CN103502173B - Glass fiber strands and comprise its enhancing product - Google Patents

Abstract

The present invention is provided to apply the aqueous size composition of glass fibre and with the fluoropolymer resin of the glass fiber reinforcement being at least partly coated with this aqueous size composition.In some embodiments, the size composition of the present invention shows by wherein there is the advantageous property that acid amide component causes.

Description

Glass fiber strands and comprise its enhancing product

Cross-Reference to Related Applications

This application claims U.S. Patent application preferential of the Serial No. 13/075,640 submitted on March 30th, 2011 Power, and this U.S. Patent application be on November 10th, 2008 submit to Serial No. 12/267,963 at first U.S. Patent application Part continuation application, this Serial No. 12/267,963 at first U.S. Patent application according to 35 U.S.C. § 119 (e) requirements The preference of the U.S. Provisional Patent Application of the Serial No. 61/002,370 that on November 8th, 2007 submits to, in these applications The full content of each is all incorporated by reference into herein.

Technical field

The present invention relates to glass yarn sizing composition, the glass fibre of starching, glass fiber strands (strands), with And the goods with the glass fiber reinforcement of starching.

Background technology

The size composition that can be used to give desired performance is typically applied to glass after glass fibre shapes On fiber.Term " size composition (sizing composition) " used herein, " slurry (sizing) ", " viscous Knot agent compositions ", " binding agent " or " spreading mass (size) " refer to the coating composition that is applied over after forming on long filament.? In some embodiments, the most immediately size composition is applied over fiber filament.Size composition can run through with After procedure of processing in protection is provided, described procedure of processing wherein fiber is through those of contact point, as by fibre Peacekeeping fiber strand is wound up into that build package (forming package) is upper, it is water base to be dried or solvent base size composition is to remove Water or solvent, add from a package (package) be twisted to bobbin, warping to be to be placed in the warp thread being typically used as in fabric by yarn The biggest package on, under wet or drying condition chopped, slubbing become bigger bundle or stock combination (groups of Strands), unwinding is for use as strengthening in thing and other downstream process.

It addition, when being positioned on the fiber strengthening polymeric matrix in the manufacture of composite and other products, on Paste composition can serve both functions.In some applications, size composition can provide protection and may be provided for fibre The compatibility between dimension and matrix polymer or resin.The most in some applications, by weaving and supatex fabric, pad, The glass fibre of rove and chopped stand (chopped strand) form is compounded with resin such as thermosetting resin and thermoplastic resin.

Summary of the invention

General introduction

Embodiment of the present invention relate to the aqueous size composition of glass fibre.And, the embodiment party of the present invention Case further relates to comprise the glass fibre of at least one glass fibre being at least partially coated with aqueous size composition of the present invention Stock.Be at least partially coated with the glass fiber strands of aqueous size composition of the present invention can be used in for include thermoplasticity and/ Or thermosetting resin interior various resins encapsulating, impregnate and strengthen application in.

Embodiment of the present invention provide the aqueous size composition comprising acid-amine component, this acid-amine component comprise with The molecule of at least one amine of at least one phosphoric acid and/or vitriolated molecular association.In some embodiments, at least one At least one phosphoric acid of molecule and this or the vitriolated molecule of planting amine are interacted by Louis's Acid-Base and associate.

In some embodiments, the amine in acid-amine component comprises one or more and is generally used for glass yarn sizing Amine chemical species in compositions, include but not limited to amino silicane coupling agent and amine lubricant.In some embodiments, Amine in acid-amine component includes amidine oxazolines, acid amidine oxazolines, ethoxylation amine oxide, poly aminolipid fatty acid derived Thing, or its mixture.

Additionally, in some embodiments, the phosphoric acid in acid-amine component includes phosphorous acid (phosphorous Acid), hypophosphorous acid (hypophosphorus acid), phosphonic acids, organic phosphorous acids (organophosphorus acids), phosphorus Acid or its mixture.It addition, in some embodiments, sulfur acid includes sulfonic acid, organic sulfonic acid class, acid sulphite (hydrogen sulfite), sulfurous acid, sulphuric acid or its mixture.In some embodiments, phosphoric acid or sulfur acid can United States Patent (USP) 6 including Schell etc., the sour form of the stabilizer described in 207,737, this patent is merged in by quoting Herein.

According to some embodiments of the present invention, the molecule of at least one amine and at least one phosphoric acid and/or sulfur acid Molecule by electrostatic interaction, covalent bond, dipolar interaction, hydrogen bond or Van der Waals interact or a combination thereof and form Close.In some embodiments, at least one phosphoric acid and/or vitriolated molecule neutralize at least one amine at least in part Molecule.Therefore, in some embodiments, phosphoric acid and/or sulfur acid can help to control aqueous size composition of the present invention PH value.

In some embodiments of the aqueous size composition of the present invention, acid-amine component comprises phosphorous with at least one The molecule of at least one amine of the molecular association of acid and/or sulfur acid and at least one other acid.In some embodiments In, this at least one other acid is selected as neutralizing amine official's energy of the amine molecule not associated with described phosphoric acid or sulfur acid Group.When neutralizing the amine functional group not associated with described phosphoric acid or sulfur acid, this at least one other acid can also help Control the pH value of aqueous size composition.

In some embodiments, the pH desired by the offer of aqueous size composition according to neutralizing amine functional group and help The ability of value selects at least one other acid described.In one embodiment, at least one other acid includes carboxylic acid. According to some embodiments, carboxylic acid can include alkanoic acid, include but not limited to formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, Enanthic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid, stearic acid, or its mixture.In other embodiments, carboxylic acid can include not Saturated carboxylic acid, such as aromatic carboxylic acid, acrylic acid or derivatives thereof.In some embodiments, carboxylic acid can include fatty acid or Keto acid, such as acetone acid and acetoacetic acid.In some embodiments, at least one other acid include carbonic acid, ascorbic acid, Or its mixture.

In another embodiment, the invention provides the size composition comprising acid-aminosilane ingredient, this acid-ammonia Base silane component comprises and at least one phosphoric acid and/or the molecule of at least one amino silane of vitriolated molecular association. Amino silane can include any amino silane for size composition well known by persons skilled in the art.Some embodiment party In case, such as amino silane can include aminopropyltrialkoxy silanes, such as gamma-amino propyl trimethoxy silicane and γ aminopropyltriethoxy silane, beta-aminoethyl triethoxysilane, N-beta-aminoethyl amino-propyl trimethoxy Silane, 3-aminopropyldimethoxy silane, or its mixture.Additionally, be suitable for associating with at least one amino silane contains Phosphorus and sulfur acid are consistent with specifically described herein those.

In some embodiments, acid-aminosilane ingredient comprises and at least one phosphoric acid and/or sulfur acid and extremely The molecule of at least one amino silane of the molecular association of few a kind of other acid.In some embodiments, at least one is another Outer acid includes carboxylic acid as described herein.

In some embodiments, acid-amine component such as acid-amino silane can give the one-tenth desired by size composition Film properties so that can eliminate or substantially reduce the amount of single film-forming components in size composition.By offer comprise with extremely The higher molecular weight chemical species of the molecule of at least one amine of few a kind of phosphoric acid and/or vitriolated molecular association, acid-amine Component can aid in film forming.

But, in some embodiments, the size composition of the present invention can comprise at least one film former further, It supplements any film forming characteristics provided by acid-amine component.In one embodiment, such as size composition comprises at least one Kind of film former and acid-amine component, this acid-amine component comprises with at least one phosphoric acid and/or vitriolated molecular association extremely The molecule of few a kind of amine.

Alternatively, when can give the film forming characteristics desired by the size composition of the present invention due to acid-amine component, one In a little embodiments, the size composition of the present invention does not comprise the chemical species acting mainly as film former.By offer comprise with The higher molecular weight chemical species of the molecule of at least one amine of at least one phosphoric acid and/or vitriolated molecular association, acid- Amine component can aid in film forming.

In some embodiments, the size composition of the present invention can comprise one or more coupling agents, profit further Lubrication prescription, biocide and/or antifoaming agent.In coupling agent and/or lubricant comprise some embodiments of amine functional group, even Connection agent and/or lubricant are in addition to outside any amino silane of the amino-functional lubricant that participation acid-amine component is formed.

Some embodiments of the present invention provide to comprise and are at least partially coated with size composition of the present invention at least The glass fiber strands of one glass fibre.In some embodiments, the size composition of the present invention is main slurry (primary sizing).In other embodiments, the size composition of the present invention is auxiliary slurry (secondary sizing).Term is " main Slurry " refer to be applied over immediately the size composition of fiber after fibre forming.Term " auxiliary slurry " refers to applying main slurry After be applied over the compositions of fiber.

In some embodiments, the starching group of the present invention of at least one film former and acid-amine component will such as be comprised Compound as main slurry application at least one glass fibre.Acid-amine component will be comprised subsequently but there is no single film former Size composition as auxiliary slurry application at least one glass fibre described.Alternatively, in other embodiments, such as will Comprise acid-amine component but do not have the size composition of the present invention of single film former as main slurry application at least one glass Fiber, and the acid-amine component size composition of the present invention with at least one film former will be comprised as auxiliary slurry application subsequently In at least one glass fibre described.

Embodiment of the present invention consider any size composition specifically described herein decide slurry or auxiliary slurry Purposes.The most main slurry comprises in some embodiments of acid-amine component, and the auxiliary slurry applied subsequently does not comprise acid-amine group Point.Additionally, the most auxiliary slurry comprises in some embodiments of acid-amine component, the main slurry being applied over glass fibre does not wraps Containing acid-amine component.

