CN107385594A - Complex yarn and cloth and silk and their manufacture method - Google Patents

Abstract

The present invention relates to complex yarn and cloth and silk and their manufacture method.The problem of the present invention is not reduced the high complex yarn of the mechanical characteristic of fiber-reinforced resin molding, productivity ratio, cloth and silk.The present invention provides a kind of complex yarn, and it is the complex yarn being made up of the reinforcing fiber beam comprising more reinforcing fibers and thermoplastic resin, wherein, total sectional area of the reinforcing fiber in 1 beam reinforcing fiber is 0.00005cm²~0.0022cm², total sectional area of the reinforcing fiber in complex yarn is 0.0007cm²~0.0085cm²。

Description

Complex yarn and cloth and silk and their manufacture method

Technical field

The present invention relates to the complex yarn being made up of reinforcing fiber beam and thermoplastic resin and the cloth being made up of complex yarn Silks (cloth and silk) and their manufacture method.

Background technology

In works of the structure member of various machineries, automobile etc., pressure vessel and tubulose etc., using in resin material In the composite material molded body added with the strengthening material such as glass fibre.It is light in order to take into account for composite material molded body Quantization and intensity, it is desirable to follow arbitrary shape.

As the material for forming composite material molded body, it is proposed that reinforcing fiber and thermoplastic resin fibre is continuous and equal The even complex yarn being obtained by mixing and the cloth and silk comprising complex yarn (for example, with reference to patent document 1,2).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2015-67926 publications

Patent document 2：Japanese Unexamined Patent Publication 4-183729 publications

The content of the invention

Invent problem to be solved

But previously known complex yarn, cloth and silk employ the mechanical strength of pursuit tension test, bend test etc. Design, but if it is considered that applied to the structural elements exposed, then it is expected also to improve impact strength.It is in addition, compound in order to improve The productivity ratio of yarn, cloth and silk, thickening yarn are effective, but when using thick reinforcing fiber, the property such as impact strength be present Can be low the problem of.

The means used to solve the problem

The present inventor etc. have made intensive studies to solve above-mentioned problem of the prior art, as a result find, by by 1 Total sectional area control of reinforcing fiber in the total sectional area and complex yarn of reinforcing fiber in beam reinforcing fiber is being advised In fixed scope, infiltration of the thermoplastic resin into reinforcing fiber beam improves, and not only tensile strength is high, and impact strength carries It is high.In addition, it has been found that having used the cloth and silk of the complex yarn by manufacture, production can be improved in the case where keeping high intensity Rate, so as to complete the present invention.

That is, complex yarn of the invention is to be made up of the reinforcing fiber beam comprising more reinforcing fibers and thermoplastic resin Complex yarn, wherein, total sectional area of the reinforcing fiber in 1 beam reinforcing fiber is 0.00005cm²~0.0022cm², it is compound Total sectional area of reinforcing fiber in yarn is 0.0007cm²~0.0085cm²。

It is preferred that there is multi beam reinforcing fiber beam.

R μm of the single fiber diameter of reinforcing fiber and density Dg/cm³Product RD be preferably 5 μm of g/cm³~100 μm of g/ cm³。

The outer peripheral face of the reinforcing fiber beam of complex yarn can be covered by thermoplastic resin.

Complex yarn can be that complex yarn obtained from mixed fibre is carried out to the fiber of reinforcing fiber beam and thermoplastic resin.

The manufacture method of the complex yarn of the present invention is the reinforcing fiber beam and thermoplastic resin that will include more reinforcing fibers The manufacture method of the compound complex yarn of fat, wherein, total sectional area by the reinforcing fiber in 1 beam reinforcing fiber is 0.00005cm²~0.0022cm²Reinforcing fiber beam and thermoplastic resin it is compound, so as to by the reinforcing fiber in complex yarn Total sectional area is adjusted to 0.0007cm²~0.0085cm²。

Can be 0.00005cm by total sectional area²~0.0022cm²Reinforcing fiber beam and thermoplastic resin it is compound and Pre-composite yarn is made, and the pre-composite yarns carry out simultaneously silk and/or plying by more, so as to which the reinforcing in complex yarn is fine Total sectional area of dimension is adjusted to 0.0007cm²~0.0085cm²。

Mixed fibre can be carried out to the fiber of reinforcing fiber beam and thermoplastic resin by fluid intertexture method.

For the cloth and silk of the present invention, the complex yarn of the invention described above is included in warp and/or parallel.

For the manufacture method of the cloth and silk of the present invention, weaved preferably by rapier loom.

Invention effect

According to the complex yarn of the present invention, cloth and silk, the mechanical characteristic of fiber-reinforced resin molding can not reduced In the case of, obtain to high production rate complex yarn, cloth and silk.Furthermore it is possible to obtain that not only tensile strength is excellent but also impact strength Also excellent fiber-reinforced resin molding.

Embodiment

Hereinafter, it is described in detail for the present invention.It should be noted that the present invention is not limited to following content, Various modifications can be carried out to implement in the range of its main idea.

<Complex yarn>

Complex yarn in the present invention refers to by the reinforcing fiber beam and thermoplastic resin including at least more reinforcing fibers The yarn of composition.Thermoplastic resin can be fibre morphology.In addition, for complex yarn, can enumerate for example：Mixed fiber yarn Line, by thermoplastic fibre and reinforcing fiber Shu Jinhang and yarn, the outer peripheral face thermoplasticity by reinforcing fiber beam obtained from silk Yarn etc. obtained from fiber covering.The a part of of the thermoplastic resin of complex yarn can melt and infiltrate to reinforcing fiber beam Inside.As the form of thermoplastic resin, can enumerate：The shape that the peripheral surface of reinforcing fiber beam is covered with thermoplastic resin State, the form for being attached with reinforcing fiber beam thermoplastic resin powder, the fiber of reinforcing fiber beam and thermoplastic resin entered Form obtained from row is mixed fine, the form for further covering the mixed fiber yarn line with thermoplastic resin etc..In addition, thermoplastic resin A part of can melt and infiltrate to the inside of reinforcing fiber beam.

From the viewpoint of infiltration during shaping, each beam preferably in complex yarn in multi beam reinforcing fiber beam is can With the state of discrimination.But without on the whole separating reinforcing fiber beam each other on the whole length direction of yarn, a part Reinforcing fiber can interlock each other.For discrimination for the reinforcing fiber beam in complex yarn, such as can be by complex yarn Cut and observed along cross-wise direction, can also be untied complex yarn with the power of the not degree of damage strengthening fiber.

From the viewpoint of the operability of the intensity and yarn of formed body in itself, the volume of reinforcing fiber and thermoplastic resin Ratio is preferably 10：90~80：20, more preferably 20：80~70：30, more preferably 30：70~60：40.

The complex yarn of the present invention may be used as the reinforcing fiber for strengthening other materials, and complex yarn can also be entered Row is processed and cloth-like is made, and as the reinforcing cloth for being used to strengthen other materials, can also be made by carrying out heating processing Fiber-reinforced resin molding.

, can be using the complex yarn of the present invention as the fibre after strengthening for the composition of fiber-reinforced resin molding Dimension, combined with the matrix resin of various thermoplastic resins, thermosetting resin and formed and mix formed body (Ha イ Block リ ッ De shaping Body), can also be by making the thermoplastic resin of composition complex yarn melt to obtain matrix resin and form formed body.

<Sectional area>

Reinforcing fiber is often used with fibre bundle state obtained from the single fiber of approximate number μm~about tens of μm is tied up. In the present invention, by comprising more approximate numbers μm~article of about tens of μm of reinforcing fiber (single fiber) is referred to as reinforcing fiber beam, 1 beam Total sectional area of reinforcing fiber (single fiber) in reinforcing fiber is necessary for 0.00005cm²~0.0022cm².Sectional area refers to The sectional area in direction at a right angle with fiber axis.Total sectional area (section of fibre bundle of reinforcing fiber in 1 beam reinforcing fiber Product) can be by the fiber number (dtex) and density (g/cm of 1 beam reinforcing fiber³) calculated by following formula.It should be noted that density can To be determined using densimeter, fiber number can determine according to JIS L1013.

