JP2018145552A - Fiber reinforced material and fiber reinforced polypropylene resin composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aramid fiber reinforced material with compatibility with a polypropylene resin for reinforcement of the polypropylene resin, and a fiber reinforced polypropylene resin composite material reinforced by an aramid fiber.SOLUTION: There are provided a fiber reinforced material used for reinforcement of a polypropylene resin and containing a polyparaphenylene terephthalamide fiber composite manufactured by penetrating and impregnating a resin dispersion into a polyparaphenylene terephthalamide fiber skeleton which has no history to have moisture content of less than 15 mass% and of which moisture content is adjusted to 15 to 200 mass%, and a fiber reinforced polypropylene resin composite material containing the fiber reinforced material.SELECTED DRAWING: None

Description

  The present invention relates to a fiber reinforcing material used to reinforce a polypropylene resin and a fiber reinforced polypropylene resin composite material including the same.

  Polyparaphenylene terephthalamide (hereinafter sometimes referred to as PPTA) fiber is formed into a highly crystallized yarn by applying concentrated sulfuric acid as a solvent for polymer dissolution during spinning to form a liquid crystal state, and then applying shear by a die to give a crystallinity. Is done. It is known that concentrated sulfuric acid, which is a solvent, is neutralized by washing and alkali immediately after spinning, dried and heat-treated at 200 ° C. or higher, and then wound up as a filament (Patent Document 1). .

  PPTA fiber is a synthetic fiber having both high functionality such as high strength, high elastic modulus, high heat resistance, non-conductivity, and no rust, flexibility that is unique to organic fibers, and light weight. Because of these features, they are used as rubber reinforcement materials for automobiles, motorcycles, bicycle tires, automobile toothed belts, conveyors, etc., or optical fiber cable reinforcements and ropes. Furthermore, it is also applied to bulletproof vests, protective clothing such as work gloves and work clothes that are difficult to cut against blades, and fire-fighting clothes that use incombustibility.

  However, since aramid fibers such as PPTA fibers are chemically stable, they have a problem that adhesion to various resins is not good. Examples of the method for improving the adhesion between the aramid fiber and the resin include a method of coating an aramid fiber with an adduct of a polyamine compound and a glycidyl ether type epoxy resin (Patent Document 2), a carbon having a Vicat softening point of 40 ° C. or higher. A method of coating with 2 to 4 olefinic copolymers (Patent Document 3) has been proposed.

As another method, Patent Document 4 discloses that a surface treatment agent composed of a silane coupling agent (a silane compound having Si and a lipophilic group) and a urethane former is used in a carbon dioxide fluid atmosphere by using a supercritical apparatus. A method for improving adhesiveness with an epoxy resin by applying heat treatment to PPTA fibers having a moisture content of 30% by weight and then heat treating has been proposed.
In Patent Document 5, an aqueous solution in which a silane coupling agent, a urethane former, and a surfactant are dissolved in water is applied to an aramid fiber having a moisture content of 30% by weight, and then subjected to heat treatment to provide adhesion to an epoxy resin. A method for improvement has been proposed.

  Patent Document 6 discloses that an aqueous solution in which 0.25% by weight of a silane coupling agent and 1.25% by weight of a urethane binder are dissolved in water is applied to an aramid fiber having a moisture content of 30% by weight and then heat-treated. There has been proposed a method of attaching a single yarn to a nylon resin to obtain a nylon resin composite material.

US Pat. No. 3,767,756 Japanese Patent Publication No. 1-12864 (Claims) Japanese Patent Laid-Open No. 4-50377 (Claims etc.) JP 2001-303456 A (claims, paragraphs [0048] to [0052], etc.) JP 2002-194669 A (claims, paragraphs [0048] to [0051], etc.) JP 2004-91540 A (claims, paragraph [0028], etc.)

  However, the method described in Patent Document 2 and Patent Document 3 is not a method in which an adduct or an olefin copolymer is reacted with an aramid fiber, but a solution of an adduct or an olefin copolymer is applied to the surface of the aramid fiber or the Since the fiber is dipped in the solution and squeezed and then dried, there is a problem that the coating is not uniform.