Comprise some of glass fiber strands of at least one fiber being at least partially coated with size composition of the present invention Embodiment can include continuous stock (continuous strand) or chopped stand (chopped strand).And, according to one A little embodiments, continuous glass fibre stock can be wound into single package such as build package or uniaxial direct tensile package.

In some embodiments, the glass fiber strands of the present invention comprises the glass fibre of a diameter of at least 21 microns.? In some embodiments, glass fiber strands comprises the glass fibre of diameter up to about 35 microns.In some embodiments, Glass fiber strands comprises the glass fibre of diameter at least about 22 microns.In some embodiments, glass fiber strands comprises mark Claim the glass fibre of diameter about 24 microns.In some embodiments, comprise larger diameter fiber and (be greater than about 21 micro- Rice) glass fiber strands can be used as in the composite to strengthen thing and may result in acquisition advantageously to have and utilize small diameter The composite of the physical property that fibre-reinforced composite is suitable.

In another aspect, the invention provides thermoplasticity or the same with thermosetting compound material of glass fiber reinforcement.At some In embodiment, the thermoplasticity of glass fiber reinforcement or same with thermosetting compound material comprise thermoplastic resin or thermosetting resin and extremely Partially it is coated with at least one glass fibre of size composition of the present invention.Provided herein it is at least partially coated with this The glass fibre of invention size composition can have any desired length.In some embodiments, at least in part The glass fibre being coated with size composition of the present invention has the size being applicable to long fiber reinforcement application, and described application includes G- LFT (granular-long fiber thermoplastic material) and D-LFT (directly-long fiber thermoplastic material).

Any desired thermoplasticity or thermosetting resin can be at least partially coated with size composition of the present invention Glass fibre is used together.In some embodiments, can include gathering with the thermoplastic resin of the glass fiber reinforcement of the present invention Alkene such as polyethylene and polypropylene, polyamide, polyphenylene oxide, polystyrene type or polyester such as polybutylene terephthalate (PBT) And polyethylene terephthalate (PET) (PBT).In some embodiments, by the heat of the glass fiber reinforcement of the present invention Thermosetting resin includes polyester resin, polyimide resin, phenolic resin and epoxy resin.

In another embodiment, the invention provides and prepare thermoplasticity or the same with thermosetting compound material of glass fiber reinforcement Method.In one embodiment, the method for the thermoplasticity or same with thermosetting compound material of preparing glass fiber reinforcement includes carrying For multiple glass fibre, coat the plurality of glass fibre at least in part with size composition of the present invention, and by multiple coatings Glass fibre arrange in thermoplasticity or thermosetting resin.Glass fibre provided herein can be assembled into continuous glass fibre Stock.Glass fiber strands can be chopped, and keeps continuously or is assembled into rove for strengthening application.

These and other embodiment it is more fully described in following detailed description.

Describe in detail

For the purpose this specification, unless otherwise indicated, use in the description is expressed as component, reaction condition etc. All numerical value will be understood as being modified by term " about " in all scenario.Therefore, unless stated to the contrary, in following description Numerical parameter described in book is approximation, its can depend on seeking by the present invention obtain desired by performance and become Change.At least and be not intended to limit doctrine of equivalents and be applied to the scope of claims, each numerical parameter should at least root According to there is the numerical value of reported significant digit and by using the typically technology of rounding off to understand.

Although the numerical range and the parameter that describe the wide scope of the present invention are approximations, but are described in specific embodiment Numerical value is reported as precisely as possible.But, any numerical value contains inherently by discovery in the test measurement of each of which The certain error that standard deviation necessarily leads to.Additionally, all ranges disclosed herein will be understood to comprise and wherein comprises Any and all subranges.Such as, described scope " 1-10 " is considered as being included between minima 1 and maximum 10 Any and all subrange of (and including end value)；That is, with minima 1 or bigger beginning, such as 1-6.1, with maximum 10 or less end, all subranges of such as 5.5-10.It addition, any list of references being referred to as " being expressly incorporated herein " is understood For being generally introduced with it.

It is further noted that the singulative used in this manual " a kind of ", " one " and " described (being somebody's turn to do) " include multiple Number object, unless understood and be limited to an object clearly.

Some embodiments of the present invention relate to the new size composition of glass fibre.Starching group specifically described herein Compound relates generally to aqueous size composition.Some embodiments of the size composition of the present invention can with various resins, including Thermosetting resin, thermoplastic resin and/or other fluoropolymer resin are compatible.Some embodiments of the present invention further relate to use starching The glass fiber strands of compositions coating.It addition, some embodiments of the present invention relate to the goods introducing glass fiber strands, such as Fibre-reinforced polymeric material.

By from its glass fibre preparation, assemble and apply in purposes the present invention is usually discussed.But, ability Field technique personnel are it will be appreciated that the present invention can be used for the processing of other textile material.

Some embodiments of the glass fiber strands of the present invention can have various performance.Such as, the one of glass fiber strands A little embodiments can coat at least partially with the size composition of the present invention, obtains showing with many resin compatibles simultaneously The broken filament of acceptable level, desired wearability and/or desired stock convergence (strand integrity) with And the glass fiber strands of at least partly coating of other performance.

In some embodiments, the invention provides the size composition comprising acid-amine component, this acid-amine component bag Contain and at least one phosphoric acid and/or the molecule of at least one amine of vitriolated molecular association.In some embodiments, extremely At least one phosphoric acid of molecule and this or the vitriolated molecule of few a kind of amine are interacted by Louis's Acid-Base and associate.

In some embodiments, the amine of acid-amine component includes having and can form, with phosphoric acid or sulfur acid, associated Individual or any amine of multiple amido.In some embodiments, amine includes primary amine, secondary amine or tertiary amine or its mixture.

In some embodiments, the amine of acid-amine component includes being generally used in the size composition of glass fibre One or more amine chemical species, it includes amino silicane coupling agent and amine lubricant.In some embodiments, acid-amine group The amine divided includes amino silicone alkanes, imidazolines, alkyl imidazoline class, ethoxylation amine oxide, polymine, poly ammonia Base derivative of fatty acid or its mixture.Suitably amino silane can include well known by persons skilled in the art for starching Any amino silane of compositions.In one embodiment, such as amino silane can include aminopropyl tri-alkoxy silicon Alkane, such as gamma-amino propyl trimethoxy silicane and γ aminopropyltriethoxy silane, beta-aminoethyl triethoxysilicane Alkane, N-beta-aminoethyl amino-propyl trimethoxy silane, 3-aminopropyldimethoxy silane, or its mixture.

In some embodiments, the acid of acid-amine component can include phosphoric acid.In some embodiments, phosphoric acid Phosphorus atoms can be any one in 3,4 or 5 oxidation state.In other embodiments, the phosphorus atoms of phosphoric acid is not the highest Oxidation state 5.In some embodiments, phosphoric acid includes phosphorous acid (phosphorus acid), hypophosphorous acid (hypophosphorus acid), hypophosphoric acid (hypophosphoric acid), phosphonic acids, phosphoric acid or organic phosphorous acids (organophosphorus acids)。

Organic phosphorous acids be applicable to some embodiments of the present invention can include those of formula (I)

Wherein R¹Be-alkyl ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl or-heteroaryl and R²Be- H ,-alkyl ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl or-heteroaryl.

In another embodiment, it is adaptable to the organic phosphorous acids in some embodiments of the present invention can include formula (II) those

Wherein R³And R⁴Independently selected from-H ,-alkyl ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl Or-heteroaryl.

In some embodiments, organic phosphorous acids can include phenyl phosphinic acid, diphenyl phosphonic acid, 4-methoxybenzene Base phosphonic acids, 4-hydroxy phenyl phosphonic acids, 4-hydroxybutyl phosphonic acids, diphenyl methyl phosphonic acids (benzylhydrylphosphonic Acid), benzylphosphonic acid, butyl phosphonic acids, dodecyl phosphonic acid, heptadecyl phosphonic acids, methylbenzylphosphonic acid, naphthyl methyl phosphonic acids, Octadecylphosphonic acid, octyl phosphonic acid, amyl group phosphonic acids, phenyl-phosphonic acid, styryl phosphonic acid or its mixture.

In some embodiments, the acid of acid-amine component can include sulfur acid.In some embodiments, sulfur acid Sulphur atom can be any one in 2,4 or 6 oxidation state.In other embodiments, vitriolated sulphur atom is not the highest Oxidation state 6.In one embodiment, sulfur acid include sulfonic acid, organic sulfonic acid, acid sulphite, sulfurous acid, sulphuric acid or its Mixture.

In some embodiments, acid-amine component comprise with at least one phosphoric acid and/or sulfur acid and at least one The molecule of at least one amine of the molecular association of acid additionally.In some embodiments, at least one other acid include as Carboxylic acid specifically described herein.

According to some embodiments of the present invention, the molecule of at least one amine passes through electrostatic interaction, covalent bond, hydrogen Key, dipolar interaction or Van der Waals interact or a combination thereof is formed with at least one phosphoric acid and/or vitriolated molecule Close.In one embodiment, such as, the molecule of at least one amine by electrostatic interaction and at least one phosphoric acid point Son associates, as shown in formula (III).