From the viewpoint of the viewpoint and operability of the intensity for improving formed body are excellent, the reinforcing in 1 beam reinforcing fiber is fine Total sectional area of dimension is preferably 0.00006cm²~0.0018cm², more preferably 0.00011cm²~0.0016cm², further Preferably 0.00019cm²~0.0012cm², most preferably 0.00023cm²~0.0006cm²。

Total sectional area of reinforcing fiber in complex yarn passes through strong in 1 beam reinforcing fiber that will be obtained using above formula Total sectional area of chemical fibre dimension is added up to and obtained by the radical for the reinforcing fiber for forming complex yarn.From raising impact strength From the viewpoint of, total sectional area of the reinforcing fiber in complex yarn is necessary for 0.0007cm²~0.0085cm², it is preferably 0.00072cm²~0.0065cm², more preferably 0.00074cm²~0.0044cm², more preferably 0.000776cm²~ 0.0022cm², most preferably 0.00078cm²~0.0017cm²。

If sectional area is added up to be 0.0007cm using only 1 beam²~0.0085cm²Reinforcing fiber beam, then can take into account drawing The mechanical characteristics such as intensity and impact strength are stretched, but is gone out from the viewpoint for making intensity and impact strength balanced in higher scope Hair, preferably using the small reinforcing fiber beam of multi beam sectional area, so as to increase total sectional area of the reinforcing fiber in complex yarn. From the viewpoint of molding time, intensity, the radical of reinforcing fiber beam is more much more preferred, but if excessive, then operates sometimes Property is poor, the beam of therefore preferably 1 beam~50, the beam of more preferably 2 beams~20, the beam of more preferably 3 beams~16, most preferably 3 beams ~10 beams.

In addition, when using multi beam reinforcing fiber beam, the fibre bundle of different rugosity can be used, but in order to obtain physical property Uniform sample, preferably using fibre bundle similar in rugosity.As index similar in rugosity, can enumerate：The section of fibre bundle Long-pending ratio.Specifically, the sectional area of most thin fibre bundle is preferably relative to the ratio of the sectional area of most thick fibre bundle More than 60%, more preferably more than 70%, more preferably more than 80%, most preferably more than 90%.In addition, relative to institute The value of the standard deviation of the average value of the sectional area of the whole fibre bundles used is preferably smaller than 15%, more preferably less than 10%, enters One step is preferably smaller than 5%, more preferably less than 3%.

Reinforcing fiber is used as raw material after being wound after spinning, can also be after spinning directly and thermoplastic resin Combination.In the latter case, the fibre bundle as obtained from 1 bushing (bushing) spinning is 1 beam reinforcing fiber.

<Reinforcing fiber>

Reinforcing fiber can use the reinforcing fiber used in common reinforced fiber composite formed body, be not limited to Following example, it can enumerate for example：Selected from fine by glass fibre, carbon fiber, aramid fibre, ultra high strength polyethylene Dimension, polyphenyl are simultaneouslyAzoles (Port リ ベ Application ザ ゾ ー Le) fiber, liquid crystalline polyester fiber, polyketone fiber, metallic fiber, ceramic fibre At least one kind of fiber in the group of composition is as preferable reinforcing fiber.From the viewpoint of mechanical properties, thermal characteristics, versatility, It is preferred that glass fibre, carbon fiber, aramid fibre, from productivity ratio aspect, preferably glass fibre.

Collecting agent is preferably used in reinforcing fiber, and is preferably used：For forming the boundary of reinforcing fiber and thermoplastic resin The end that the coupling agent in face, the operability for improving reinforcing fiber and the interface of assist thermoplastic's resin and coupling agent are formed Agent (Knot beams drug), operational lubricant for improving reinforcing fiber etc..From the sight that even spread is carried out on reinforcing fiber Point sets out, collecting agent application preferably in the form of liquid or be gasiform.In the situation using the high compound of fusing point, boiling point Under, can be heated while be coated with, it can also be made to be dissolved in solvent and be coated, can also be emulsified and Used in the form of water system.

The alternatively species of collecting agent, the method for amount, can be enumerated for example：Using as described in patent document 1 Droplet is tested obtaining with matrix resin boundary strength.But collecting agent can be volatilized or gone bad due to heat sometimes, thus it is excellent The experiment is carried out after being selected in thermal history when applying shaping.

Hereinafter, the example of collecting agent during for selection glass fibre as reinforcing fiber illustrates.As collecting agent, Preferably comprise silane coupler, lubricant and finisher.

(silane coupler)

Silane coupler is typically used as the surface conditioning agent of glass fibre, is favorably improved interface adhesive strength.

As silane coupler, following example is not limited to, can be enumerated for example：Gamma-amino propyl trimethoxy silicon The amino silicone alkanes such as alkane and N- β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane；γ-mercaptopropyi trimethoxy The hydrosulphonyl silane class such as base silane and γ-Mercaptopropyltriethoxysilane；Epoxy silane class；Vinyl silanes class etc..In order to promote Enter the reaction of fiberglass surfacing and silane coupler, the preferably presence in water, the acid as catalyst, alkali, metallic compound Under handled.

(lubricant)

Lubricant is favorably improved the fibrillation of glass fibre.

As lubricant, any lubriation material of common liquid or solid can be used according to purpose, be not limited to Under example, can enumerate for example：The wax of the animal-plant types such as Brazil wax, lanolin wax or mineral type；Fatty acid amide, fat Surfactants such as fat acid esters, aliphatic acid ether, aromatic ester, aromatic ether etc..

(finisher)

Finisher is favorably improved the convergence of glass fibre and improves interface adhesive strength.

As finisher, thermosetting resin, thermoplastic resin, low molecular compound can be used according to purpose.

[thermosetting resin]

As the thermosetting resin of finisher, following example is not limited to, can be enumerated for example：By m-phenylenedimethylim- Isocyanates and the polyester such as diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isoflurane chalcone diisocyanate Class or the polyurethane resin of polyethers glycol synthesis.Alternatively, it is also possible to suitably using for example：Bisphenol-type epoxy resin and curing agent (amine, acid anhydrides), acrylic resin.

[thermoplastic resin]

As the thermoplastic resin as finisher, following example is not limited to, can be enumerated for example：Acrylic compounds tree It is fat, polyolefin resin, polyamide-based resin, polyacetal-based resins, polycarbonate resin, polyester resin, polyether-ketone, poly- Ether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluorine-containing resin and obtained from they are modified Modified thermoplastic resin etc..

For the thermoplastic resin as finisher, if with the matrix resin identical type of composite shaped body Thermoplastic resin and/or modified thermoplastic resin, then after composite shaped body is formed, glass fibre and thermoplastic resin it is gluing Property improve, therefore be preferable.In addition, preferably used from the viewpoint of glass fibre interfascicular not residual clearance after shaping Viscosity is low compared with matrix resin and/or the thermoplastic resin and/or modified thermoplastic of fusing point low (glass transition temperature is low) Resin.For example, can be by using the resin lower than matrix resin molecular weight or if crystalline resin then introduces destruction The structure of crystallization or the length for increasing side chain, so as to obtain low viscosity and/or low melting point (lower glass transition temperatures).

As the acrylic resin as finisher, can enumerate：The homopolymer of acrylic acid, acrylic acid and other it is total to The copolymer of polycondensation monomer and they with the salt of primary amine, secondary amine and tertiary amine etc..Homopolymer and copolymer as acrylic acid come To say, weight average molecular weight is preferably 1000~90000, and more preferably 1000~25000.

As the copolymerisable monomer for the copolymer for forming acrylic acid and other copolymerisable monomers, following example is not limited to Son, it can enumerate for example：In the monomer with hydroxyl and/or carboxyl, selected from by acrylic acid, maleic acid, methacrylic acid, second More than a kind (its in the group that alkenyl acetic acid, crotonic acid, iso-crotonic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid are formed In, do not include the situation of only acrylic acid).It is preferred that with more than a kind of esters monomer as copolymerisable monomer.

As the homopolymer of acrylic acid and the salt with primary amine, secondary amine and tertiary amine of copolymer, example below is not limited to, can To enumerate for example：Triethylamine salt, triethanolamine salt, glycinate etc..From improve with it is other and with reagent (silane coupler etc.) Mixed solution stability, reduce amine it is smelly from the viewpoint of, degree of neutralization is preferably 20%~90%, more preferably 40%~ 60%.

The weight average molecular weight of the polymer of the acrylic acid of forming salt is not particularly limited, preferably 3000~50000 model Enclose.From the viewpoint of the convergence for improving glass fibre, preferably more than 3000, from the spy improved when composite shaped body is made From the viewpoint of property, preferably less than 50000.

In addition, further improve reinforcing fiber and cover the reinforcing fiber thermoplastic resin adhesivity, by boundling In the case that agent is adhered on the glass fibers in the form of aqueous dispersions, from the ratio that can reduce emulsifier component or not The viewpoints such as emulsifying agent are needed to set out, as the thermoplastic resin as finisher, preferably modified thermoplastic resin.

Herein, modified thermoplastic resin refers to：In addition to it can form the monomer component of main chain of thermoplastic resin, it is Change the character of the thermoplastic resin, different monomer components is copolymerized with it, so that hydrophily, crystallinity, thermodynamics The modified resin such as characteristic.

Modified thermoplastic resin as finisher, following example is not limited to, can enumerated for example：Modified acroleic acid Resinoid, improved polyalkene resinoid, modified polyamide resinoid, modified poly ester resinoid etc..