  In the methods described in Patent Documents 4 to 6, since an aqueous solution of a low-concentration silane coupling agent and a urethane former is imparted to the PPTA fiber, it is difficult to increase the impregnation amount of the urethane former into the PPTA fiber. Moreover, when PPTA fiber to which a silane coupling agent is added is used as a fiber reinforcing material, there is a concern that the mechanical properties of the resin molded product are deteriorated. As for the matrix resin, Patent Documents 4 and 5 disclose an epoxy resin, and Patent Document 6 merely discloses a nylon resin. There is no mention of polypropylene resin.

  Among various matrix resins, polypropylene resin, in particular, has not only excellent chemical resistance and impact resistance, but also easy to mold, so it can be used for all types of molding such as film, sheet, blow and injection. It is used in a wide range of fields from daily necessities to industrial products. On the other hand, aramid fibers are widely used for reinforcement of rubber and resin, taking advantage of excellent properties such as high strength, high elastic modulus, impact resistance, wear resistance, heat resistance, non-conductivity, and lightness. Yes. Therefore, a composite material having high functionality and versatility can be expected by combining aramid fibers with polypropylene resin. However, only a few examples have been reported in which aramid fiber bundles are impregnated with polypropylene resin by pultrusion to form a composite.

  An object of the present invention is to provide an aramid fiber reinforcing material for reinforcing a polypropylene resin, which has an affinity for the polypropylene resin, and a fiber reinforced polypropylene resin composite material reinforced with an aramid fiber.

As a result of intensive studies to obtain a polyparaphenylene terephthalamide fiber having an affinity for polypropylene resin, the inventor has a moisture content of 15 to 200% by mass having no history of less than 15% by mass. It has been found that polyparaphenylene terephthalamide fiber having affinity with polypropylene resin can be obtained by infiltrating the resin dispersion into the adjusted polyparaphenylene terephthalamide fiber skeleton, and has reached the present invention.
That is, the present invention is as follows.

(1) Polyparaphenylene terephthalamide fiber which is a fiber reinforcing material used to reinforce a polypropylene resin and is adjusted to a moisture content of 15 to 200% by mass having no history of moisture content of less than 15% by mass. A fiber reinforcing material comprising a polyparaphenylene terephthalamide fiber composite formed by impregnating and impregnating a resin dispersion in a skeleton.
(2) The resin in the dispersion is 0.1% by mass or more and 20.0% by mass or less permeation with respect to the fiber mass when the water content of the polyparaphenylene terephthalamide fiber is converted to 0% by mass. -The fiber reinforcement as described in said (1) formed by impregnation.
(3) The fiber reinforcing material according to (1) or (2), wherein the resin is at least one selected from a urethane resin and an epoxy resin.
(4) The fiber reinforcing material according to any one of (1) to (3), wherein the resin is at least one selected from a polyether-based urethane resin, a polycarbonate-based urethane resin, and a bisphenol-type epoxy resin.
(5) A fiber reinforced polypropylene resin composite material comprising the fiber reinforced material according to any one of (1) to (4).
(6) An automotive part or member using the fiber-reinforced polypropylene resin composite material according to (5).

  Since the fiber reinforcing material of the present invention includes a fiber composite in which a resin dispersion is impregnated and impregnated into a polyparaphenylene terephthalamide fiber skeleton, it has excellent adhesion to a polypropylene resin compared to a conventional aramid fiber. Not only is the peel load high, but there is little decrease in strength at high temperatures when it is combined with polypropylene resin, and it has the high tensile strength, bending strength, and bending elastic modulus inherent to aramid fibers. Moreover, the fiber reinforced polypropylene resin composite material including the fiber reinforcing material is excellent in mechanical properties, heat resistance, and frictional wear. Therefore, it is possible to provide a fiber reinforced resin (FRP) suitable for automobiles, ships, electrical / electronic equipment, AV equipment, OA equipment, architectural parts or members.

  The polyparaphenylene terephthalamide (PPTA) in the present invention is a polymer obtained by polycondensation of terephthalic acid and paraphenylene diamine, but a polymer obtained by copolymerizing a small amount of dicarboxylic acid and diamine can also be used. Or, the molecular weight of the copolymer is usually preferably 20,000 to 25,000.

  Ordinary PPTA fiber is made by dissolving PPTA in concentrated sulfuric acid, extruding the viscous solution from a spinneret, spinning into air or water, and neutralizing with an aqueous sodium hydroxide solution. Finally, it is obtained by drying and heat treatment at 120 to 500 ° C.

