CN103889916B - sizing composition for glass fibre - Google Patents

Abstract

The present invention relates to a kind of sizing composition for glass fibre, comprising: (a) silane based coupling agents mixture, (b) film former, (c) additive, it is characterized in that, at least one of at least one dialkoxy silicane that described silane based coupling agents mixture comprises (d) at least 15 weight % and (e) at least 20 weight % comprises the beta-unsaturated esters silane of the olefinic double bond activated by ester functional group, and wherein R can be H, CH₃、‑C₂H₅, wherein R' can be H, CH₃、‑CH₂COOR, wherein R " can be H, CH=CH₂, COOH, phenyl, CH₃CH=CH, COOR, and wherein m is 0～8, preferably 2～4, more preferably m=3, and n=0～2, preferably 0 or 1.

Description

Sizing composition for glass fibre

Technical field

The present invention relates to the technical field of the composite of glass fiber reinforcement, more particularly, to for glass The silylation sizing material of glass fiber, which raises and be combined with the polymer of the glass fiber reinforcement being coated with this sizing material The mechanical performance of material.The sizing composition of the present invention is suitable for strengthening various types of polymeric matrix, example As, epoxy resin, unsaturated polyester (UP) and vinyl ester resin.

Background technology

Polymeric material has many noticeable performances, but their mechanical performance is for many structures Application deficiency.Wherein by diameter about 6～25 μm, there is the fiber of high rigidity and/or intensity (typically Have carbon, glass or aramid fibre) the fibre-reinforced composite tool that embeds in polymeric matrix There is significantly higher mechanical performance, it is allowed to reach the ratio of very favorable mechanical performance and density.The fibre strengthened Dimension can be short, length or continuous print.In the latter case, depend on being executed to specific part The stress field added, continuous print fiber can have different orientation.The fiber strengthened can with the form of fabric such as Non-woven fabrics, the fabric of different pattern, braid or knitted fabric are arranged, or can they be placed Place them on filament winding body in a mold or according to predetermined pattern.

When fibre-reinforced composite stands stress field, stress is transferred to by matrix-fiber interface On fiber.If the combination of matrix-fiber interface is strong, the most whole load can transfer to fiber, thus machinery Performance is high.If on the other hand the interface cohesion between matrix and fiber is weak, then may start occur that crack is also And propagate along fiber-matrix interface, thus cause the most destroyed.Therefore, improve matrix and fiber it Between combination be very important.

In order to carry out the process of fiber (generally in loom) and improve and by the matrix embedded by fiber Interfacial adhesion, coats this fiber with sizing material, and the composition of this sizing material depends on will be fine by the enhancing of applying glue The character tieed up and the matrix being used together with fiber.Glass fibre carrys out applying glue through conventional silylation compositions, On the one hand this is because can obtain at fiberglass surfacing with by the hydrolysis of the alkoxy silane of sizing material Silanol between, on the other hand and between adjacent silicon alcohol groups, form Si-O-Si covalent bond, thus Cross-linked structure is formed on the surface of glass fibre.This cross-linked structure seems to improve the corrosion resistance of fiber, allusion quotation Type ground hydrolytic resistance.By the organo-functional group of silane coupler and improve sizing material and base by film former The adhesion of body, its character depends on used matrix.Sizing composition often comprises other additive Such as lubricant, antistatic additive etc..The multiple sizing material for glass fibre is in prior art, such as, WO2006007169, US2006204763, EP2053078 or WO200410948 propose, and At document E.P.Pluedemann, " Silane Coupling Agents(silane coupler) ", Plenium goes out Version society (1982) is commented.

In european patent application EP11171653, present inventors have proposed and subtract on the surface of glass fibre The amount of few crosslinking, its objective is especially to prevent the crosslinking of the silanol between adjacent fiber.This is by making apparatus The silane coupler having dialkoxy silicane and the high-load ratio of trialkoxy silane realizes, the most at least The silane coupler being present in compositions of 75 weight % should be dialkoxylated.This causes raising Fiber dispersion, and with expected conversely, because improve by the wettability of matrix moistening fiber surface, Result in excellent corrosion resistance.

Use for such as air vane, pressure vessel contour applicable major part glass fiber compound material Epoxy resin is as matrix, this is because its higher machinery and physical property.Polymer containing vinyl is such as Unsaturated polyester resin and vinyl ester resin are generally cheap than epoxy resin, but, no matter to each type Matrix resin, coated glass fiber has identical sizing material or is coated with specific sizing material, using the former base Body is compared with using epoxy resin-base, and the mechanical performance of the composite of glass fiber reinforcement is the lowest.