Improved polyalkene resinoid as finisher refers to：The olefin monomers such as ethene, propylene and unsaturated carboxylic acid etc. The copolymer for the monomer that can be copolymerized with olefin monomer, can be manufactured by known method.Improved polyalkene resinoid can To be random copolymer obtained from making olefin monomer and unsaturated carboxylic acid copolymerization or arrive unsaturated carboxylic acid graft Graft copolymer obtained from alkene.

As olefin monomer, following example is not limited to, can be enumerated for example：Ethene, propylene, 1- butylene etc..This A little monomers can individually be used only a kind, or two or more can also be applied in combination.As what can be copolymerized with olefin monomer Monomer, it can enumerate for example：Acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, different crotons Unsaturated carboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc., these monomers can individually be used only a kind, can also Two or more is applied in combination.

As olefin monomer and can with the olefin monomer be copolymerized monomer copolymerization ratio for, by the conjunction of copolymerization Meter quality is set to 100 mass %, and preferred alkenes class monomer is 60~95 mass %, the monomer that can be copolymerized with olefin monomer is 5~40 mass %, more preferably olefin monomer are 70~85 mass %, the monomer that can be copolymerized with olefin monomer is 15~30 Quality %.If olefin monomer is more than 60 mass %, good with the compatibility of matrix, in addition, if olefin monomer Quality % be below 95 mass %, then the water dispersible of improved polyalkene resinoid is good, easily carry out on reinforcing fiber Uniform attachment.

In improved polyalkene resinoid as finisher, alkalescence can be used by being copolymerized the modified groups such as the carboxyl introduced Compound is neutralized.As alkali compounds, following example is not limited to, can be enumerated for example：Sodium hydroxide, hydroxide The bases such as potassium；Ammonia；The amines such as MEA, diethanol amine.The weight average molecular weight of improved polyalkene resinoid as finisher It is not particularly limited, preferably 5000~200000, more preferably 50000~150000.From the convergence for improving glass fibre From the viewpoint of, preferably more than 5000, it is excellent from the viewpoint of the emulsion stability in the case where being adjusted to water dispersible Elect less than 200000 as.

Modified polyamide resinoid as finisher refers to introduce poly- alkylene oxide group chain, tertiary amine composition in strand Deng the modified polyamide compound of hydrophilic radical, can be manufactured by known method.

In the case of poly- alkylene oxide group chain is introduced in strand, such as it can manufacture in the following manner：Make poly- second Material obtained from part or all of glycol, polypropylene glycol etc. are modified to diamine or dicarboxylic acids is copolymerized.Drawing In the case of entering tertiary amine composition, such as it can be manufactured in the following manner：Make aminoethylpiperazine, double (aminopropyl) piperazines Piperazine, alpha-alpha-dimethyl amino epsilon-caprolactams etc. are copolymerized.

Modified poly ester resinoid as finisher refers to polybasic carboxylic acid or the copolymer of its acid anhydrides and polyalcohol and wrapped There is the resin of hydrophilic radical in molecular skeleton containing end, can be manufactured by known method.

As hydrophilic radical, can enumerate for example：Poly- alkylene oxide group, sulfonate, carboxyl, their neutralization salt etc..As Polybasic carboxylic acid or its acid anhydrides, can be enumerated for example：Aromatic binary carboxylic acid, the aromatic binary carboxylic acid containing sulfonate, aliphatic Dicarboxylic acids, ester ring type dicarboxylic acids, more than trifunctional polybasic carboxylic acid etc..

As aromatic binary carboxylic acid, following example is not limited to, can be enumerated for example：Phthalic acid, terephthaldehyde Acid, M-phthalic acid, phthalic acid, 1,5- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, phthalate anhydride etc..

As the aromatic binary carboxylic acid containing sulfonate, following example is not limited to, can be enumerated for example：Terephthaldehyde Sour sulfonate, M-phthalic acid 5- sulfonate, phthalic acid 5- sulfonate etc..

As aliphatic dicarboxylic acid or ester ring type dicarboxylic acids, following example is not limited to, can be enumerated for example：It is rich Horse acid, maleic acid, itaconic acid, butanedioic acid, adipic acid, azelaic acid, decanedioic acid, dimeric dibasic acid, 1,4 cyclohexanedicarboxylic acid, butanedioic acid Acid anhydride, maleic anhydride etc..

As polybasic carboxylic acid more than trifunctional, following example is not limited to, can be enumerated for example：Trimellitic acid, Benzenetetracarboxylic acid, trimellitic anhydride, pyromellitic dianhydride etc..

Among those, from improve modified poly ester resinoid heat resistance from the viewpoint of, preferably whole polybasic carboxylic acids into 40~99 moles of % divided are aromatic binary carboxylic acid.In addition, from emulsification when modified poly ester resinoid to be made to aqueous dispersions From the viewpoint of stability, 1~10 mole of % of preferably whole polybasic carboxylic acid compositions is the aromatic binary carboxylic acid containing sulfonate.

As the polyalcohol for forming modified poly ester resinoid, can enumerate：Polyalcohol more than dihydric alcohol, trifunctional etc..

As dihydric alcohol, following example is not limited to, can be enumerated for example：Ethylene glycol, diethylene glycol, polyethylene glycol, Propane diols, polypropylene glycol, polytetramethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,6-HD, neopentyl glycol, polytetramethylene Glycol, 1,4- cyclohexane diols, 1,4 cyclohexane dimethanol, bisphenol-A or its alkylene oxide addition product etc..More than trifunctional Polyalcohol, it can enumerate for example：Trimethylolpropane, glycerine, pentaerythrite etc..

For the polybasic carboxylic acid or the copolymerization ratio of its acid anhydrides and polyalcohol for forming modified poly ester resinoid, it will be copolymerized Total quality of composition is set to 100 mass %, preferably polybasic carboxylic acid or its acid anhydrides be 40~60 mass %, polyalcohol be 40~60 Quality %, more preferably polybasic carboxylic acid or its acid anhydrides are 45~55 mass %, polyalcohol is 45~55 mass %.

The weight average molecular weight of modified poly ester resinoid is preferably 3000~100000, and more preferably 10000~30000.From From the viewpoint of the convergence for improving glass fibre, preferably more than 3000, from the breast in the case where being adjusted to water dispersible From the viewpoint of changing stability, preferably less than 100000.

[low molecular compound]

Low molecular compound as finisher preferably has the functional group of reactivity.For example, using the bases such as polyamide In the case of body resin, the compound to be reacted with the carboxy termini of polyamide and/or amide groups end is preferably used.As Such compound, it can enumerate for example：Compound with epoxy radicals, the compound with anhydride group.As with acid anhydrides The compound of base, it can enumerate for example：Succinic anhydride, phthalate anhydride, maleic anhydride, benzoyl oxide etc., modification can be passed through And used after being suitably adjusted to easy-to-handle molecular weight.

Thermosetting resin, thermoplastic resin and low molecular compound as finisher can individually be used only a kind, also may be used With and use two or more.

The total amount of finisher is set to 100 mass %, preferably using more than 50 mass %, more preferably use 60 mass % More than the homopolymer selected from acrylic acid, acrylic acid and other copolymerisable monomers copolymer and they and primary amine, secondary amine and More than a kind of polymer in the salt of tertiary amine.

(composition of glass fiber sizing agent)

In the case where using glass fibre as reinforcing fiber, in the collecting agent of glass fibre, preferably comprise：0.1 ~2 mass % silane couplers, 0.01~1 mass % lubricants, 1~25 mass % finishers.It is preferred that by these composition water Dilution, and gross mass is adjusted to 100 mass %.

From the convergence for improving glass fibre and improve interface adhesive strength and the mechanical strength of raising composite shaped body From the viewpoint of, the use level of the silane coupler in glass fiber sizing agent is preferably 0.1~2 mass %, more preferably 0.1~1 mass %, more preferably 0.2~0.5 mass %.

From the viewpoint for assigning sufficient lubricity and from improving the joint yarn (Department ぎ yarn) that is obtained using empty twister From the viewpoint of tensile break strength and improving mixes the fibrillation in fine process, lubricant in glass fiber sizing agent is matched somebody with somebody Resultant is preferably more than 0.01 mass %, more preferably more than 0.02 mass %.From raising interface adhesive strength and improve compound From the viewpoint of the mechanical strength of formed body, the use level of the lubricant in glass fiber sizing agent be preferably 1 mass % with Under, more preferably below 0.5 mass %.

From the convergence and raising interface adhesive strength of control glass fibre and the mechanical strength for improving composite shaped body From the viewpoint of, the use level of the finisher in glass fiber sizing agent is preferably 1~25 mass %, and more preferably 3~15 Quality %, more preferably 3~10 mass %.

(the use form of glass fiber sizing agent)

Glass fiber sizing agent can be adjusted to the aqueous solution, the form of colloidal dispersions, use according to occupation mode Any one form such as the form of the emulsion of emulsifying agent, but from improving the dispersion stabilization of collecting agent, improve heat resistance Viewpoint is set out, preferably the form of the aqueous solution.