In the present invention, the PPTA fiber adjusted to a moisture content of 15 to 200% by mass can be obtained, for example, as follows. That is, PPTA is dissolved in concentrated sulfuric acid to obtain a viscous solution of 18 to 20% by mass, which is discharged from a spinneret, spun into air for a short time, and then spun into water (at this time, It is preferable to set the shear rate at the time of discharge to 25,000 to 50,000 sec ⁻¹ ), and after the water washing neutralization treatment, the obtained raw yarn is dried at 100 to 160 ° C., preferably for 5 to 20 seconds. To do. If the moisture content is less than 15% by mass, it is difficult to uniformly infiltrate the resin dispersion into the fiber skeleton. On the other hand, if the moisture content exceeds 200% by mass, the impregnated resin dispersion becomes insoluble until the winding process. When it comes into contact with a guide or the like, it may fall off with moisture, and the fiber winding process becomes difficult. The moisture content of the PPTA fiber is preferably 15 to 100% by mass, more preferably 20 to 50% from the viewpoints of the permeability of the resin dispersion into the PPTA fiber skeleton, the ease of moisture adjustment of the PPTA fiber, and the production efficiency. It is 35 mass%, Most preferably, it is 35-50 mass%.

  The PPTA fiber of the present invention maintains the crystal size of the PPTA fiber below 50 angstroms and the moisture content of 15 to 200% by weight while changing the heat treatment conditions at a temperature of 100 to 160 ° C. It is obtained by making a PPTA fiber and impregnating and impregnating a resin dispersion into the PPTA fiber skeleton. When the crystal size of the PPTA fiber is 50 angstroms or more, it becomes difficult to penetrate the resin dispersion into the fiber skeleton.

  Further, it is desirable that the PPTA fiber does not have a history of drying after spinning to a moisture content of less than 15% by mass. This is because by using PPTA fibers whose moisture content is always adjusted to 15% by mass or more, a state in which the resin dispersion can easily permeate can be maintained.

  The resin dispersion to be infiltrated and impregnated into the PPTA fiber skeleton adjusted to the water content of 15 to 200% by mass may be a resin dispersion or a resin emulsion, and the type of resin is not particularly limited. By infiltrating and impregnating as a resin dispersion, a larger amount of resin can be infiltrated than in the case of infiltrating and impregnating the resin into an aqueous solution, and as a result, improving the affinity (particularly adhesiveness) with polypropylene resin. Can do. Moreover, the effect by the resin adhering to the PPTA fiber surface when permeating can be expected.

  The resin constituting the resin dispersion is preferably a urethane resin or an epoxy resin in terms of excellent adhesiveness (adhesion) with PPTA fibers and polypropylene resin, and at least one resin selected from these resins Can be used.

Urethane resin is a block copolymer in which polyisocyanate component and polyol component are alternately present in one molecule, and the urethane and urea bonds that make up the polyisocyanate component have a strong cohesive force in the molecule and between molecules, and are hard. Segments and polyol components are called soft segments because their glass transition point (Tg) is below room temperature, molecular chains are easy to rotate, and cohesion is weak, and each segment forms a structure with microphase separation. For this reason, it originates in the cohesive force of a hard segment, is excellent in adhesiveness and abrasion resistance, originates in the low glass transition temperature (Tg) of a soft segment, and is excellent in flexibility and a low temperature characteristic.
Epoxy resins are excellent in adhesiveness, flexibility, heat resistance, wear resistance, and the like.

  The resin concentration in the resin dispersion is not particularly limited, but a dispersion having a resin concentration of 10% by mass or more, preferably about 30 to 50% by mass is used. As the resin particle diameter, those having a small particle diameter are preferable in terms of excellent penetration and impregnation properties. Specifically, the average particle diameter (according to electron microscopy) is more preferably 100 nm or less, and 20 to 20 More preferably, it is about 600 nm. The pH of the resin dispersion is preferably in the range of 6-10.

  As the solvent for the resin dispersion, water, an aqueous solvent or a mixed solvent thereof is preferable, and water is particularly preferable. Examples of the aqueous solvent include esters, aliphatic alcohols, (poly) alkylene glycol ethers, ketones and the like, and two or more kinds of mixed solvents may be used. Moreover, organic solvents other than these may be mixed.