Wherein R¹-R⁴Independently selected from-H ,-alkyl ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl or- Heteroaryl.While not wishing to be bound by any theory, it is believed that phosphoric acid Louis's Acid-Base interact in by electrophilic Hydrion is supplied to amido to neutralize described amido.Positive charge is placed on the nitrogen of amido by the transfer of hydrogen, thus promotes and dissociation Phosphoric acid formed electrostatic interaction.When neutralizing amine functional group alkaline, phosphorous and/or sulfur acid molecule can help control The pH of controlling the water circulation size composition.

In some embodiments, the amine molecule of acid-amine complex comprises the list for associating with phosphoric acid or sulfur acid One amine functional group.In some embodiments, amine molecule comprises for forming with one or more phosphoric acid and/or sulfur acid molecule The multiple amine functional groups closed.

In some embodiments, such as, in phosphorous and/or vitriolated molecule and the amine of substantially all of amine molecule Functional group.In other embodiments, phosphoric acid and/or vitriolated molecule neutralize the amine less than substantially all of amine molecule Functional group.

In some embodiments, the size composition of the present invention comprises phosphoric acid and/or the sulfur acid of stoichiometric proportion Molecule and amine molecule.In other embodiments, the size composition of the present invention comprise non-stoichiometric phosphoric acid and/ Or vitriolated molecule and amine molecule.

In some embodiments, the mol ratio of phosphoric acid and/or vitriolated molecule and amine molecule is based in amine molecule The mole of the amine functional group existed.In these embodiments, such as, phosphoric acid and/or sulfur acid are determined according to formula (IV) Mol ratio with amine:

In some embodiments, the mol ratio determined according to formula (IV) is less than about 1.In some embodiments, according to The mol ratio that formula (IV) determines is less than about 0.75 or less than about 0.5.In some embodiments, according to formula (IV) determine mole Ratio less than about 0.25 or less than about 0.10.In other embodiments, the mol ratio determined according to formula (IV) is greater than about 1.One Planting in embodiment, the mol ratio determined according to formula (IV) is greater than about 2 or greater than about 3.

In the operation of formula (IV), such as, amine molecule can comprise two amine functional groups.Therefore, if at sizing composition Thing provides 1 molar amine molecule, then there are 2 molar amine functional groups.If comprising amine molecule additionally, 1 mole of phosphoric acid added Size composition and do not have vitriolated molal quantity to add, then formula (IV) becomes (1+0)/2, and it provides phosphoric acid and amine Mol ratio be 0.5.

In some embodiments, based on total solid, size composition comprises the acid-amine of consumption at most about 100 weight % Component.Based on total solid, size composition can comprise consumption the most at most about 80 weight %, or at other The acid-amine component of at most about 60 weight % in embodiment.In some embodiments, based on total solid, size composition bag The acid-amine component of 1 weight % it is greater than about containing consumption.In some embodiments, based on total solid, size composition comprises consumption The greater than about acid-amine component of 10 weight %.In one embodiment, based on total solid, size composition comprises consumption and is more than The acid-amine component of 40 weight %.In some embodiments, size composition can comprise and effectively gives size composition and wished The acid-amine component of any amount of the performance hoped.

As described herein, in some embodiments, the acid-amine component of aqueous size composition includes acid-amino silicone Alkane component, this acid-aminosilane ingredient comprises at least one ammonia with at least one phosphoric acid and/or vitriolated molecular association The molecule of base silane.The molecule of at least one amino silane by electrostatic interaction, covalent bond, dipole-dipole interaction, Hydrogen bond or Van der Waals interact or a combination thereof and at least one phosphoric acid and/or vitriolated molecular association.Real at some Execute in scheme, in the formation of acid-aminosilane ingredient, the molecule of at least one amino silane by least one phosphoric acid and/ Or vitriolated molecule at least partly neutralizes.In one embodiment, such as, the phosphoric acid of the sour form comprising stabilizer can By with in upper formula (III) provide consistent in the way of at least part of neutralization of ammonia base silane.

The non-limiting examples of commercially available amino silane includes the A-1100 γ-ammonia deriving from OSi Specialties Base propyl-triethoxysilicane, A-1120N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, and other A- Amino-functional silane in 1100 series, and derive from the Degussa AG of Dusseldorf ,GermanyAMEO APTES.

In some embodiments, the size composition of the present invention can comprise at least one further can supplemental acid-amine The film former of the film forming characteristics of component.In some embodiments, the size composition of the present invention can comprise multiple film former. Not inconsistent with the purpose of the present invention any film former well known by persons skilled in the art can be used.In some embodiments In, suitable coalescing agents such as can be compatible with one or more fluoropolymer resins.

The selection of film former can be depended on improving resin by being enhanced and using the size composition painting comprising film former The fluoropolymer resin of the compatibility between the glass fibre covered.It addition, the selection of film former can depend on the fiber treating starching Type.

Many film former can be used in each embodiment of the present invention.Film forming for each embodiment of the present invention The non-limiting examples of agent includes the polyolefin of chemical modification, polyurethane, epoxide, or its mixture or aqueous dispersion. In some embodiments, film former can include polyacrylate, polyester or poly-(vinyl acetate).

In some embodiments, the polyolefinic film former comprising chemical modification is provided as water-based emulsion.Term " polyolefin of chemical modification " refers to sour or the anhydride modified amorphous or polyolefin of crystallization, such as by being described in detail in U.S. Method in state's patent No.3,416,990, United States Patent (USP) No.3,437,550 and United States Patent (USP) No.3,483,276 prepare that A bit, each patent is both incorporated herein by reference.The discussion of these polyolefin, their modification and emulsifying can be special in the U.S. Profit No.5, finds in 130,197, and this patent is incorporated herein by.

In some embodiments of the present invention, the example of the carboxylation polyacrylic polymer that can serve as the crystallization of membrane is Can be from Bloomington, the Hercules of Del, Inc. are commercially availableType resin.Amorphous The example of carboxylation polyacrylic polymer be can be from Longview, the Westlake Chemical Corporation of TX is purchased ObtainE-43 resin.Another kind of suitably film former material is can be at trade mark Novacer 1841 breast From the water-based emulsion of EPOLENE E-43 resin commercially available for Byk-Cera under liquid.Can be from Chemical Corporation CHEMCOR 43C30 unbodied carboxylation polypropylene water-based emulsion commercially available for of America applies to some embodiment party Another example of the film former of case.Another of water polyolefin emulsion that can serve as membrane in some embodiments can Commercially available form is with trade mark Protolube RL-5440 poly-third from National Starch, Procter Division The carboxylation amorphous polypropylene that alkene emulsion is sold.Another kind of suitably film former is can be from the DSM of Holland, and B.V. is with trade mark The water-based emulsion of the polypropylene emulsion of the maleic anhydride grafting of the high molecular that Neoxil 605 is commercially available.

Suitable film formers for some embodiments includes polyurethane.In some embodiments, polyurethane film-forming material Material can be used for polyamide and strengthens application.In some embodiments, polyurethane film-forming compositions provides as water-based emulsion, Such as provided by Crompton Corporation-Uniroyal ChemicalSeries, bag Include but be not limited to,W-290H andW-296.Commercially available is poly- The other example of urethane aqueous dispersion includes the Aquathane 516 deriving from Reichhold Chemical Company and obtains From the Hydrosize U2-01 of Hydrosize Technologies, Inc.

In some embodiments, polyurethane finishing agent includes by organic isocyanate or polyisocyanates with organic many The aqueous solution of the polyether polyols with reduced unsaturation that the reaction between polyethers or polyester polymers that hydroxylated compounds or hydroxyl terminate is formed. In some embodiments, dispersions of polyurethanes can contain crosslinked group.

Another example of suitable polyurethane is derived from the water of the polyether-polyurethane NAJ-1037 of Bayer Chemical Property emulsion.It addition, polyurethane can be a part for the dispersion comprising polyurethane and blocked isocyanate.Such as, below Polyurethane/blocked isocyanate emulsion go for the size composition of the present invention: WITCOBOND 60X (Crompton), Baybond 403(Bayer)、Baybond PU-130(Bayer)、Baybond XP-7055(Bayer)、Nopco D641 (Henkel), Neoxil 6158 (DSM) and Vestanat EP-DS-1205 (Degussa).

In some embodiments of the present invention, at least one film former can include epoxide composition.At some In embodiment, epoxide filmogen can be used for polyethylene terephthalate or polybutylene terephthalate (PBT) increases Strong application.According to some embodiments, including as the suitable epoxide composition of film former can be from Columbus, Ohio EPON epoxide commercially available for Hexion Specialty Chemicals and EPI-REZ epoxide.

In some embodiments, based on total solid, the size composition of the present invention comprises consumption at most about 85 weight % At least one film former.In other embodiments, based on total solid, size composition comprises consumption at most about 75 weight % At least one film former.In some embodiments, based on total solid, size composition comprises consumption at most about 60 weight % At least one film former.In some embodiments, based on total solid, size composition comprises consumption at most about 50 weight % At least one film former.In another embodiment, based on total solid, size composition comprises consumption and is greater than about 5 weight % At least one film former.

In addition to participating in any amino-functional coupling agent that acid-amine component is formed, the one of the size composition of the present invention A little embodiments comprise one or more non-amino-functional coupling agents further.The non-limiting examples of non-amino-functional coupling agent Including γ-isocyanate group propyl-triethoxysilicane, vinyl-trimethoxy silane, vinyl-triethoxysilane, allyl Base-trimethoxy silane, mercaptopropyi trimethoxy silane, Mercaptopropyltriethoxysilane, glycidoxypropyl group three second TMOS, glycidoxypropyltrime,hoxysilane, 4,5-epoxy cyclohexylethyl trimethoxy silane, chloropropyl three Methoxy silane and chloropropyl triethoxysilane.