It can continuously obtain forming the complex yarn of the present invention and the glass fibre of cloth and silk in the following manner：Known Glass fibre manufacturing process in, above-mentioned collecting agent is applied to glass fibre using method known to roll shape spreader etc. On, and manufactured glass fibre is dried.

Relative to the mass % of glass fibre 100, collecting agent is in terms of total quality of silane coupler, lubricant and finisher It is preferred that applying 0.1~3 mass %, more preferably apply 0.2~2 mass %, further preferably apply 0.2~1 mass %.

From the viewpoint of the convergence of control glass fibre and raising interface adhesive strength, relative to glass fibre 100 Quality %, the applied amount of collecting agent be preferably 0.1 mass % in terms of total quality of silane coupler, lubricant and finisher with On；The viewpoint of the fibrillation in fine process is mixed from the tensile break strength and raising for improving the joint yarn obtained using empty twister Set out, preferably below 3 mass %.

It should be noted that in the case where selection carbon fiber is as reinforcing fiber, collecting agent preferably comprises lubricant, knot Beam agent.For collecting agent, lubricant, finisher species, be not particularly limited, known material can be used.As specific Material, can use for example：Material described in patent document (Japanese Unexamined Patent Publication 2015-101794 publications).

In the case of using other reinforcing fibers, according to the characteristic of reinforcing fiber, suitably select to be used for glass fibre, carbon Species, the imparting amount of the collecting agent of fiber, preferably set the species of collecting agent according to the collecting agent for carbon fiber, assign The amount of giving.

<The shape of reinforcing fiber beam>

Reinforcing fiber beam is the multifilament for including more reinforcing fibers, from the fibrillation in mixed fine process and the viewpoint of operability Set out, single fiber dimension is preferably 30~15000.From the viewpoint of the viewpoint and operability of intensity, the list of reinforcing fiber Fibre diameter is preferably 2 μm~30 μm, more preferably 4 μm~25 μm, more preferably 6 μm~20 μm, most preferably 8 μm~ 15μm。

The single fiber diameter of reinforcing fiber generally produces variation due to manufacturing process in reinforcing fiber Shu Zhonghui.Close In the variation of single fiber diameter, it is not particularly limited, but the shadow that scattered small single fiber diameter changes to the physical property of formed body Sound is small, therefore is preferable.Therefore, when measuring the distribution of single fiber diameter, preferably single dispersing.In addition, single fiber diameter Standard deviation be preferably less than 3 μm, more preferably less than 2 μm, more preferably less than 1 μm, most preferably 0.8 μm with Under.

From complex yarn operability and formed body intensity from the viewpoint of, the single fiber diameter R (μm) of reinforcing fiber with Density D (g/cm³) product RD be preferably 5~100 μm of g/cm³, more preferably 10~50 μm of g/cm³, more preferably 15 ~45 μm of g/cm³, it is still more preferably 20~45 μm of g/cm³.When product RD is defined scope, it will particularly strengthen fine When dimension beam and thermoplastic fibre carry out mixed fine, the damage of reinforcing fiber beam, reinforcing fiber Shu Rongyi fibrillation, two kinds of fibers can be suppressed It is easily continuous and equably mix, therefore be preferable.

Density D can utilize densimeter to determine.On the other hand, single fiber diameter (μm) can be by density (g/cm³) and it is fine Spend (dtex), single fiber dimension (root) is calculated using following formula.

In order to which the product RD of reinforcing fiber is adjusted into defined scope, for the commercially available reinforcing fiber that can be obtained, according to The density that reinforcing fiber has, suitably select fiber number (dtex) and single fiber dimension (root).Such as make using glass fibre In the case of reinforcing fiber, density is about 2.5g/cm³, therefore selection single fiber diameter is for 2 μm~40 μm of glass fibre Can.Specifically, when the single fiber diameter of glass fibre is 9 μm, by selecting fiber number 660dtex and single fiber dimension 400 Glass fibre, product RD be 23.In addition, when the single fiber diameter of glass fibre is 17 μm, by selecting fiber number 11500dtex And the glass fibre of single fiber dimension 2000, product RD are 43.In the case where using carbon fiber as reinforcing fiber, density is about 1.8g/cm³, therefore selection single fiber diameter is 2.8 μm~55 μm of carbon fiber.Specifically, when the single fiber of carbon fiber When tieing up a diameter of 7 μm, by selecting fiber number 2000dtex and single fiber dimension 3000 carbon fiber, product RD is 13.Using virtue In the case that polyamide fiber is as reinforcing fiber, density is about 1.45g/cm³, therefore it is 3.4 μm to select single fiber diameter ~68 μm of aramid fibre.Specifically, when the single fiber diameter of aramid fibre is 12 μm, pass through The aramid fibre of fiber number 1670dtex and single fiber dimension 1000 is selected, product RD is 17.

Reinforcing fiber can be any form, but be wound into yarn, spinning cake, DWR (direct roving (ダ イ レ Network ト ワ イ Application ド ロ ー PVC Application グ)) when, productivity ratio in the process of covering resin, production stability can be improved, therefore be preferred 's.From the viewpoint of productivity ratio, most preferably DWR, from the viewpoint of production stability, most preferably yarn.

<Thermoplastic resin>

The thermoplastic resin for forming the complex yarn of the present invention can be the form of thermoplastic fibre or with thermoplastic Property resin form covering reinforcing fiber or the form that is attached on reinforcing fiber beam.

(species)

Thermoplastic resin can use the thermoplastic resin used in known complex yarn.

Thermoplastic resin is not limited to following example, can enumerate for example：The TPO tree such as polyethylene, polypropylene Fat；The polyamide-based resins such as polyamide 6, polyamide 66, polyamide 46；Polyethylene terephthalate, poly terephthalic acid The polyester resins such as butanediol ester, PTT；The polyacetal-based resins such as polyformaldehyde；Polycarbonate-based tree Fat；Polyether-ketone；Polyether-ether-ketone；Polyether sulfone；Polyphenylene sulfide；Thermoplastic polyetherimide；The thermoplastics such as tetrafluoroethylene-ethylene copolymer Property fluorine resin, and by these be modified obtained from modified thermoplastic resin, preferably by least one kind of heat in them Plastic resin carries out continuous fiber obtained from melt spinning.

It is preferred polyolefm resinoid, polyamide-based resin, polyester resin, polyether-ketone, poly- in these thermoplastic resins Ether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide and thermoplastic fluorine-containing resin；From mechanical properties, the sight of versatility Point sets out, more preferably polyolefin resin, improved polyalkene resinoid, polyamide-based resin and polyester resin；If add The viewpoint of hot physical property, then further preferred polyamide-based resin and polyester resin.In addition, from for repeating the (Kuri り that are further applied load Return loading Negative lotuses) durability from the viewpoint of, still more preferably polyamide-based resin can suitably use polyamide 66。

Thermoplastic resin can be used only a kind, can also and with a variety of.In addition, even in the same resin of use In the case of, it is also preferred that the different resin of viscosity, fusing point is applied in combination.Particularly, from the viewpoint of infiltration property is improved, preferably simultaneously With the resin of low viscosity and/or low melting point.The resin of low viscosity and/or low melting point can be by reducing molecular weight or by one It is partially modified or addition crystallisation inhibitors and obtain.

[polyester resin]

Polyester resin refers to the high-molecular compound on main chain with-CO-O- (ester) key.

As polyester resin, following example is not limited to, can be enumerated for example：Polyethylene terephthalate, Polybutylene terephthalate (PBT), poly terephthalic acid 1,4- butanediol esters, poly terephthalic acid -1,4 cyclohexane dimethanol Ester, poly- 2,6- (ethylene naphthalate)s etc..

Polyester resin can be homopolymerization polyester or copolyester.

In the case of copolyester, preferably suitably make the 3rd composition and material obtained from homopolymerization polyethylene terephthalate copolymer.As 3 compositions, following example is not limited to, can enumerated for example：The dihydric alcohols such as diethylene glycol, neopentyl glycol, PAG Dicarboxylic acids composition such as composition, adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, 5-sodium sulfo isophthalate etc..

Alternatively, it is also possible to use：Use from polyester resin obtained from the raw material of biomass resource, do not limited In following example, can enumerate for example：The fat such as PLA, poly butylene succinate, poly-succinic tetramethylene adipate Aromatic polyester-based resins such as fat adoption esters resin, polyadipate mutual-phenenyl two acid bromide two alcohol ester etc..

[polyamide-based resin]

Polyamide-based resin refers to the high-molecular compound on main chain with-CO-NH- (acid amides) key.