(Urethane resin)
The urethane resin dispersion may be either an emulsion type emulsion in which a urethane resin is forcibly emulsified using a surfactant as an emulsifier, or a self-emulsification type emulsion in which a hydrophilic group is introduced into the urethane resin. In the case of the self-emulsifying urethane resin emulsion, an anionic self-emulsifying urethane resin emulsion having a carboxylic acid group or a sulfonic acid group having good reactivity with the surface functional group of the PPTA fiber, or excellent in pH stability. Nonionic self-emulsifying urethane resin emulsions and the like are preferred.

There is no restriction | limiting in particular as a urethane resin, A well-known urethane resin can be used individually by 1 type or in mixture of 2 or more types. Urethane resins include urethane resins having different structures depending on the type of polyol, and examples thereof include polyether-based urethane resins, polyester-based urethane resins, and polycarbonate-based urethane resins.
Examples of the polyether polyol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene oxypropylene glycol, polyoxytetramethylene glycol, and alkylene oxide adducts having 2 to 4 carbon atoms of bisphenols.
Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, polycaprolactone diol, and polyvalerolactone diol.
Examples of the polycarbonate polyol include polyhexane methylene carbonate diol.

  Examples of the polyisocyanate include diphenylmethane-4,4′-diisocyanate (MDI), 3,3′-dimethyl-diphenylmethane-4,4′-diisocyanate, and 3,3′-dimethyl-4,4′-biphenylene. Diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 1,3- or 1,4-phenylene Aromatic diisocyanates such as diisocyanate and p-xylene diisocyanate; Aliphatic diisocyanates such as ethylene diisocyanate, tetramethylene-1,4-diisocyanate and hexamethylene-1,6-diisocyanate (HDI); Dicyclohexylmethane diisocyanate and the like Cycloaliphatic diisocyanate; and, one or a mixture of two or more selected from modified products thereof and the like.

  The polyether-based urethane resin may be synthesized from the above polyether polyol, the above polyisocyanate, and a carboxylic acid-containing polyol such as dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolvaleric acid.

  Among the above urethane resins, polyether urethane resins and polycarbonate urethane resins are preferable from the viewpoint of excellent water resistance, and polyether urethane resins are preferable from the viewpoint of excellent chemical resistance.

(Epoxy resin)
There is no restriction | limiting in particular as an epoxy resin, A well-known urethane resin can be used individually by 1 type or in mixture of 2 or more types. For example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester Glycidyl etherified products such as epoxy resin, glycidylamine epoxy resin, and polyalkylene glycol epoxy resin. The epoxy resin dispersion may be an emulsion type water-based epoxy resin. Among these epoxy resins, an epoxy resin that is liquid at room temperature, particularly a bisphenol type epoxy resin is preferable, and a general-purpose type bisphenol A type epoxy resin is particularly preferable.

  The epoxy resin dispersion may be an aliphatic polyamine (for example, diethylenetriamine, triethylenetetramine), an aromatic polyamine (for example, m-phenylenediamine, m-xylylenediamine), an acid anhydride (for example, phthalic anhydride), etc. Known curing agents can be included.

  When the resin dispersion is infiltrated and impregnated into a PPTA fiber skeleton adjusted to a moisture content of 15 to 200% by mass having no history of moisture content of less than 15% by mass, the moisture content of the PPTA fiber is 0%. It is preferable to impregnate and impregnate 0.1 to 20.0 mass% as a solid content (resin) with respect to the fiber mass converted to. More preferably, it is 0.5-15.0 mass%, More preferably, it is 1.0-12.0 mass%, Most preferably, it is 3.0-10.0 mass%. If the amount permeated and impregnated is small, the effect of imparting adhesiveness may not be sufficiently exhibited.

  For example, the PPTA fiber impregnated and impregnated with the resin dispersion is wound around the bobbin in the winding process, then unwound from the bobbin, heat-treated to remove moisture, and the moisture content is made less than 15% by mass. The PPTA fiber composite of the invention can be produced.