The non-restrictive embodiments of the size composition of the present invention can also comprise multiple coupling agent, and some of them can be joined With acid-amine component formed and other are not involved in the formation of acid-amine component.The use of multiple coupling agent can advantageously obtain To the size composition compatible with various resins (including thermosetting resin, thermoplastic resin and other resin).For the present invention The amount of each coupling agent in size composition and kind can be based on resin compatible, impacts on glass fiber strands performance (the most less broken filament, wearability, stock convergence and stock rubbing action) and the phase of other component with size composition Capacitive selects.

In some embodiments, based on total solid, the size composition of the present invention comprises consumption at most about 40 weight % At least one coupling agent.In another embodiment, based on total solid, size composition comprises consumption at most about 25 weight % Or at most about 15 at least one coupling agents of weight %.In some embodiments, based on total solid, size composition comprises use Amount at most about 10 weight % or at least one coupling agent of at most about 5 weight %.In other embodiments, based on total solid, Size composition comprises consumption at most about 3 weight % or at least one coupling agent of at most about 1 weight %.Above-mentioned amount is corresponding to upper Paste composition is not involved in the coupling agent that acid-amine component is formed.

In one embodiment, the size composition of the present invention does not comprise coupling agent.

In some embodiments, the size composition of the present invention can comprise at least one lubricant further.Permissible Use not inconsistent with the purpose of the present invention any lubricant well known by persons skilled in the art.Lubricant can such as be used for To help internal lubrication (abrasion of such as fiber and fiber) and to help external lubrication (such as glass in the size composition of the present invention Glass and the abrasion of contact point).In some embodiments, at least one lubricant can include that at least one cation lubricates Agent.In other embodiments, at least one lubricant can include at least one non-ionic lubricant.In another embodiment In, at least one lubricant can include at least one cationic lubricant and at least one non-ionic lubricant.

In embodiments of the invention, cationic lubricant can such as be adapted to assist in internal lubrication, such as by subtracting The abrasion of the youthful and the elderly's silk and long filament or glass and glass (glass-to-glass).It is said that in general, those skilled in the art are The most of cationic lubricants known can be used in embodiment of the present invention.Sun be applicable to size composition of the present invention from The non-limiting examples of sub-lubricant includes having the lubricant of amido, have the lubricant of ethoxylation amine oxide and have The lubricant of ethoxylated fatty amides.The non-limiting examples of the lubricant with amido is modified polymine, such as EMERY 6717, it is can be from Charlotte, the polyethylene of the partial amides commercially available for Pulcra Chemicals of NC Imines.Another example that can be used for the cationic lubricant in embodiment of the present invention is ALUBRASPIN 226, and it is can Polymine from the partial amides commercially available for BASF Corp. of Parsippany, New Jersey.

In some embodiments, lubricant includes the partial ester of one or more branched carboxylic acids copolymers.Described partial ester and Its derivant is to have pendant hydrocarbon chain and the polymer of ethoxylation ester chain.Suitably the partial ester of branched carboxylic acids copolymer can business Available from form be with trade mark Ketjenlube 522 partial ester from the Akzo Chemie America of Chicago, Illinois (conduct in the pastGE 202 partial ester sell) obtain that.

In some embodiments, non-ionic lubricant includes at least one wax.It is applicable to the example bag of the wax of the present invention Include the oxidized derivatives of Tissuemat E, paraffin, polypropylene wax, microwax and these waxes.It is applicable to the Tissuemat E of the present invention One example is Protolube HD-A, and it is can be from Pittsburgh, the height commercially available for Bayer Corporation of Pa Density polyethylene wax.The example of the paraffin being applicable to embodiment of the present invention is Elon PW, its be can from Concord, N.C's The paraffin wax emulsions that Elon Specialties is commercially available.

As provided herein, in some embodiments, the lubricant comprising one or more amine functional group can be joined Formation with acid-amine component.

In some embodiments, based on total solid, size composition comprises at least the one of consumption at most about 10 weight % Plant lubricant.In another embodiment, based on total solid, size composition comprises at least the one of consumption at most about 5 weight % Plant lubricant.In another embodiment, based on total solid, size composition comprises at least the one of consumption less than about 1 weight % Plant lubricant.In some embodiments, based on total solid, size composition comprises at least one of consumption at least 1 weight % Lubricant.Above-mentioned amount is corresponding to being not involved in the lubricant that acid-amine component is formed in size composition.

In some embodiments, the size composition of the present invention can comprise at least one biocide further. Biocide can add relevant to yeast, mycete, aerobe and other biological product to avoid as preventive measure Potential problems.The known to those skilled in the art organic growth controlled in glass yarn sizing composition any Biocide is generally used in the embodiment of size composition of the present invention.Can be used for biocide non-of the present invention Limit example include organotin biocide, sulfonium methylide cyanate (methylene thiocyanate) biocide, Nitro biocide and chlorination and brominated compound.The commercially available of embodiment for size composition of the present invention obtains The non-limiting examples of the biocide obtained is derived from Bioban BP-30's or Schulke and Mayr of Dow ChemicalDF35。

In some embodiments, the size composition of the present invention has the pH of about 5.0-about 10.5.Other embodiment party In case, the size composition of the present invention has the pH of about 6.0-about 8.0.In some embodiments, the sizing composition of the present invention Thing can have less than about 5.0 or the pH of greater than about 10.5.In some embodiments, the pH of regulation size composition falls into and appoints What aforementioned pH scope.

Some embodiments of the present invention provide to comprise and are at least partially coated with size composition of the present invention at least The glass fiber strands of one glass fibre.In some embodiments, the size composition of the present invention is Your Majesty's paste composition.

In some embodiments, such as, the present invention of at least one film former and at least one acid-amine component will be comprised Size composition is applied at least one glass fibre as Your Majesty's paste composition.Subsequently, acid-amine component will be comprised but not have single The size composition of only film former is applied at least one glass fibre described as auxiliary size composition.Alternatively, at it In its embodiment, such as, acid-amine component will be comprised but there is no the size composition of the present invention of single film former as main slurry Material is applied at least one glass fibre, and will comprise the starching group of the present invention of acid-amine component and at least one film former subsequently Compound as auxiliary slurry application at least one glass fibre described.

In some embodiments, comprise and be at least partially coated with at least one fiber of size composition of the present invention Glass fiber strands can comprise chopped stand.In some embodiments, short glass fiber stock can have about 3mm-about 25mm Length.In other embodiments, short glass fiber stock can have the length of about 5mm-about 25mm.Implement at another In scheme, short glass fiber stock has less than about 5mm or the length of greater than about 25mm.

Comprise some of glass fiber strands of at least one fiber being at least partially coated with size composition of the present invention Embodiment can include continuous stock.Additionally, according to some embodiments, continuous glass fibre stock can be wound into single volume Fill such as build package or uniaxial direct tensile package.In some embodiments, will comprise and be at least partially coated with in the present invention Multiple glass fiber strands of at least one fiber of paste composition are assembled into rove.

It would be recognized by those skilled in the art that the present invention can the production of many glass fibre, assemble and apply in real Execute.Not inconsistent with the purpose of the present invention any glass fibre well known by persons skilled in the art can be used.

Generally, the glass fibre of arbitrary diameter can be used to form the glass fiber strands of the present invention and/or for strengthening again Condensation material.In some embodiments, the glass fibre of relatively large diameter can be used to form glass fiber strands and/or for increasing Strong composite.In some embodiments, glass fibre can have the diameter of at least 21 microns.In some embodiments, Glass fibre can have the diameter of the most about 35 microns.The glass fibre used in certain embodiments can have at least The diameter of about 22 microns.In some embodiments, glass fibre may have about the nominal diameter of 24 microns.Real at some Executing in scheme, the glass fiber strands comprising larger diameter fiber (being greater than about 21 microns) is used as in composite Strengthen thing and may result in acquisition advantageously there is the physical property suitable with utilizing the fibre-reinforced composite of small diameter Composite.

Can by appropriate method well known by persons skilled in the art, such as but not limited to, by making glass fibre with quiet State or dynamically coating equipment such as roll coater or band are coated with machine contact, or by spraying, or otherwise by the present invention's Size composition is applied over glass fibre.Can according to manner of application to be used, the feature of the glass fibre treating starching and on The weight of the dry slurry coating desired by intended application of slurry glass fibre, regulates in size composition non-in wide scope The total concentration of volatile component.In some embodiments, size composition can be applied over glass in the shaping operation of fiber Glass fiber.

The amount of the size composition on glass fibre can be measured as " loss on ignition " or " LOI ".Term used herein " loss on ignition " or " LOI " refers to the weight percent of the dry size composition being present on glass fibre determined by equation 1 Ratio:

LOI=100X [(W_{It is dried}-W_Exposed)/W_{It is dried}] (equation 1)

Wherein W_{It is dried}It is that after 220 °F (about 104 DEG C) are dried 60 minutes, the weight of coating adds glass fibre in an oven Weight, and W_ExposedIt is in an oven glass fibre to be heated 20 minutes in 1150 °F (about 621 DEG C) and in exsiccator, be cooled to room The weight of bare glass fiber after temperature.

In some embodiments, the glass fiber strands of the present invention has the LOI of about 0.05-about 1.5.Implement at another In scheme, the glass fiber strands of the present invention has the LOI of about 0.1-about 0.5.In another embodiment, the glass of the present invention Fiber strand has the LOI of about 0.4.