As polyamide-based resin, following example is not limited to, can be enumerated for example：Pass through the ring-opening polymerisation of lactams Obtained from polyamide, as obtained from the self condensing of omega-amino carboxylic acid polyamide, by making diamine and dicarboxylic acids contract Polyamide obtained from conjunction and their copolymer.

Polyamide-based resin can be used alone, and can also use mixture of more than two kinds.

As lactams, following example is not limited to, can be enumerated for example：Pyrrolidones, caprolactam, acyl in 11 Amine or lauric lactam.As omega-amino carboxylic acid, following example is not limited to, can be enumerated for example：Profit as lactams The omega-amino aliphatic acid of the opened loop compound obtained with water.For lactams or omega-amino carboxylic acid, 2 are each can be used together The monomer of the kind above simultaneously makes its condensation.

As diamine (monomer), following example is not limited to, can be enumerated for example：Hexamethylene diamine, five methylenes The aliphatic diamine of the straight-chains such as base diamines；The aliphatic of the branched chain types such as 2 methyl pentamethylenediamine, 2- ethyl hexamethylene diamines Diamine；The aromatic diamines such as p-phenylenediamine, m-phenylene diamine (MPD)；The alicyclic rings such as cyclohexane diamine, pentamethylene diamines, cyclooctane diamines Formula diamine.

As dicarboxylic acids (monomer), following example is not limited to, can be enumerated for example：Adipic acid, pimelic acid, the last of the ten Heavenly stems two The aliphatic dicarboxylic acids such as acid；The aromatic binary carboxylic acids such as phthalic acid, M-phthalic acid；The ester ring types such as cyclohexane cyclohexanedimethanodibasic two First carboxylic acid.Diamine and dicarboxylic acids as monomer can be by being each used alone a kind or and making it with two or more Condensation.

As polyamide-based resin, following example is not limited to, can be enumerated for example：(poly- α-the pyrrolidines of polyamide 4 Ketone), polyamide 6 (polycaprolactam), polyamide 11 (nylon 11), polyamide 12 (poly-lauramide), polyamide 46 (gather oneself Two acyl butanediamine), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6 T (poly- terephthaldehydes Acyl hexamethylene diamine), polyamide 9T (poly-paraphenylene terephthalamide's nonamethylene diamine) and polyamide 6 I (poly-6I hexamethylene isoterephalamide) and comprising Their copolyamides as constituent.

As copolyamide, following example is not limited to, can be enumerated for example：Hexamethylene adipamide and terephthaldehyde The copolymer and hexamethylene terephthalamide of the copolymer of acyl hexamethylene diamine, hexamethylene adipamide and 6I hexamethylene isoterephalamide With the copolymer of paraphenylene terephthalamide's 2 methyl pentamethylenediamine.

(form of thermoplastic fibre)

From improve it is pre- twist with the fingers process, mix fibrillation in fine process from the viewpoint of, the thermoplastic fibre that is used in the present invention Preferably substantially non-twist and substantial no intertexture.It is substantially non-twist to refer to except adjoint debatching (unwinding) etc. unintentionally Sth. made by twisting beyond non-twist state, twisting count is 10 times/below m.Substantially refer to without intertexture by common intertextures such as fluid intertextures For intentional intertexture caused by means to keep the state of the number of the bottom line of operability, intertexture number is 5 times/below m.

From the viewpoint of the fibrillation in mixed fine process and operability, the single fiber dimension of thermoplastic resin fibre is preferably 30~20000.

<The manufacture method of complex yarn>

(regulation of the sectional area of reinforcing fiber)

The regulation of total sectional area of reinforcing fiber in complex yarn is by using the reinforcing fiber beam for providing sectional area Carried out as raw material.For reinforcing fiber Shu Eryan, it can be shaped after spinning with the state of winding and release fiber And use, it can also directly be released and used by the spinning process of reinforcing fiber.In the latter case, using by 1 bushing Fibre bundle obtained from spinning is as 1 bundle fiber beam.

The regulation of total sectional area of reinforcing fiber in complex yarn can formed together with thermoplastic resin it is compound It is adjusted, for example can also answers 1 beam (or multi beam) reinforcing fiber and thermoplastic resin after complex yarn is formed during yarn Close and form pre-composite yarn, and the more pre-composite yarns are subjected to simultaneously silk and/or plying to be adjusted.In the former feelings Under condition, the more reinforcing fiber beams as raw material can be supplied as needed, thus adjust the reinforcing fiber in complex yarn Total sectional area.In the latter case, can be by by more of the pre-composite yarn of the state of more total sectional areas deficiencies Tie up, the complex yarn for the total sectional area for meeting reinforcing fiber is made.The method tied up can be by the shape after yarn and silk State, or the state after plying, but from the viewpoint of the operability of process afterwards, the state preferably pooled capital. As plying method, can enumerate for example：Mixed fibre (fluid, mechanics), close sth. made by twisting, covering, braiding etc..Tying up process can be independently Set, can also be carried out in the process after weaving etc..

(thermoplastic resin is covered in the method on reinforcing fiber beam)

As method thermoplastic resin being covered on reinforcing fiber beam, can enumerate such as Japanese Unexamined Patent Publication 8- Method described in No. 336879 publications.

As described above, in order to improve infiltration, during using the resin of low viscosity and/or low melting point as thermoplastic resin, It is preferred that the thermoplastic resin of low viscosity and/or low melting point is configured near reinforcing fiber beam to cause thermoplastic resin easily to enter Enter between reinforcing fiber beam.As method of the configuration near reinforcing fiber beam, such as the spray of extruding thermoplastic resins can be made The structure of mouth forms multilayer, and the resin of low viscosity and/or low melting point is flow to inner side, thus configures in reinforcing fiber beam Near.

It is preferred that the outer peripheral face in reinforcing fiber beam equably covers thermoplastic resin, the viscous of thermoplastic resin is preferably adjusted The compatibility of degree, the proportion of reinforcing fiber beam, density, thermoplastic resin and reinforcing fiber beam.In regulation importantly, right The thermoplastic resin and reinforcing fiber beam of melting make its contact, and regulation reinforcing fiber beam and melting in the state of applying pressure Thermoplastic resin contact and discharge the shape of die portion, the tension force of reinforcing fiber beam, thermoplastic resin melting temperature, Line speed.The particularly importantly shape of die head.

The shape of optimal mould is according to the species of the reinforcing fiber beam used, shape, surface conditioning agent, the resin covered Species and it is different, the resin of molten condition and the pressure of resin of the part of reinforcing fiber beam contact is uniformly set Meter.In order to which equably control pressure, the diameter for the outlet for preferably making to discharge in the state of contacting with reinforcing fiber beam are less than The resin of melting is introduced to the diameter of the entrance of mould, and improves the pressure of the part of reinforcing fiber beam and molten resin contact. It is preferred that by adjusting the pressure of the resin transfer of melting to mould, the viscosity of resin, the production linear speed for pulling out reinforcing fiber beam Degree, so that the pressure of the part of reinforcing fiber beam and molten resin contact keeps constant.

The manufacture device of complex yarn is by the conveying device of fiber, the device for making resin melting, die head, cooling device, inspection Device, up- coiler etc. is surveyed to form.Extruded type apparatus for coating, impregnated apparatus for coating etc. can be used.It is preferred that it is easily controlled resin The extruded type apparatus for coating of thickness.

As long as the melting temperature of resin is the high temperature of the fusing point than thermoplastic resin, but from suppressing heat deterioration Viewpoint is set out, preferably+100 DEG C of the fusing point of+10 DEG C of the fusing point of thermoplastic resin~thermoplastic resin, more preferably fusing point+20 DEG C~+80 DEG C of fusing point, more preferably+30 DEG C of fusing point~+70 DEG C of fusing point.Make the device of resin melting for example using extruder .It is preferred that the shape of the viscosity adjusting screw rod according to resin, send molten resin into die head at suitable pressures.According to need Will, preferably carry out nitrogen purging, ventilation etc..

Cooling can be air cooling, can also be carried out by being impregnated in water-bath, can also be by chill roll And carry out.Furthermore it is possible to sprayed while on chill roll with water.It is excellent in the case where water to be used to cool down Choosing is arranged as required to drier.Drying can use the fluids such as air to carry out, and can also apply temperature, can also use cloth etc. Physically remove water.Detector for example can optically detect the stability of diameter, the inspection by the amplitude of fiber Survey and detect the skew of center of gravity.Up- coiler can be automatically controlled, and can also be controlled manually.

From the viewpoint of productivity ratio and production stability, the speed of fiber is preferably 10~2000m/ minutes, more preferably For 50~1800m/ minutes, preferably 100~1500m/ minutes.

Die head, the cooling device that conveying device, reinforcing fiber beam and the resin of melting of fiber contact are preferably arranged to directly Line.It is preferred that before and after each device, as desired by the slightly larger guider of the diameter than fiber, control before and after die head Fiber position.