  In the present invention, the resin dispersion liquid may be used by being included in an oil agent or may be used in a step separate from the oil agent when the resin dispersion is infiltrated into the PPTA fiber skeleton adjusted to a moisture content of 15 to 200% by mass. Examples of the oil agent include general oil agents used for PPTA fibers, such as low molecular weight fatty acid esters having 18 or less carbon atoms, polyethers, and mineral oils. When the resin is used by being included in an oil agent, the oil agent is preferably contained in an amount of about 20 to 60% by mass, more preferably 30 to 50% by mass.

  The method for applying the resin dispersion or the oil containing the resin dispersion to the PPTA fiber is not particularly limited, and any conventionally known method may be employed, for example, immersion oil supply method, spray oil supply method, roller oil supply method, It is applied to PPTA fiber by a method such as a guide oiling method using a metering pump.

  The PPTA fiber composite impregnated with and impregnated with the resin dispersion is wound on the bobbin continuously as it is or once in the winding process, and then the wound PPTA fiber composite is unwound from the bobbin and heat treated. Therefore, the moisture content should be less than 15% by mass, more preferably less than 10% by mass. The conditions for the heat treatment are not particularly limited. For example, when heat treatment is performed at 80 to 300 ° C., preferably 100 to 250 ° C., the moisture content can be less than 15% by mass. By this heat treatment, the crystal size of PPTA is enlarged, and the resin can be fixed in the PPTA fiber skeleton by narrowing the gap between crystals.

The PPTA fiber composite of the present invention has significantly improved adhesion to the polypropylene resin compared to PPTA fibers that have not been impregnated / impregnated with the resin dispersion. The reason is not clear, but it is considered as follows.
A PPTA fiber skeleton whose water content is adjusted to 15 to 200% by mass is impregnated and impregnated with a resin dispersion having an ether group, an ester group, a carbonate group, or a glycidyl ether group, and then heat treated to remove the water. Thus, a resin having an ether group, an ester group, a carbonate group, a glycidyl ether group or the like is fixed in the PPTA fiber skeleton. In the case of a urethane resin, the urethane bond constituting the hard segment has high affinity with the PPTA fiber, and the ether bond constituting the soft segment has close affinity with the polypropylene resin.
On the other hand, most of the surface functional groups of PPTA fibers are amide groups, but there are amine groups and carboxyl groups due to hydrolysis of the amide groups, though only a little. The resin fixed in the PPTA fiber skeleton reacts with the functional group of the PPTA fiber under non-heating and / or heating to be fixed in the PPTA fiber skeleton. The PPTA fiber composite thus obtained has good adhesion to the polypropylene resin. In addition, although the reactivity changes with the kind of resin to introduce | transduce and the drying conditions after introduction | transduction, it is thought that it reacts easily on the conditions heated rather than unheated conditions.

  The PPTA fiber composite obtained in the present invention is suitably used as a fiber reinforcing material for reinforcing a polypropylene resin. The polypropylene resin may be a propylene homopolymer, an ethylene-propylene copolymer, a modified polypropylene resin, or the like. Other than that, it is also useful as a fiber reinforcement with rubber materials and various resin materials other than polypropylene resin.

  When used for rubber reinforcement, a method of subjecting the PPTA fiber composite of the present invention to a dipping treatment with a known resorcin formalin latex (RFL) and the like can be mentioned. For example, 100 parts by weight of rubber latex is added to the PPTA fiber composite. A method in which an RFL treatment solution containing about 5 to 25% by mass of a solid content concentration of a mixture containing 2 to 20 parts by mass of a resorcin-formaldehyde initial condensate is heat-treated at 100 to 260 ° C. Can be mentioned.

  Examples of rubber latex include vinylpyridine-styrene-butadiene copolymer rubber latex, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, chloroprene rubber latex, chlorosulfonated polyethylene rubber latex, acrylate rubber latex, and natural rubber. Examples of the resorcin-formaldehyde initial condensate include novolak condensates obtained by condensing resorcin-formaldehyde in the presence of an acid catalyst or an alkali catalyst. In the treatment liquid, one or more compounds selected from a blocked polyisocyanate compound, an ethyleneimine compound, a reaction product of polyisocyanate and ethyleneimine, and the like may be mixed.

  In the PPTA fiber composite of the present invention, the resin dispersion is infiltrated and impregnated into the PPTA fiber skeleton, so that the adhesion of the RFL treatment liquid is good and the strength of the cord is reduced when the RFL high temperature treatment is performed. Hateful.