Some embodiments of the present invention relate to thermoplasticity or the same with thermosetting compound material of glass fiber reinforcement.Real at some Executing in scheme, the thermoplasticity of glass fiber reinforcement or same with thermosetting compound material comprise thermoplasticity or thermosetting resin with at least part of Be coated with at least one glass fibre of size composition of the present invention.In some embodiments, by the glass fibers of the present invention The thermoplastic resin that dimension strengthens includes polyolefin such as polyethylene and polypropylene, polyamide, polyphenylene oxide, polystyrene type or polyester Such as polybutylene terephthalate (PBT) (PBT) and polyethylene terephthalate (PET).In some embodiments, with this The thermosetting resin of the glass fiber reinforcement of invention includes polyester resin, polyimide resin, phenolic resin and epoxy resin.

Glass fibre may be used for utilizing chopped stand, company in any moulding technology known to those skilled in the art Continuous stock or its mixture strengthen polymeric matrix.For example, it is possible to by chopped strand stock and matrix polymer resin melt mixed.With After can be with molded composites melt with prepared polymer elements or finished article.In some embodiments, by glass fibre Mix with dry powder mixture with matrix polymer resin.

The glass fibre being at least partially coated with size composition of the present invention can have any desired length.? In some embodiments, it is at least partially coated with the glass fibre of size composition of the present invention and has and be applicable to long fiber reinforcement The size of application (including G-LFT (granular-long fiber thermoplastic material) and D-LFT (directly-long fiber thermoplastic material)).? In some embodiments of fibre-reinforced thermoplastic composite, glass fibre has the draw ratio of about 5-50.Used here as " draw ratio " refer to that the length of glass fibre is divided by glass fiber diameter.In some embodiments, coat at least in part The glass fibre having size composition of the present invention has the draw ratio of at least 100 or at least 200.

In some embodiments, fibre-reinforced thermoplasticity or same with thermosetting compound material comprise any desired amount of at least It is partially coated with the glass fibre of size composition of the present invention.In one embodiment, multiple glass fibre can be down to The amount of about 90 weight % of many composites exists.In another embodiment, multiple glass fibre are with at most composite The amount of about 80 weight % exists.In some embodiments, multiple glass fibre are with about 65 weight % of at most composite Amount exists.In some embodiments, multiple glass fibre exist with the amount of about 10 weight % more than composite.At some In embodiment, multiple glass fibre exist with the amount of about 20 weight % more than composite.In another embodiment, many Individual glass fibre exists with the amount of about 30 weight % more than composite.

In some embodiments, the composite of the present invention may utilize the coating at least in part with relatively large diameter There is the glass fiber reinforcement of size composition as described herein.Such as, some embodiments of composite may utilize diameter Being at least 21 microns, a diameter of at least 22 microns or nominal diameter are of about the glass fiber reinforcement of 24 microns.

In some embodiments, the composite utilizing relatively large diameter glass fibers to strengthen may result in acquisition advantageously There is the composite of the mechanical performance suitable with utilizing the fibre-reinforced composite of small diameter.Polypropylene is thermoplastic resin One example of fat, when utilizing relatively large diameter glass fibers to strengthen, it can have and utilizes small diameter fiber reinforcement with it Time suitable mechanical performance.The limiting examples of these performances includes hot strength, stretch modulus, flexural strength and flexure mould Amount.

Embodiment of the present invention additionally provide the side of thermoplasticity or the same with thermosetting compound material preparing glass fiber reinforcement Method.In one embodiment, the method for the thermoplasticity or same with thermosetting compound material of preparing glass fiber reinforcement includes: offer is many Individual glass fibre, coats the plurality of glass fibre at least in part with the size composition of the present invention, and by the plurality of The glass fibre of coating is arranged in thermoplasticity or thermosetting resin.Glass fibre provided herein can be assembled into continuous glass Glass fiber strand.Glass fiber strands can be chopped, keeps continuous or be assembled into rove and strengthen for thermoplasticity or thermosetting plastics Application.

Detailed description of the invention

Now by following concrete but non-limiting example illustrates some exemplary of the present invention.

Embodiment 1

The non-limiting embodiments of size composition of the present invention is prepared according to following formula:

Sizing instruction (20 liters)

Composition	Consumption (g)	% solid
			Soften water	7000	0
Acetic acid (80%)	87.2	0
			Silane1	523.3	36.13
Hypophosphorous acid (50%)	156.0	8.67
			Film former2	1367.5	53.20
Lubricant3	18.0	2.00
			Biocide4	0.018	0.0007
Want the softening water of filling	10847.9	0

¹DYNASYLAN AMEO APTES, from the Degussa AG of Dusseldorf ,Germany

²Neoxil 604, from the DSM, B.V of Holland

³DAPRAL GE 202, from the Akzo Chemie of Chicago, Illinois

⁴PARMETOL DF35, from Schulke and Mayr

The sizing composition of embodiment 1 is prepared equipped with in the main mixing channel of agitator by being provided by about 7 liters of softening water Thing.The acetic acid of specified amount is added and becomes owner of mixing channel, and by gained solution stirring 5 minutes.After stirring, by the amino silicone of specified amount Alkane adds becomes owner of mixing channel, and by gained solution stirring 10 minutes.Subsequently the hypophosphorous acid of specified amount is added and become owner of mixing channel, and By gained solution stirring 10 minutes.Hypophosphorous acid result in the addition of main mixing channel the acid that comprises amino silane and hypophosphorous acid- Amine component.

The most under agitation the film former of specified amount is added described mixing channel.Hot water is added premix groove, and will refer to Quantitative lubricant adds premix groove.Subsequently gained mixture is stirred 10 minutes with dispersed lubricant.Then lubricant is divided A prose style free from parallelism adds becomes owner of mixing channel.The biocide of specified amount is added and becomes owner of mixing channel, and add softening water to be supplied by formula To 20 liters.The size composition of preparation has the pH value of about 7.5.

Embodiment 2

The non-limiting embodiments of size composition of the present invention is prepared according to following formula:

Sizing instruction (20 liters)

Composition	Consumption (g)	% solid
			Soften water	7000	0
Acetic acid (80%)	87.2	0
			Silane1	523.3	24.07
Hypophosphorous acid (50%)	156.0	5.78
			Film former2	2655.0	68.82
Lubricant3	18.0	1.33
			Biocide4	0.018	0.0005
Want the softening water of filling	9560.4	0

¹DYNASYLAN AMEO APTES, from the Degussa AG of Dusseldorf ,Germany

²Neoxil 604, from the DSM, B.V of Holland

³DAPRAL GE 202, from the Akzo Chemie of Chicago, Illinois

⁴PARMETOL DF35, from Sculke and Mayr

The sizing composition of embodiment 2 is prepared equipped with in the main mixing channel of agitator by being provided by about 7 liters of softening water Thing.The acetic acid of specified amount is added and becomes owner of mixing channel, and by gained solution stirring 5 minutes.After stirring, by the amino silicone of specified amount Alkane adds becomes owner of mixing channel, and by gained solution stirring 10 minutes.Subsequently the hypophosphorous acid of specified amount is added and become owner of mixing channel, and By gained solution stirring 10 minutes.Hypophosphorous acid to the addition of main mixing channel result in provided herein comprise amino silane and The acid-amine component of hypophosphorous acid.

The most under agitation the film former of specified amount is added described mixing channel.

Hot water is added premix groove, and the lubricant of specified amount is added premix groove.Subsequently gained mixture is stirred 10 minutes with dispersed lubricant.Then lubricant dispersion is added and become owner of mixing channel.The biocide of specified amount is added and becomes owner of Mixing channel, and add softening water formula to be complemented to 20 liters.The size composition of preparation has the pH value of about 7.5.

Embodiment 3

The non-limiting embodiments of size composition of the present invention is prepared according to following formula:

Sizing instruction (20 liters)

Composition	Consumption (g)	% solid
			Soften water	7000	0
Acetic acid (80%)	139.6	0
			Silane1	837.4	38.25
Hypophosphorous acid (50%)	156.0	5.74
			Film former2	2124.6	54.69
Lubricant3	18.0	1.32
			Biocide4	0.018	0.0005
Want the softening water of filling	9724.5	0

¹DYNASYLAN AMEO APTES, from the Degussa AG of Dusseldorf ,Germany

²Neoxil 604, from the DSM, B.V of Holland

³DAPRAL GE 202, from the Akzo Chemie of Chicago, Illinois

⁴PARMETOL DF35, from Sculke and Mayr

The sizing composition of embodiment 2 is prepared equipped with in the main mixing channel of agitator by being provided by about 7 liters of softening water Thing.The acetic acid of specified amount is added and becomes owner of mixing channel, and by gained solution stirring 5 minutes.After stirring, by the amino silicone of specified amount Alkane adds becomes owner of mixing channel, and by gained solution stirring 10 minutes.Subsequently the hypophosphorous acid of specified amount is added and become owner of mixing channel, and By gained solution stirring 10 minutes.Hypophosphorous acid to the addition of main mixing channel result in provided herein comprise amino silane and The acid-amine component of hypophosphorous acid.

The most under agitation the film former of specified amount is added described mixing channel.

Hot water is added premix groove, and the lubricant of specified amount is added premix groove.Subsequently gained mixture is stirred 10 minutes with dispersed lubricant.Then lubricant dispersion is added and become owner of mixing channel.The biocide of specified amount is added and becomes owner of Mixing channel, and add softening water formula to be complemented to 20 liters.The size composition of preparation has the pH value of about 7.5.