(manufacture method of mixed fiber yarn line)

Known method can be utilized by reinforcing fiber beam and thermoplastic resin fibre mix the method for fibre.It can enumerate Such as：Using electrostatic force, the external force such as pressure, pressure for being pressed against on roller etc. carries out fibrillation, Ran Hou as caused by fluid spray Make to be pooled capital in the state of reinforcing fiber beam and thermoplastic resin fibre's fibrillation and the fibrillation of silk plying method, fluid interweave and (handed over Knit, Taslan (タ ス ラ Application)) method.It is preferred that use can suppress the damage of reinforcing fiber beam, fibrillation it is excellent, can be equably The fluid intertexture method of mixing.As fluid intertexture method, such as it is preferably used in the method described in patent document 1.Can be appropriate Rugosity, the radical of the reinforcing fiber beam as raw material are adjusted, manufacturing condition can also be adjusted in the lump.

In the past, for mixed fiber yarn line, admixture is more good more preferred.Although it is preferred that reinforcing fiber beam and thermoplastic resin The good situation of the admixture of fat fiber, but using in the case of multi beam reinforcing fiber beam, preferably reinforcing fiber beam are each other Less interweave in high degree, because the dispersity in formed body becomes appropriate, intensity has elevated tendency.As The method for not making reinforcing fiber beam make it interweave with thermoplastic resin fibre in the case of interweaving in high degree each other, can be enumerated Such as：Processing is individually interleaved to a branch of reinforcing fiber beam and thermoplastic resin fibre, it is low then to carry out simultaneously silk, progress respectively The method of the interleaving treatment of degree, after by multi beam reinforcing fiber beam and Duo Gen thermoplastic resin fibres and silk, enter under low pressure Method that row fluid interweaves etc..During implementation interleaving treatment multiple to reinforcing fiber, intensity reduces sometimes, therefore is preferably handed over Knit the few situation of number of processing.Pressure condition during as progress fluid intertexture under low pressure, preferably 5kg/cm²Hereinafter, Preferably 4kg/cm²Hereinafter, most preferably 3kg/cm²Below.

As described above, in order to improve infiltration, it is fine preferably using the fiber of low viscosity and/or low melting point as thermoplasticity Dimension, in order to obtain the balance with long-time quality, preferably and with high viscosity and/or dystectic thermoplastic fibre.Low viscosity and/or The mode that the thermoplastic fibre of low melting point is configured in the periphery of reinforcing fiber beam improves the effect height of infiltration property, therefore is carrying out And the used time, it can enumerate：Using more thermoplastic fibres and when carrying out mixed fine, by low viscosity and/or the thermoplasticity of low melting point Fiber is carried out in reinforcing fiber beam side and silk, mixed fine method.

<The intermediate materials such as fabric>

It is not particularly limited using the method for the complex yarn manufacture fiber-reinforced resin molding of the present invention, preferably It is to make intermediate materials according to the shape of target fibers reinforced resin formed body, uses the intermediate materials manufacturing objective fiber Reinforced resin formed body.

Intermediate materials are not particularly limited, and can enumerate：By complex yarn along obtained from after specific direction and silk it is single To strengthening material, the cloth and silk for having used complex yarn, such as textile, knitting, mesh fabric (レ ー ス), felt, non-woven fabrics, Film, plate body etc..

As intermediate materials, from the viewpoint of product having shape-following-up properties when manufacturing fiber-reinforced resin molding, in mould Set out, it is however preferred to have unidirectional strengthening material, textile, knitting, mesh fabric, felt, the non-woven fabrics of flexibility, it is fine from strengthening The bending of dimension less and is easily obtained from the viewpoint of intensity, more preferably knitting, unidirectional strengthening material, textile shape, from From the viewpoint of morphological stability, more preferably knitting, textile shape.

The weave of knitting is not particularly limited, and can enumerate：Plain weave weave, twill, satin weaves, leno (Li り Woven), yarn weave etc..

From the viewpoint of the intensity of fiber-reinforced resin molding, the low twill of the weave shrinkage of more preferably reinforcing fiber Weave.

From the viewpoint of intensity, knitting is preferably for example referred to as the multi-axial tricot of non-crimp fabric, compiles The woollen yarn knitting method of fabric can be enumerated：Warp-knitting, composite algorithm (U Application ビ ネ ー シ ョ Application) etc..

The method for obtaining these intermediate materials is not particularly limited, and can be selected according to purposes, purpose.

For example, textile uses the Weaving-machines, at least one such as loom, rapier loom, jet type loom, water-jet loom Complex yarn is included in point.As preferable method, can enumerate for example：By the way that parallel wedging is made to include complex yarn Fiber alignment obtained from method obtained from warp.Wherein, from the damage for suppressing reinforcing fiber, fabric is stably obtained From the viewpoint of, preferred rapier loom.The amplitude of rapier loom is preferably more than 60cm, more preferably more than 80cm, further Preferably more than 100cm, because being easy to the tension stability for making fabric, obtain the fabric of uniform quality.If amplitude is Size more than certain, then stay in grade, it is preferred that being set as wieldy amplitude according to used fiber.Strengthening When in fibre bundle using glass fibre, carbon fiber, amplitude is preferably below 6m, more preferably below 5m, more preferably 4m Hereinafter, most preferably below 3m.

Knitting can by using braiders such as circular knitting machine, weft machine, warp knitting machine, La Sheer braiders, It is woven into the fiber comprising complex yarn at least a portion and obtains.

Non-woven fabrics can be by making the fiber formation referred to as sheet of mesh comprising complex yarn at least a portion Fiber assembly, then utilize the heat of the physical action of needing machine, knit-stitch machine, columnar flow machine (Zhu Zhuan Liu Machine) etc., knurling rolls etc. Effect, adhesive, make fiber be bonded to each other and obtain.

Form on other intermediate materials etc., can be suitably using described in Japanese Unexamined Patent Publication 2015-101794 publications Method.

<Fiber-reinforced resin molding and its manufacture method>

Above-mentioned complex yarn, intermediate materials can be manufactured fiber-reinforced resin molding as constituent material.

It should be noted that the manufacture method of fiber-reinforced resin molding is not limited to following example, can apply Various methods.

For example, by form the base material of fiber-reinforced resin molding, preferably textile product shape base material according to desired Formed body is cut, and is considered the thickness of target product and is laminated the piece number of needs, and is configured according to the shape of mould.This When, by using above-mentioned intermediate materials, compared with being impregnated with the conventional composite plate of resin in common reinforcing fiber, for The free degree can be improved for mould, difference of height in formed body be present, can also be molded with high freedom shape. Before setting in a mold, the process for drying base material can be included.Drying process before cutting and/or can be cut laggard OK.

Cutting for base material can be carried out with 11 ground, can also be by the overlapping rear progress of desired number.From productivity ratio Viewpoint is set out, and is preferably cut in the state of overlapping.The method cut can be arbitrary method, can enumerate for example： Sprinkler, knife press, hot knife press, laser, plotter etc..It is preferred that hot knife press, because cross sectional shape is excellent, and Overlapping multi-disc simultaneously makes when being cut end face welding good so as to operability.Appropriate severing shape can by repeat trial and error and It is adjusted, it is preferred that by being simulated according to the shape of mould using CAE (computer-aided engineering analysis) to set.

After base material is arranged in mould, closes mould and be compressed.Then, by the temperature adjustment of mould to structure Temperature into more than the fusing point of the thermoplastic resin of fiber-reinforced resin molding, so that thermoplastic resin melts, and carry out Shaping.Clamping pressure does not have special provision, preferably more than 1MPa, more preferably more than 3MPa.In addition, in order to be exhausted Deng, can also temporary transient matched moulds, and after compression forming temporarily release clamping pressure.

In the manufacturing process of fiber-reinforced resin molding, intermediate materials can be arranged in mould and close mould Tool, is pressurizeed, after the defined time, thermoplastic resin composition as defined in further injection fillers is simultaneously molded, and is made Thermoplastic resin engages with defined thermoplastic resin composition, and thus manufacture mixes formed body.

The opportunity of thermoplastic resin composition as defined in injection fillers have the boundary strength two kinds of thermoplastic resins compared with It is big to influence.The opportunity of thermoplastic resin composition as defined in injection fillers is preferably that intermediate materials are being arranged in mould and closed After mold closing tool, mold temperature is warming up to the fusing point of thermoplastic resin, it is more than glass transition temperature after 30 seconds within.

Mold temperature as defined in injection fillers during thermoplastic resin composition is preferably to form fiber-reinforced resin shaping More than the fusing point of the thermoplastic resin of body or more than glass transition temperature.More preferably form fiber-reinforced resin molding More than+10 DEG C of more than+10 DEG C of the fusing point of thermoplastic resin or glass transition temperature, more preferably more than+20 DEG C of fusing point Or more than+20 DEG C of glass transition temperature, even more preferably for+30 DEG C of more than+30 DEG C of fusing point or glass transition temperature with On.