  In addition, a flock-like short fiber composite obtained by cutting the PPTA fiber composite of the present invention that has been subjected to immersion treatment with RFL into 0.1 to 5 mm is also useful as a reinforcing material for rubber belts.

  The PPTA fiber composite of the present invention is a flock-like short fiber composite that is cut to 0.1 to 5 mm without being subjected to RFL treatment. Paper used for gears, sheets for printed wiring boards, non-woven fabrics, Useful for resin additives.

  In addition to the above, the fiber reinforcement of the present invention is used in various forms such as short fibers cut from PPTA fiber composites, fiber bundles made of PPTA fiber composites, woven fabrics, knitted fabrics, twisted yarns, processed yarns, etc. There is no particular limitation.

  The fiber reinforced polypropylene resin composite material of the present invention is a composite of the above fiber reinforcement and polypropylene resin, and the composite form is not particularly limited. For example, the fiber reinforced polypropylene resin composite material of the present invention can be obtained by a method such as sticking or twisting fiber reinforcing materials to a polypropylene resin sheet by hot press molding or the like. The fiber reinforcing material may be dispersed in polypropylene resin, the fiber reinforcing material bundle or woven or knitted fabric may be impregnated with polypropylene resin, or the fiber reinforcing material bundle or woven or knitted fabric may be laminated with a polypropylene resin sheet.

  The fiber reinforced polypropylene resin composite material can be used as automobiles, ships, electrical / electronic devices, AV devices, OA devices, building parts or members, and the like.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only the following Examples. In addition, each measured value in an Example followed the following method.

(1) Moisture content (mass%)
A mass of about 5 g of the sample is measured, a heat treatment is performed at 105 ° C. × 1 hour, the sample is left at 24 ° C. and 55% RH for 5 minutes, and then the mass is measured again. The moisture content used here is a dry base moisture content obtained by [mass before drying−mass after drying] / [mass after drying] × 100.

(2) Amount of resin adhering to fiber (% by mass)
The fibers before the treatment with the resin dispersion are sampled at a predetermined length, treated at 105 ° C. for 4 hours, and measured after being left at 24 ° C. and 55% RH for 5 minutes. Next, the fibers after the resin dispersion treatment are sampled at the same length, and the mass after treatment at 105 ° C. for 4 hours is measured. The resin adhesion amount to the fiber used here is obtained by [mass after treatment−mass before treatment] × 100 / [mass before treatment].

(3) Peeling load (N)
Using a tensile tester, install a resin sheet with long fibers that are not attached to the resin surface about 20 mm from the end on a jig designed so that the plate-shaped resin sample moves smoothly in the horizontal direction. Then, the end portion that was not attached was sandwiched between chucks that moved in the vertical direction, and the load when the chuck was moved upward (90-degree direction) was measured to obtain a peeling load.

Example 1
1 kg of PPTA (molecular weight of about 20,000) obtained by a usual method is dissolved in 4 kg of concentrated sulfuric acid, and discharged from a die having 1000 holes with a diameter of 0.1 mm so that the shear rate is 30,000 sec ⁻¹ . After spinning in water at 4 ° C., it was neutralized with a 10% by weight aqueous sodium hydroxide solution at 10 ° C. for 15 seconds, and then dried at a low temperature of 110 ° C. for 15 seconds to give a moisture content of 35%. % PPTA fiber (fineness 1670 dtex when converted to 0% by mass moisture content). Furthermore, this PPTA fiber was passed through a dip bath of a polyether-based urethane resin dispersion (Sanyo Kasei Co., Ltd. Chemitylene (R) GA-500), squeezed with a roll, the amount of adhesion was adjusted, 105 ° C., 4 hours By drying, PPTA fibers were produced by impregnating and impregnating 7.6% by mass (resin equivalent) of the resin with respect to the fiber having a moisture content of 0% by mass.

