded body was forcibly peeled 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 and part of the reinforcing fiber were observed to be broken.)

<Example 2>
Modified polypropylene is modified to 0.8% by weight maleic anhydride-modified polypropylene (according to ASTM D1238, melt flow rate measured at 190 ° C., load 2.16 kg, 220 g / 10 min, melting point 160 ° C.) A winding pipe was obtained in the same manner as in Example 1 except that the weight ratio of J106MG and modified polypropylene was changed to 90/10 (weight average molecular weight corresponding to 290,000). The content of the carboxylic acid group-containing structural unit was 0.0035% by mass.

  The appearance of the wound molded body was that the resin was not squeezed out, the fibers did not jump out, the surface slipperiness was good, and the surface gloss was good.

  The tape of the winding molded body was forcibly peeled 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 and part of the reinforcing fiber were observed to be broken.)

<Comparative Example 1>
A winding pipe was obtained in the same manner as in Example 1 except that the weight ratio of J106MG and modified polypropylene was w090 / 10 (weight average molecular weight corresponding to 310,000). The content of the carboxylic acid group-containing structural unit was 0.023% by mass.

  The tape of the winding molded body was forcibly peeled 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, but no breakage of the reinforcing fiber was observed.)

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

  Since the tape winding molded body of the present invention has excellent surface properties, it can be expected to have excellent handling properties and high mechanical properties. For this reason, it can expand | deploy to various uses including a pipe and a pressure vessel. It is particularly suitable for automobile parts, electrical / electronic parts, household / office electrical product parts.

Claims (4)

(I) 20 to 80% by mass of a polymer having a carboxylic acid group having an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or glass transition temperature of 50 to 300 ° C., and (C) reinforcing fibers 20 to 80 mass%
A fiber reinforced resin composition containing a carboxylic acid group and having a carboxylic acid group content of 0.025 to 0.1% by mass (provided that the component (I) and the component (C Tape winding molding method using a tape containing a total component of 100).   (II) A dye that absorbs light having a wavelength of 300 to 3000 μm is further contained in an amount of 0.01 to 5% by mass (provided that the total of the component (I) and the component (C) is 100% by mass). The tape winding molding method according to 1. (I) 20 to 80% by mass of a polymer having a carboxylic acid group having an olefin-derived unit having 2 to 20 carbon atoms and having a melting point and / or glass transition temperature of 50 to 300 ° C., and (C) reinforcing fibers 20 to 80 mass%
A fiber-reinforced resin composition for tape winding molding in which the content of the structural unit having a carboxylic acid group is 0.025 to 0.1% by mass (provided that the component (I) above) And the total of the component (C) is 100% by mass).   (II) A dye that absorbs light having a wavelength of 300 to 3000 μm is further contained in an amount of 0.01 to 5% by mass (provided that the total of the component (I) and the component (C) is 100% by mass). 3. A fiber-reinforced resin composition for tape winding molding according to 3.