Preferably, in formed body is mixed, the thermoplastic resin of fiber-reinforced resin molding is formed and by being injected into Type and the bonding part of thermoplastic resin composition that is formed forms the concaveconvex structure mutually mixed.

By mold temperature set for the fusing point for the thermoplastic resin composition to be injected more than, and when improving injection moulding The holding pressure of resin, for example it is set as more than 1MPa, is effective in terms of boundary strength is improved.It is strong in order to improve interface Degree, preferably pressure will be kept to be set as more than 5MPa, be more preferably set as more than 10MPa.

From the viewpoint of boundary strength is improved, the time length of pressure, such as more than 5 seconds, preferably 10 seconds are preferably kept More than, more preferably maintained until mold temperature reach below the fusing point of thermoplastic resin composition between time.

(resin of injection moulding)

As the thermoplastic resin composition for manufacturing the injection moulding for mixing formed body, as long as common be used for Injection molding thermoplastic resin composition, is just not particularly limited.

As thermoplastic resin composition, following example is not limited to, can be enumerated for example：It is mixed with polyethylene, gathers Propylene, polyvinyl chloride, acrylic resin, styrene resin, polyethylene terephthalate, poly terephthalic acid fourth two It is alcohol ester, polyarylate, polyphenylene oxide, modified polyphenylene ether resin, Wholly aromatic polyester, polyacetals, makrolon, PEI, poly- Resin combination obtained from more than one or both of ether sulfone, polyamide-based resin, polysulfones, polyether-ether-ketone, polyether-ketone etc..

In addition, various packing materials can be coordinated in these thermoplastic resin compositions.

As various packing materials, can enumerate：As the discontinuous strengthening material with reinforcing fiber for same material Chopped fiber, long fiber material etc..

When in discontinuous strengthening material using staple glass fibre, long fibre, the complex yarn possessed with the present invention Reinforcing fiber can similarly use collecting agent.

Collecting agent preferably comprises silane coupler, lubricant and finisher.On silane coupler, lubricant, finisher Species, the collecting agent identical material with above-mentioned reinforcing fiber can be used.

From the interface of fiber-reinforced resin molding part and thermoplastic resin composition part obtained from injection moulding From the viewpoint of intensity, it is preferred for injection molding thermoplastic resin composition with forming the heat of fiber-reinforced resin molding Plastic resin is similar, more preferably identical type.Specifically, in the thermoplastic resin for forming fiber-reinforced resin molding When having used Nylon66, the resin material of the thermoplastic resin composition of injection moulding is preferably polyamide 66.

<The purposes of products formed>

Fiber-reinforced resin molding can be suitable for the structural material purposes of aircraft, vehicle, construction material etc..

In vehicular applications, following example is not limited to, can be used for for example：Chassis/vehicle frame, hull, driving class portion Part, internal part, external component, functional part, other parts.

Specifically, it is suitable as with lower component：Steering spindle, fixture, skylight, pedal, cresting part, car door gadget, OK Lee's case, boot lid, hood, mounting, backrest, constriction device, reflective mirror support frame, clutch, gear, cunning Wheel, cam, AG axles, spring beam, buffer, lamp, reflective mirror, classification connection, front-end module, back door inner side, brake pedal, direction Disk, Denso material, sound-absorbing material, car door exterior material, interior panel, instrument board, back door, skylight beam, seat, seat frame, Windshield wiper frame, EPS (electric boosting steering system), miniature motor, radiator, ECU (control unit of engine) case, ECU shells, turn To gearhousing, plastic housing, EV (electric automobile) motors framework, wire harness, onboard instruments, stacked switch, miniature motor, bullet Spring, baffle plate, wheel, wheel cap, vehicle frame, subframe, side frame, cart frame, fuel tank, food tray, inlet manifold, propeller shaft, driving With motor, monocoque, hydrogen tank, the electrode of fuel cell, panel, floor panel, outer plate panel, door, cabin, top, cover, Valve, EGR (exhaust gas recirculatioon) valve, variable valve timing unit, connecting rod, casing bore, part (engine frame), preceding floor Cloth, sufficient nest cloth, seat cloth, inner side, the cloth at car rear portion, draft hitch, post reinforcer, front side, front panel, top, instrument board Cloth, steering wheel), passage, insertion section, collision case, collision orbit, corrugated plating, top guide rail, upper body, side guide, lace, Around door component, air bag component, body pillar, collision twin columns support frame, suspension pylon, bumper, body pillar bottom, front of the car Post, assistant reinforcement plate (instrument board, guide rail, top, front truck Shenzhu, top guide rail, top side face guide rail, control stick, door opener, preceding bottom Bottom, front truck Shenzhu top, front truck Shenzhu bottom, newel, newel hinge, door opener side panel), side lateral surface Plate, front door window frame, MICS (Minimum Intrusion Cabin System, minimum invasion cabin systems) main body, torsion box, Radiator bearer, radiator fan, water pump, petrolift, Electronic Control throttle body, engine control ECU, starter, friendship Flow generator, manifold, gearbox, clutch, instrument board, instrument board mat insulation, door side protection beam, bumper beam, Men Liang, dividing plate, outer pad, interior pad, back seat bar, door-plate, vehicle door plaque sub-component, acceptor of energy (bumper, impact absorbing), punching Hit absorber, impact absorbing decoration, post decoration, top side interior trim, resin muscle, side rails front baffle, side rails rear bulkhead, seat band Preloader, air bag inductor, arm (suspension, bottom, foot hinge), suspension connection, impact absorbing bracket, mudguard support, change To before device bracket, commutator module, foot wainscot, foot panel, hood heat emission hole, hood top outer Plate, hood top outer panel, bottom plate muffler, overturning seat, foot insulator, mud guard side panel protector, start Hood insulator, hood top portion ventilation device set mouthpart, cylinder head cover, tire deflector, mud guard support, compression member Tower bar, task central passage, backplane channel, radiator core support, luggage panel, luggage bottom plate etc..

Embodiment

Specific embodiment of the invention described below and comparative example, but the present invention is not limited to following embodiments.

[stretching test method of fiber-reinforced resin molding]

Using Instron 100kN universal testing machines, by length 70mm, width 10mm, thickness 3mm bar shaped test film Clamped along its length with 30mm interval, tensile strength is determined in the environment of speed 5mm/ minutes, 23 DEG C of 50%RH.

[method of the impact test of fiber-reinforced resin molding]

Implement according to JIS K7211-2.Experimental rig uses Shimadzu HYDRO SHOT HITS-P10, in striker diameter 20mm φ, receive diameter 40mm φ, test speed 4.4m/ seconds, experiment plate shape 60mm × 60mm × 2mmt, 23 DEG C of test temperature Under conditions of carry out.

[complex yarn output]

The fiber number (dtex) of complex yarn obtained by measure, the operating speed of up- coiler when being produced according to complex yarn Degree, calculate the output of every 1 minute complex yarn.It should be noted that for winding speed, work is produced in complex yarn Stability (in the case where not breaking can steady running at least more than 1 hour), the quality of complex yarn of sequence are (lint-free Hair) in good scope, it is set as at high speed.

[Fypro]

Use：Trade name：Leona (registration mark) 470/144BAU (Asahi Chemical Ind's system), fiber number 470dtex, single fiber dimension 144.

[glass fibre]

Use：It is attached with following collecting agents, the E glass (alkali-free glass) of 1.0 mass % emulsion form.Fiber number and list Fiber count is changed as shown in table 1.Form is wound using substantially non-twist spinning cake form.

(collecting agent a composition (being converted by solid constituent))：

Silane coupler：Mass % [the trade names of γ aminopropyltriethoxy silane 0.6：KBE-903 (SHIN-ETSU HANTOTAI's chemistry Industrial Co., Ltd's system)]

Lubricant：Mass % [the trade names of wax 0.1：Brazil wax (Co., Ltd. adds rattan foreign firm system)]

Finisher：Mass % [the trade names of acrylic acid/maleic acid salt 5：Aqualic TL (Japanese catalyst strain formulas Commercial firm's system)]

[manufacture method of textile]

Using rapier loom (woven pieces 2m) or knitting machine (woven pieces 30cm), using being made in embodiment 1~9, comparative example 1~4 The complex yarn made is weaved as warp, parallel.Textile density is adjusted to reach the weight per unit area shown in table 1.

[manufacture method of fiber-reinforced resin molding]

(the compression forming process of fabric)

Forming machine uses the toshiba machine system (S100V-8A) that maximum clamping force is 300 tons.

Prepare fiber-reinforced resin molding (longitudinal 200mm, horizontal 200mm, height 120mm, the wall for obtaining box Thick 2mm) mould.It is provided for securing the fabric to the pin of the corner of mould.

The fabric for providing piece number is overlapping, the shape of matched mold is cut into using hot blade guillotine.Now, cutting part It is fused due to heat, is integrally formed shape.