Embodiment 4

Operation sequence preparation according to embodiment 1 has the non-limiting enforcement of the size composition of the present invention of formula A and B Scheme.Size composition A and B each includes the phosphoric acid comprising hypophosphorous acid, and it results in and comprises amino silane and hypophosphorous acid Acid-amine component.

Sizing instruction (20 liters)

The contrast size composition with formula C, D and E is prepared according to the operation sequence of embodiment 1.Described contrast starching Compositions does not include the phosphoric acid for forming acid-amine component or sulfur acid.In size composition D and E, hypophosphorous acid component by Hydrochlorate-replace from the sodium hypophosphite of Holland's Transmare, B.V. acquisition.Size composition C does not have in addition to acetic acid Acid content.

Sizing instruction (20 liters)

¹DYNASYLAN AMEO APTES, from the Degussa of Dusseldorf ,Germany AG

²50% solution

³Neoxil 605, from the DSM, B.V (35% solid) of Holland

⁴DAPRAL GE 202, from the Akzo Chemie of Chicago, Illinois

⁵DYNASYLAN AMEO APTES, from the Degussa of Dusseldorf ,Germany AG

⁶Neoxil 605, from the DSM, B.V (35% solid) of Holland

⁷DAPRAL GE 202, from the Akzo Chemie of Chicago, Illinois

Use starching coating machine that size composition A is at least partly applied over continuous glass fibre long filament.By glass fibre Long filament integrated fibers stock and fiber strand is assembled into continuous rove.Become build package also reeling roving the most on the winder And use routine techniques to be dried.For each size composition B-E, it is independently repeated and aforesaid apply, assemble, wind and be dried Process, prepares independent rove build package hence for each size composition.

The continuous rove of the filament of glass fiber coated at least partially by size composition A is comprised according to following methods test Resisting fractre long filament (flyings) property.It is connected to continuous rove on winding drum and in flyings box, crosses over 5 tension rails draw Stretch time enough, stretch the about 0.5kg-continuous rove of about 1kg crossing over tension rail.Collected by crossing over tension force by flyings box Any broken filament that bar stretching rove obtains.At the end of stretching, weigh the weight of the broken filament collected in flyings box.This Outward, the weight of the continuous coarse yarn length of stretching on 5 tension rails is also weighed.Flyings value (fly is determined subsequently according to formula (V) Value):

[(weight of broken filament)/(weight of the rove of stretching)] x 1000mg/kg (V)

For each build package corresponding with size composition B-E, continuous rove is independently repeated above-mentioned flying Flower test method.Flyings result of the test provides in tablei.

Table I flyings result of the test

Size composition	Average flyings (mg/kg)
		A	5
B	7
		C	21
D	19
		E	26

As Table I provides, comprise the glass fibers at least partially by size composition A or the B coating comprising acid-amine component The continuous rove of dimension, compared with the continuous rove of size composition C-E, shows the disconnected of order of magnitude lower in flyings are tested Split long filament.The minimizing of the broken filament number of size composition A and B illustrates size composition and is fully spread over fiber table Face, to provide protection for fiber during process of the test.Comprise the spreadability desired by size composition A and B of acid-amine component Energy can be owing to the filming performance of acid-amine component.Comprise the glass fibre at least partially by size composition D or E coating Rove shows the broken filament of significantly higher quantity continuously.Size composition D and E does not contains acid-amine component, because phosphoric acid Salt is used for preparing these size compositions.

Embodiment 5

Operation sequence preparation according to embodiment 1 has the non-limiting enforcement of the size composition of the present invention of formula F-K Scheme.Each size composition F-K includes the phosphoric acid comprising hypophosphorous acid, and it results in and comprises amino silane and hypophosphorous acid Acid-amine component.

Sizing instruction (20 liters)

⁸DYNASYLAN AMEO APTES, available from the Degussa of Dusseldorf ,Germany AG

⁹50% solution

¹⁰Neoxil 605, available from the DSM, B.V. (35% solid) of Holland

¹¹DAPRAL GE 202, available from the Akzo Chemie of Chicago, Illinois

Operation sequence preparation according to embodiment 1 has the contrast size composition of formula L-Q.Described contrast sizing composition Thing does not include the phosphoric acid for forming acid-amine component or sulfur acid.In size composition L-Q, hypophosphorous acid component is by acid Salt-replace from the sodium hypophosphite of Holland's Transmare, B.V. acquisition.

Sizing instruction (20 liters)

¹²DYNASYLAN AMEO APTES, available from the Degussa of Dusseldorf ,Germany AG

¹³Neoxil 605, available from the DSM, B.V. (35% solid) of Holland

¹⁴DAPRAL GE 202, available from the Akzo Chemie of Chicago, Illinois

Use starching coating machine that size composition F is applied over continuous glass fibre long filament, and by continuous glass fibre Long filament integrated fibers stock.Subsequently continuous glass fibre stock is chopped into 4.5mm glass fiber strands, and does according to standard technique Dry.For each size composition G-Q, repeat aforesaid to apply, assemble, chopped and dry run, to prepare corresponding to each The short glass fiber stock of size composition G-Q.

The picking resistance of the short glass fiber stock of each size composition F-Q is tested subsequently according to following operation sequence. It is weighed to wherein be placed with in the first steel bowl of Antistatic cloth by 120g chopped strand stock.120g chopped strand stock is weighed to it In be placed with in the second steel bowl of the second Antistatic cloth.Two steel bowls containing short glass fiber stock are fastened to by In the vibrator that the Red Devil Equipment Company of Plymouth, Minnesota produces and carry out vibrating 6 points Clock.After vibration, the short glass fiber stock of the first steel bowl is sieved, to isolate any fine hair produced by vibration processing.Claim Measure any fine hair.Additionally the short glass fiber stock of the second steel bowl is sieved, and weigh the fine hair of any gained.By by floss Gross weight amount is divided by 120g and income value is multiplied by 100 to calculate the % fine hair of the short glass fiber stock of each steel bowl.Then The % fine hair of the short glass fiber stock of the first and second steel bowls is average, to produce final % fine hair value.

The short glass fiber stock of each size composition F-Q is completed fluffing test.Fluffing result of the test provides at table In II.

Table II fluffing result of the test

As shown in Table II, comprise and coat at least partially by the size composition of the present invention (F-K) comprising acid-amine component The short glass fiber stock of glass fibre shows than the size composition order of magnitude lower without acid-amine component and one The % fine hair of low two orders of magnitude in the case of Xie.

The minimizing of the % fine hair of size composition F-K illustrates size composition and is fully spread over fiber surface, to carry The convergence of high short glass fiber stock.The spreading property desired by size composition F-K comprising acid-amine component can be with attribution Filming performance in acid-amine component.Comprise the staple glass of the glass fibre coated at least partially by one of size composition L-Q Fiber strand shows significantly higher % fine hair.Size composition L-Q does not contains acid-amine component, because the salt of phosphoric acid is used for Prepare these size compositions.

Embodiment 6

The non-limiting embodiments of size composition of the present invention is prepared according to following formula:

Sizing instruction (1000kg)

Composition	Consumption (kg)	% solid
			Soften water	370.00
Acetic acid (glacial acetic acid)	9.12
			Silane15	67.90	24.09
Hypophosphorous acid (50%)	20.18	5.76
			Film former16	342.50	68.48
Lubricant17	2.34	1.34
			Thermal softening water for lubricant	10.00
Antifoaming agent18	0.10	0.00
			Biocide19	1.63	0.33
Cold softening water for biocide	10.00
			Acetic acid (glacial acetic acid)	0.36
Want the softening water of filling	165.87	0

¹⁵DYNASYLAN AMEO-P APTES, available from the Degussa of Dusseldorf ,Germany AG

¹⁶Neoxil 605, available from the DSM, B.V. of Holland

¹⁷DAPRAL GE 202, available from the Akzo Chemie of Chicago, Illinois

¹⁸Drewplus L-140, available from the Ashland Inc. of Covington, KY

¹⁹Kathon LX 1.5%, available from the Rohm and Haas Company of Coventry UK

Above-mentioned sizing composition is prepared equipped with in the main mixing channel of agitator by being provided by about 370kg softening water Thing.The acetic acid of specified amount is added and becomes owner of mixing channel, and by gained solution stirring 5 minutes.After stirring, by the amino silicone of specified amount Alkane adds becomes owner of mixing channel, and by gained solution stirring 10 minutes.Subsequently the hypophosphorous acid of specified amount is added and become owner of mixing channel, and By gained solution stirring 10 minutes.Hypophosphorous acid to the addition of main mixing channel result in provided herein comprise amino silane and The acid-amine component of hypophosphorous acid.Check pH value and utilize acetic acid to be adjusted to 6.3.

The most under agitation the film former of specified amount is added mixing channel.

Hot water is added premix groove, and the lubricant of specified amount is added premix groove.Subsequently gained mixture is stirred 10 minutes with dispersed lubricant.Then lubricant dispersion is added and become owner of mixing channel.Then antifoaming agent is added and become owner of mixing channel.Will Cold water adds premix groove and the biocide of specified amount adds premix groove.Then gained mixture is stirred 10 minutes.So After by biocidal agent composition add main mixing channel.Add and soften water to supply formula to 1000kg.Finally, by other second Acid adds becomes owner of mixing channel so that final ph reaches about 7.0.Preparation size composition have about 7.0 pH value and The total solid content of 17.5 weight %.