To the obtained PPTA fiber, 2.08 times / inch of single twist was added.
After aligning the seven PPTA fiber composites so that the length is 265 mm or more at 1 mm intervals in the vertical direction, the fiber end portion is determined, and the length from the end portion to the fiber alignment direction is 20 mm. A polypropylene resin sheet (density: 0.91 g / cm ³ , tensile strength: 265 mm long and 4 mm thick, manufactured by Toray Plastic Seiko Co., Ltd.) 29 MPa) using a 3.8 mm spacer in a hot press molding machine and processing at 180 ° C. for 15 minutes under a load of 30 kg / cm ² to melt the resin, then, at room temperature, 70 kg / cm ² Under the conditions, the PPTA fiber reinforced plastic with PPTA fiber affixed onto a 3.8 mm thick non-reinforced polypropylene resin sheet by cooling and solidifying the mold to 50 ° C. or less. To obtain a propylene resin sheet. The peel load of the PPTA fiber in this sheet test piece was 15N.

(Example 2)
A polycarbonate urethane resin dispersion (U2-04 made by MICHELMAN®) was used as the dipping liquid for dipping the PPTA fiber having a moisture content of 35% by mass obtained in Example 1, and the moisture content was determined in the same manner as in Example 1. PPTA fiber was produced by impregnating and impregnating 4.3% by mass (resin equivalent) of the resin with respect to the fiber when the rate was converted to 0% by mass.
A PPTA fiber reinforced polypropylene resin sheet having a PPTA fiber attached thereto was obtained in the same manner as in Example 1 using the obtained PPTA fiber added with 2.08 turns / inch single twist. The peel load of the PPTA fiber in this sheet test piece was 12N.

(Example 3)
A bisphenol A type epoxy resin dispersion (Yukaresin KE-307-N manufactured by Yoshimura Oil Chemical Co., Ltd.) was used as the dip solution passed through the PPTA fiber before treatment having a moisture content of 35% by mass obtained in Example 1, and Example 1 and In the same manner, PPTA fiber was produced by impregnating and impregnating 6.6% by mass (resin equivalent) of the resin with respect to the fiber having a moisture content of 0% by mass.
Using a PPTA fiber obtained by adding 2.08 times / inch single twist, a sheet on which PPTA fiber was attached was obtained in the same manner as in Example 1. The peel load of the PPTA fiber in this sheet test piece was 12N.

(Comparative Example 1)
PPTA not applied with a resin dispersion in the same manner as in Example 1 except that it was dried without passing the dip solution through the PPTA fiber before treatment having a moisture content of 35% by mass obtained in Example 1. A PPTA fiber reinforced polypropylene resin sheet to which fibers were attached was obtained. The peel load of PPTA fiber in this sheet test piece was 9N.

  From the results in Table 1, the PPTA fiber reinforced polypropylene resin of Example 1 infiltrated and impregnated with the polyether-based urethane resin dispersion is compared with the PPTA fiber reinforced polypropylene resin not infiltrated and impregnated (Comparative Example 1). It was confirmed that the adhesion of PPTA fibers to polypropylene resin was improved by 1.7 times. In addition, the PPTA fiber reinforced polypropylene resin composite material of Examples 2 and 3 impregnated with and impregnated with a polycarbonate-based urethane resin dispersion or bisphenol A type epoxy resin has an adhesiveness to the polycarbonate resin of 1.3 compared to Comparative Example 1. A double improvement was observed.

  The polyparaphenylene terephthalamide fiber reinforcement of the present invention and the fiber-reinforced polypropylene resin composite material containing the same are useful for various industrial materials.

Claims (6)

  A fiber reinforcing material used to reinforce a polypropylene resin, in a polyparaphenylene terephthalamide fiber skeleton adjusted to a water content of 15 to 200% by mass having no history of moisture content of less than 15% by mass A fiber reinforcing material comprising a polyparaphenylene terephthalamide fiber composite formed by impregnating and impregnating a resin dispersion.   The resin in the dispersion is infiltrated and impregnated in an amount of 0.1% by mass to 20.0% by mass with respect to the fiber mass when the water content of the polyparaphenylene terephthalamide fiber is converted to 0% by mass. The fiber reinforcement according to claim 1, wherein   The fiber reinforcement according to claim 1 or 2, wherein the resin is at least one selected from a urethane resin and an epoxy resin.   The fiber reinforcing material according to any one of claims 1 to 3, wherein the resin is at least one selected from a polyether-based urethane resin, a polycarbonate-based urethane resin, and a bisphenol-type epoxy resin.   A fiber-reinforced polypropylene resin composite material comprising the fiber reinforcing material according to claim 1.   An automotive part or member using the fiber-reinforced polypropylene resin composite material according to claim 5.