The mould for being previously heated to 300 DEG C is opened, yarn fabric is arranged on to the assigned position of mould, and consolidated with pin It is fixed.Then, with mold clamping force 240MPa matched moulds, it is compressed shaping.

Mould is opened, and takes out formed body.

(embodiment 1)

As shown in table 1, by after 4 beam glass fibres, 4 beam Fypros plying/and silk, it is essentially vertically supplied To fluid interlaced jet, fluid intertexture is carried out under the following conditions, so as to obtain complex yarn.Use the single fiber of glass fibre The monodispersed glass fibre that a diameter of average about 9 μm, standard deviation is 0.1 μm.

Glass fibre is batched (translocation Ga takes り) by spinning cake form.

Thermal finalization：It will carry out and before silk, using heating part 1m, 240 DEG C of heater, carry out Fypro Thermal finalization.

Fypro shrinks because of thermal finalization, therefore adjusts quantity delivered.

The expansion and contraction of reinforcing fiber is small, and fiber easily occurs and rocks, therefore adjusts fiber channel and rocked with reducing fiber.

Fluid interlaced jet：KYOCERA KC-AJI-L (1.5mm diameters, drive-in)

Air pressure：2kg/cm²

Process velocity：100m/ minutes

Indoor environment is adjusted to 25 DEG C, humidity 50%.

Dry air is flowed through winding part, prevent polyamide moisture absorption.

(embodiment 2)

Using with 20mm double screw extruders (L/D=33), stenter, up- coiler AIKI company system coating machines.It is right In glass fibre, batched (translocation Ga takes り) by spinning cake form.From the releasing of glass fibre until die head, cooling, volume Around, by glass fibre turn into straight line in a manner of configured.Before immediately die head, after immediately being contacted with cooling water, Immediately from cooler come out after, before immediately up- coiler, the guider of fiber is set.Using relative to fiber as 90 degree of angle Degree sets extruder.Cooled down using water-bath, blown away moisture using air after cooling.The speed of fiber is set as 200m/ minutes, it is controlled using up- coiler.Extruded at 280 DEG C~295 DEG C.With the contact portion with glass fibre The mode smaller than the lead-in portion of resin is using the die head for inserting flow controller, to cause the polyamides after the inner molten of die head Polyimide resin (trade name：Leona (registration mark) 1402S (Asahi Chemical Corp's system)) with glass fibre in micro- pressurization shape Contacted under state, and the extruded velocity of fine adjustment extruder, so as to manufacture complex yarn.

(embodiment 3)

By 1 beam glass fibre, 1 beam Fypro pool capital/and silk after, it is essentially vertically supplied to fluid Interlaced jet, pre-composite yarn is obtained under conditions of similarly to Example 1.

The pre-composite yarn of 4 beams is pooled capital, is twisted under conditions of 40 times/m and 1 complex yarn is made.

(embodiment 4)

1 beam glass fibre, 1 beam Fypro pool capital/and silk after, it is essentially vertically supplied to fluid Interlaced jet, pre-composite yarn is obtained under conditions of similarly to Example 1.

In weaving, 4 pre-composite yarns are subjected to simultaneously silk and 1 complex yarn is made, so as to be weaved.

(embodiment 5~7)

In addition to used kinds of fibers, radical being set as shown in table 1, in a manner of similarly to Example 1, Complex yarn is obtained.

(embodiment 8)

Except the stainless steel fibre (trade name using the above-mentioned collecting agent for being attached with 1.0 mass %：Naslon, Japan's essence Line Co. Ltd. system) beyond, in a manner of similarly to Example 1, obtain complex yarn.

(embodiment 9)

In addition to the complex yarn of embodiment 1 is weaved using knitting machine, in the same way, obtain compound Yarn.

(embodiment 10)

Except air pressure is set as into 4.2kg/cm²In addition, in a manner of similarly to Example 1, composite yarn has been obtained Line.States different from other embodiments, interweaving in high degree each other for reinforcing fiber.

(embodiment 11)

Using 1 1350dtex, 14 μm of single fiber diameter, 0.2 μm of standard deviation, monodispersed glass fibre, 6 1500dtex, 11 μm of single fiber diameter, 0.1 μm of standard deviation, monodispersed glass fibre, using 15 Fypros, Under conditions of similarly to Example 10, complex yarn has been obtained.

(embodiment 12)

After 1 1350dtex, the glass fibre of 14 μm of single fiber diameter and 15 Fypros are carried out into mixed fibre, will To complex yarn and 6 1500dtex, the glass fibre of 11 μm of single fiber diameter carry out mixed fibre again under identical condition. Mixed fibrid is same as in Example 10.

(comparative example 1,2)

In addition to used kinds of fibers, radical being set as shown in table 1, in a manner of similarly to Example 1, Complex yarn is obtained.

(comparative example 3)

By reinforcing fiber, Fypro are utilized respectively after electrostatic fibrillation pool capital/and silk and then reuse The fibrillation plying method that electrostatic implements fibrillation is carried out mixed fine (fluid intertexture is not carried out).It is fine using 1 beam reinforcing fiber, 10 beam polyamide Dimension.

(comparative example 4)

Reinforcing fiber shown in table 1, each 1 beam of Fypro are subjected to fluid intertexture under the following conditions.

Fluid interlaced jet：KYOCERA KC-AJI-L (1.5mm diameters, drive-in)

Air pressure：4kg/cm²

Process velocity：250m/ minutes

Use obtained complex yarn, production unit area weight 1430g/m², 4 axles (0 degree/- 45 degree/90 degree/45 degree) Stacking cloth.For the staples of each layer of fixation, identical Fypro is used.

As shown in table 1, the productivity ratio of complex yarn of the invention is high, and the formed body manufactured using the complex yarn Tensile strength, impact strength it is high.On the other hand, as shown in comparative example 1,2, due to adding up to for the reinforcing fiber in complex yarn Sectional area is not in prescribed limit, thus the output of complex yarn is low, and impact strength is also low.Although comparative example 3,4 outputs Height, but because total sectional area of 1 beam reinforcing fiber is not in prescribed limit, the infiltration of formed body because obtained from is poor, The tensile strength of formed body, the performance of impact strength are low.

Industrial applicability

The structure member of the complex yarn and cloth and silk of the present invention as various machineries, automobile etc. etc., require high-caliber machine The reinforcing material of the material of tool physical property, and the composite molding as thermoplastic fibre composite and thermoplastic resin composition Body has industrial applicability.

Claims (10)

1. a kind of complex yarn, it is the composite yarn being made up of the reinforcing fiber beam comprising more reinforcing fibers and thermoplastic resin Line, wherein, total sectional area of the reinforcing fiber in reinforcing fiber described in 1 beam is 0.00005cm²~0.0022cm², it is described multiple Total sectional area of reinforcing fiber in yarns is 0.0007cm²~0.0085cm²。

2. complex yarn as claimed in claim 1, it has reinforcing fiber beam described in multi beam.

3. complex yarn as claimed in claim 1 or 2, wherein, R μm of the single fiber diameter of the reinforcing fiber and density Dg/ cm³Product RD be 5 μm of g/cm³~100 μm of g/cm³。

4. such as complex yarn according to any one of claims 1 to 3, wherein, the outer peripheral face of the reinforcing fiber beam is by described Thermoplastic resin covers.

5. such as complex yarn according to any one of claims 1 to 3, it is to the reinforcing fiber beam and the thermoplastic resin The fiber of fat carries out complex yarn obtained from mixed fibre.

6. a kind of manufacture method of complex yarn, it is to answer the reinforcing fiber beam comprising more reinforcing fibers and thermoplastic resin The manufacture method of the complex yarn of conjunction, wherein, it is by total sectional area of the reinforcing fiber in reinforcing fiber described in 1 beam 0.00005cm²~0.0022cm²Reinforcing fiber beam and the thermoplastic resin it is compound, so as to will be strong in the complex yarn Total sectional area of chemical fibre dimension is adjusted to 0.0007cm²~0.0085cm²。

7. the manufacture method of complex yarn as claimed in claim 6, wherein, it is 0.00005cm by total sectional area²~ 0.0022cm²Reinforcing fiber beam and the thermoplastic resin it is compound and pre-composite yarn is made, and by the more pre-composite yarns Line carries out and silk and/or plying, so as to which total sectional area of the reinforcing fiber in the complex yarn is adjusted into 0.0007cm² ~0.0085cm²。

8. the manufacture method of complex yarn as claimed in claims 6 or 7, wherein, fibre is strengthened to described by fluid intertexture method The fiber of dimension beam and the thermoplastic resin carries out mixed fibre.

9. a kind of cloth and silk, wherein, complex yarn according to any one of claims 1 to 5 is included in warp and/or parallel.

10. a kind of manufacture method of the cloth and silk described in claim 9, wherein, weaved using rapier loom.