Embodiment 7

Also been evaluated utilization and be at least partially coated with the composite wood that the glass fibre of size composition of the present invention is strengthened The performance of material.In this embodiment, three kinds of different glass fiber products are compounded as G-LFT (granular-long fiber thermoplastic material Material) and test in reinforced polypropylene compound material.

Lower Table III describe be test for three kinds of composites and provide about carry out some test information and Result.Composite A uses following product to prepare, and this product is the business of PPG4588 products, it is with poly- Propylene is compatible and comprises the glass fibre with 17 Am nominal diameters.Composite B and C is each is freely coated with enforcement above Prepared by the glass fibre of the size composition described in example 6.The glass fibre used in composite B has the mark of 17 microns Claim diameter, and the glass fibre used in composite C has the nominal diameter of 24 microns.

Then the glass fiber strands comprising the glass fibre being at least partially coated with size composition is used to prepare multiple Condensation material.Composite A-C each uses identical device and operation sequence to prepare.When preparing each composite, glass fibers Dimension rove (comprise appointment glass fibre) is processed by crosshead formed by extrusion and tension G-LFT line, cause acquisition to have～12mm (～ 0.5 inch) the pill of nominal length.It is available commercially from Total for forming the fluoropolymer resin of described pill The 3860X homopolymer polypropylene of Petrochemicals.It is (a) Polyram for forming other composition of described pill1001, it is maleic anhydride modified polypropylene homopolymer, and wherein maleic anhydride is with about 1 weight The amount of amount % exists；(b) conventional thermal stabilizer bag (package)；And (c) white carbon black.Maleic anhydride modified polypropylene homo Thing serves as coupling agent and amount use (in terms of gross weight based on the mixture comprising glass fibre) by about 2 weight %.Control The glass content of pill grain is to produce in the composite～the target weight of 50% glass.As noted above, pill is cut It is slit into the nominal length of 12mm.Then described pill is dried four hours at 120 DEG C, and measures each sample after molding The moisture of product.Maximum allowable moisture after molding is 0.6% based on gross weight.

Van Dorn 55 injection molding machine is used to carry out molded sample.Check (non-return) valve will be flowed freely before starting this work It is installed on screw rod head.Mould therefor is standard ISO tensile sample mould, has major diameter cast gate and runner and large radius is bent Rate.Gate is the sector gate for tensile sample.Mould is the equilibrated type design that per injection produces two tensile samples.Punching Hit and cut from stretching rod by removing the label segment of sample with transverse test-piece.All samples meet ISO requirement.

Composite is carried out substantial amounts of test and result provides in table iii.

Table III G-LFT composite

Described data demonstrate, by the glass of the size composition being at least partially coated with one embodiment of the invention Composite B prepared by fiber is the commonly provided more physically better performance than composite A, and composite A utilizes at least partly Be coated with the glass fibre of the commercial paste composition compatible with acrylic resin and prepare.And, utilize and there are 24 microns of marks Claim prepared by the glass fibre of diameter and the size composition that is at least partially coated with one embodiment of the invention is compound Material C also demonstrates the physical property of generally better than composite A.Such as, even if glass content is lower by 4% than composite A, multiple Condensation material C still demonstrates some higher modulus, hot strength, flexural strength and non-notch charpy impact intensity.

Embodiment 8

In this embodiment, three kinds of different glass fiber products are in D-LFT (directly-long fiber thermoplastic material) technique Middle compounding is to produce the PP composite material of glass fiber reinforcement.

Lower Table IV describe be test for three kinds of composites and provide about carry out some test information and Result.Composite D uses following product to prepare, and this product is commercially available fibre glass roving, and it is with polypropylene compatible also And comprise the glass fibre with 17 Am nominal diameters.Composite E and F is each to be freely coated with described in example 6 above The glass fibre of size composition prepare.The glass fibre used in composite E and F each has the nominal of 24 microns Diameter.

Then the glass fiber strands comprising the glass fibre being at least partially coated with size composition is used to prepare D- LFT composite.Composite D-F each uses identical equipment and operation sequence to prepare.Use available commercially from The 40mm double screw extruder with 8 regions of Coperion GmbH prepares composite.This extruder is set in district Fibre glass roving is direct supplied to extruder by territory 4.This Coperion extruder utilizes one group to be specially designed for D-LFT life The screw rod produced is improved.Resin and conventional additive are supplied to extruder in region 1.For formed every kind these be combined The resin of material be withHGZ-1200 is available commercially from Phillips Sumika Polypropylene The 120MFI polypropylene homopolymer of Company.Other additive being fed to extruder in region 1 together with resin is: (a) Polyram's1001 chemical coupling agents, it is maleic anhydride modified polypropylene homopolymer, wherein Maleic anhydride exists with the amount of about 1 weight %；And (b) conventional thermal stabilizer masterbatch, it comprises white carbon black.The resin of each batch with The polypropylene homopolymer of 9.3 pounds, the chemical coupling agent of 0.2 pound, 0.5 pound heat stabilizer masterbatch ration mixing.In region 1 This mixture is fed to extruder.This mixture is mixed, melts and be fed downwardly into extruder through region subsequently.

Fibre glass roving is incorporated into the region 4 (it is a low sheraing district) of extruder, then by extruder spiral shell A set of pieces in bar is by its fixed length cutting (cut to length).By regulating the feeding rate of polymer, by being fed to The number of the rove of extruder, and by using technical controlling extruder well known by persons skilled in the art screw rod per minute Revolution (RPM), thus control the amount of glass in the length of glass fibre and composite.For composite D-F, four to six Rove is supplied to extruder to produce polypropylene D-LFT blank, and wherein the nominal amount of glass is 30 weight %.These hot blanks It is then transferred in the mould in compression presses and is molded as flat board.Then these flat boards are dimensioned cutting for machine Tool is tested.For composite D (having the glass fibre of 17 Am nominal diameters), greater number of rove is supplied to extrusion Machine is to obtain suitable glass content.Due to bigger nominal fi diameter, composite E and F needs less glass fibre Achieve that desired glass content.Other details about composite extrusion provides in lower Table IV.

All test specimens all meet ISO requirement.Composite is carried out substantial amounts of test and result provides in table iv.

Table IV D-LFT composite

In D-LFT injection molding technique, glass fibre tends to take in the flowing direction during mould filling To.Glass fibre generally keeps this orientation in the composite of solidification.The composite formed in this way is usually in flowing Direction (flow direction in mould stowing operation) and cross-wind direction (with this flow direction perpendicularly or transversely) the two direction Upper test.Owing to glass fibre is orientated, the expection of composite property such as hot strength is the highest.Typical case Ground, the minimum thing that the consumer of composite manufacturer or composite manufacturer will specifically note on composite cross-wind direction Rationality energy, because flow direction is generally of physically better performance.

Result in Table IV demonstrates, represents composite E and F and the contrast composite wood of some embodiments of the present invention Material D compares has significantly higher hot strength in the flowing direction.Especially, composite E and F drawing on cross-wind direction Stretch intensity close to comparative composite D hot strength in the flowing direction.Flow direction and cross-wind direction have this High tensile strength properties utilize 24 lim diameter fibre strengthen composite (especially with the fibre utilizing 17 micron diameters The composite that dimension strengthens is when comparing) production be unexpected because the physical property of composite is tended to along with glass The increase of glass fibre diameter and deteriorate.These data demonstrate the dispersibility and improvement that glass fibre improves in the composite Fiber retain.Other performance in Table IV demonstrate relative to composite D relevant to composite E and F quite or The performance improved.

Embodiment 9

In the present embodiment, five kinds of different glass fiber products are in D-LFT (directly-long fiber thermoplastic material) technique Middle compounding is to produce the PP composite material of glass fiber reinforcement.

Lower Table V and VI describe be test for eight kinds of composites and provide about carry out some test information with And result.In Table V, composite has the nominal glass content of 30%, and in Table VI, identical glass fibre is at mark Glass content be called 40% composite in be evaluated.Composite G and K uses following product to prepare, and this product is PPG Business4588 products, it is with polypropylene compatible and comprises the glass fibre that nominal diameter is 17 microns.Multiple Condensation material H and L uses following product to prepare, and this product is the business of PPG4599 products, itself and polypropylene Compatible and comprise the glass fibre that nominal diameter is 17 microns.Composite I and M uses nominal diameter to be 17 microns and be coated with Prepared by the glass fibre being covered with the size composition described in example 6 above.Composite J and N uses nominal diameter to be 24 Micron and be coated with the glass fibre of the size composition described in example 6 above and prepare.

Then the glass fiber strands comprising these glass fibre being at least partially coated with size composition is used to system Standby D-LFT composite.Comprise the glass fiber strands of the glass fibre being at least partially coated with size composition then by with Prepare D-LFT composite.Composite D-F each uses identical equipment and operation sequence to prepare.Use commercially available Composite is prepared from the 40mm double screw extruder with 8 regions of Coperion GmbH.This extruder is set to Fibre glass roving is direct supplied to extruder by region 4.This Coperion extruder utilizes one group to be specially designed for D-LFT The screw rod produced is improved.Resin and conventional additive are supplied to extruder in region 1.For forming every kind, these are multiple The resin of condensation material be withHGZ-1200 is available commercially from Phillips Sumika Polypropylene The 120MFI polypropylene homopolymer of Company.Other additive being fed to extruder in region 1 together with resin is: (a) Polyram's1001 chemical coupling agents, it is maleic anhydride modified polypropylene homopolymer, wherein Maleic anhydride exists with the amount of about 1 weight %；And (b) conventional thermal stabilizer masterbatch, it comprises white carbon black.The resin of each batch with The polypropylene homopolymer of 9.3 pounds, the chemical coupling agent of 0.2 pound, 0.5 pound heat stabilizer masterbatch ration mixing.In region 1 This mixture is fed to extruder.This mixture is mixed, melts and be fed downwardly into extruder through region subsequently.

Fibre glass roving is incorporated into the region 4 (it is a low sheraing district) of extruder, then by extruder spiral shell A set of pieces in bar is by its fixed length cutting.By regulating the feeding rate of polymer, by being fed to the rove of extruder Number, and by using technical controlling extruder well known by persons skilled in the art screw rod revolution (RPM) per minute, thus The amount of glass in the length of control glass fibre and composite.For composite G-J, four to six rove are supplied to squeeze Going out machine to produce polypropylene D-LFT blank, wherein the nominal amount of glass is 30 weight %.For composite K-N, eight rove Being supplied to extruder to produce polypropylene D-LFT blank, wherein the nominal amount of glass is 40 weight %.These hot blanks are then It is transferred in the mould in compression presses and is molded as flat board.Then these flat boards are dimensioned cutting for machinery survey Examination.For composite G-I and K-M (having the glass fibre of 17 Am nominal diameters), greater number of rove is supplied to Extruder is to obtain suitable glass content.Due to bigger nominal fi diameter, composite J and N needs less glass Fiber achieves that desired glass content.All samples all meet ISO requirement.

Composite is carried out substantial amounts of test and result and (there is the composite wood of 30% nominal glass content in Table V Material) and the middle offer of VI (there is the composite of 40% nominal glass content).

Table V D-LFT composite (nominal 30% glass content)

Table VI D-LFT composite (nominal 40% glass content)

Although many visual reports can be provided with regard to the data in Table V and VI, but to point out some exemplary visual reports. First, under the nominal glass content of 40%, comprise the glass fibre being at least partially coated with size composition of the present invention Composite (i.e. composite M-N) has the hot strength usually above comparative composite.Additionally, composite M-N exists Tensile strength values on cross-wind direction and the tensile strength values height about the same on flow direction, this shows that fiber is in resin Good dispersion.Composite N (24 micron diameter glass fibers) demonstrates in the flexural strength value of cross-wind direction and in flowing Value on direction is almost identical.This isotropic performance for end user design composite material component time permissible It is useful, this is because, for instance, it is not necessary to the design compensating generally lower-performance value on flow direction is possible.

The desired characteristic can brought by embodiment of the present invention may include but be not limited to: provides and has favourable filming performance The size composition comprising acid-amine component, thus eliminate or reduce the amount of film former in size composition；There is provided with on this The broken filament that can show minimizing quantity during processing conditions of paste composition coating and the glass fiber bundle of fine hair；Carry For can be used for strengthening the glass fiber strands being coated with size composition of composite；Offer can be used on long fiber thermoplastic material The glass fiber strands being coated with size composition in application；Offer can be used in relatively large diameter glass when strengthening composite Size composition on fiber；There is provided and have quite for the fibre-reinforced composite of small diameter or improve The composite of the use larger diameter glass fiber reinforcement of physical property；And other etc..

Each embodiment of the present invention is described in the case of realizing each purpose of the present invention.Should be realized that this A little embodiments are merely illustrative the principle of the present invention.In the case of without departing from the spirit and scope of the present invention, the present invention Many modifications and variations be readily apparent for those skilled in the art.

Claims (35)

1. glass fiber strands, comprises:

It is at least partially coated with at least one glass fibre of the aqueous size composition comprising acid-amine component, this acid-amine group Subpackage contains and at least one phosphoric acid or the molecule of at least one primary amine of vitriolated molecular association, wherein this at least one amine At least one phosphoric acid of molecule and this or vitriolated molecule interacted by Louis's Acid-Base and associate, and wherein This at least one glass fibre has a diameter of at least 21 microns, and wherein this at least one phosphoric acid or sulfur acid and this amine Mol ratio as follows: 0.1 < this mol ratio < 3.

Glass fiber strands the most according to claim 1, wherein this at least one glass fibre has up to 35 microns Diameter.

Glass fiber strands the most according to claim 1, wherein this at least one glass fibre has at least 22 microns straight Footpath.

Glass fiber strands the most according to claim 1, wherein the nominal diameter of this at least one glass fibre is 24 microns.

Glass fiber strands the most according to claim 1, wherein this phosphoric acid includes phosphorous acid, hypophosphorous acid, phosphonic acids, You Jihan Phosphoric acid or its mixture.

Glass fiber strands the most according to claim 1, wherein this aqueous size composition comprises at least one further Membrane.

Glass fiber strands the most according to claim 1, wherein this aqueous size composition comprises at least one occasionally further Connection agent.

8. composite, comprises:

Fluoropolymer resin；With

Multiple glass fibre of the glass fiber strands from claim 1 being arranged in this fluoropolymer resin.

Composite the most according to claim 8, the most the plurality of glass fibre is with up to 90 weights of composite The amount of amount % exists.

Composite the most according to claim 8, wherein this fluoropolymer resin includes thermoplastic resin.

11. composites according to claim 10, wherein this thermoplastic resin includes polyolefin, polyamide, polyphenyl second Alkene, polyphenylene oxide, polyester or its copolymer or mixture.

12. composites according to claim 8, wherein this fluoropolymer resin includes thermosetting resin.

13. glass fiber strands, comprise:

It is at least partially coated with at least one glass fibre of the aqueous size composition comprising acid-aminosilane ingredient, should Dividing of at least one amino silane of the molecular association that acid-aminosilane ingredient comprises the phosphoric acid with at least one lower formula (I) Son:

Wherein R¹Be-alkyl ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl or-heteroaryl and R²It is-H ,-alkane Base ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl or-heteroaryl, and

Wherein this at least one amino silane comprises primary amine, and wherein this at least one glass fibre has at least 21 microns Diameter, and wherein this at least one phosphoric acid or sulfur acid are as follows with the mol ratio of this amine: 0.1 < this mol ratio < 3.

14. glass fiber strands according to claim 13, wherein this at least one glass fibre has up to 35 microns Diameter.

15. glass fiber strands according to claim 13, wherein this at least one glass fibre has at least 22 microns Diameter.

16. glass fiber strands according to claim 13, wherein the nominal diameter of this at least one glass fibre is 24 micro- Rice.

17. glass fiber strands according to claim 13, wherein this aqueous size composition comprises at least one further Film former.

18. glass fiber strands according to claim 13, wherein this at least one phosphoric acid and this amino silane mole Ratio is less than 1.

19. composites, comprise:

Fluoropolymer resin；With

Multiple glass fibre of the glass fiber strands from claim 13 being arranged in this fluoropolymer resin.

20. composites according to claim 19, the most the plurality of glass fibre is with up to 90 weights of composite The amount of amount % exists.

21. composites according to claim 19, wherein this fluoropolymer resin includes thermoplastic resin.

22. composites according to claim 21, wherein this thermoplastic resin includes polyolefin, polyamide, polyphenyl second Alkene, polyphenylene oxide, polyester or its copolymer or mixture.

23. composites according to claim 19, wherein this fluoropolymer resin includes thermosetting resin.

24. glass fiber strands, comprise:

It is at least partially coated with at least one glass fibre of the aqueous size composition comprising acid-aminosilane ingredient, should Acid-aminosilane ingredient comprises at least one primaryamino-silane of the molecular association of the phosphoric acid with at least one lower formula (II) Molecule:

Wherein R³And R⁴Independently selected from-H ,-alkyl ,-thiazolinyl ,-alkynyl ,-cycloalkyl ,-cycloalkenyl group ,-heterocycle ,-aryl or-miscellaneous Aryl, and

Wherein this at least one glass fibre has the diameter of at least 21 microns, and wherein this at least one phosphoric acid or sulfur-bearing Acid is as follows with the mol ratio of this amine: 0.1 < this mol ratio < 3.

25. glass fiber strands according to claim 24, wherein this at least one glass fibre has up to 35 microns Diameter.

26. glass fiber strands according to claim 24, wherein this at least one glass fibre has at least 22 microns Diameter.

27. glass fiber strands according to claim 24, wherein the nominal diameter of this at least one glass fibre is 24 micro- Rice.

28. glass fiber strands according to claim 24, wherein this aqueous size composition comprises at least one further Film former.

29. glass fiber strands according to claim 24, wherein this at least one phosphoric acid and this amino silane mole Ratio is less than 1.

30. composites, comprise:

Fluoropolymer resin；With

Multiple glass fibre of the glass fiber strands from claim 24 being arranged in this fluoropolymer resin.

31. composites according to claim 30, the most the plurality of glass fibre is with up to 90 weights of composite The amount of amount % exists.

32. composites according to claim 30, wherein this fluoropolymer resin includes thermoplastic resin.

33. composites according to claim 32, wherein this thermoplastic resin includes polyolefin, polyamide, polyphenyl second Alkene, polyphenylene oxide, polyester or its copolymer or mixture.

34. composites according to claim 30, wherein this fluoropolymer resin includes thermosetting resin.

35. glass fiber strands according to claim 1, wherein this aqueous size composition comprises Tissuemat E or poly-third further At least one in alkene wax.