The present invention proposes the sizing composition for glass fibre, and it produces in polyester matrix complex In mechanical performance and epoxy matrix complex, produced mechanical performance is close, and in some cases, very To producing identical mechanical performance.The sizing material of the present invention also produces the most excellent when being used together with epoxy resin Good mechanical performance, thus expands the scope of the matrix that this sizing material can be advantageously used together.Below Introduce this advantage and the further advantage of the present invention.

Summary of the invention

In the present invention defined in appended independent claims.Define in the dependent claims preferably Embodiment.In particular it relates to a kind of sizing composition for glass fibre, comprise:

(a) silane based coupling agents mixture；

(b) film former or film former mixture；

(c) additive,

It is characterized in that, described silane based coupling agents mixture comprises:

At least one dialkoxy silicane of (d) at least 15 weight %；With

E at least one of () at least 20 weight % comprises the insatiable hunger of the olefinic double bond activated by ester functional group With ester alkoxy silane,

Wherein, described weight % is to measure relative to the gross activity solids weight of silane based coupling agents.

Described beta-unsaturated esters alkoxy silane preferably includes selected from (methyl) acrylate, fumarate, mountain Part in pears acid esters, cinnamate, maleate, itaconate, citraconate and aconitate, excellent Selecting described beta-unsaturated esters silane is (methyl) acrylate or sorbate.Specifically, described beta-unsaturated esters Alkoxy silane can have a below formula:

R"-CH=(CR')-(C=O)-O-(CH₂)_m-Si(R)_n(OR)_3-n

Wherein R can be-H-,-CH₃、-C₂H₅, wherein R' can be-H ,-CH₃、-CH₂-COOR, its Middle R " can be-H ,-CH=CH₂,-COOH, phenyl, CH₃-CH=CH-,-COOR, Yi Jiqi Middle m is 0～8, preferably 2～4, more preferably m=3, and n=0～2, preferably 0 or 1.

In a preferred embodiment, the film former mixture of one or more in following material:

(i) based on bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin, cresol-novolak ring The epoxy resin latex of any one of epoxy resins；

(ii) epoxy ester resin emulsion；

(iii) epoxy polyurethane resin emulsion；

(iv) polyester emulsion；

(v) vinyl esters ((methyl) acrylate epoxy resin) emulsion；

(vi) polyurethane polyureas ester group dispersion.

Described film former preferably comprises bisphenol A based epoxy resin emulsion, its with above-mentioned emulsion in one or Multiple emulsion premixing is to improve by the wettability of particular substrate moistening.

Silane based coupling agents mixture can comprise the dialkoxy silicane of at least 20 weight %, preferably at least 35 weight %, more preferably at least 60 weight %, and the dialkoxy silicane of more preferably at least 95 weight %, Wherein said weight % is to measure relative to the gross activity solids weight of silane based coupling agents.Described two Alkoxy silane is preferably selected from dialkoxy-epoxy-silane, dialkoxy-vinyl-silane, dialkoxy One or more in-(methyl) acryloxy-silane or dialkoxy-amino silane.In concrete reality Executing in mode, all or part of (methyl) acryloxy silane is (methyl) acryloxy-dialkoxy Silane.

Described beta-unsaturated esters alkoxy silane preferably in described silane based coupling agents mixture with at least 25 weights Amount %, preferably at least 45 weight %, more preferably at least 75 weight %, and more preferably at least 95 weight % Amount exist, wherein weight % of beta-unsaturated esters alkoxy silane is the gross activity relative to silane based coupling agents Solids weight is measured.Beta-unsaturated esters alkoxy silane is preferably selected from (methyl) third in following material Alkene acyloxy silane:

(i) (methyl) acryloyl group dialkoxy silicane, such as, γ-(methyl) acryloxypropyl Dimethoxy-silane, γ-(methyl) acryloxypropyl-diethoxy silane, ((methyl) acryloyl-oxy Ylmethyl)-methyl dimethoxysilane；

(ii) (methyl) acryloyl group trialkoxy silane, such as, γ-(methyl) acryloxypropyl front three TMOS, γ-(methyl) acryloxypropyl triethoxysilane；And/or

(iii) methyl monoalkoxysilane, such as, (methyl) acryloxypropyl-dimethylethyloxy silicon Alkane, (methyl) acryloxypropyl dimethyl methoxy silane.

Amino silane may be used in the compositions of the present invention, but its content should keep low.If there is Amino silane, then amino silane should be less than 5 weights of the gross activity solids weight of silane based coupling agents Amount %.Preferably, silane based coupling agents mixture comprises the amino silane less than 3 weight %, the least In 2 weight %, more preferably less than 1 weight %.Major part preferred embodiment in, silylation is even Connection agent composition is not containing amino silane.If there is amino silane in sizing material, then amino silane can select One or more in amino dialkoxy silicane or amino-trialkoxy silane.

The sizing composition of the present invention can comprise one or more additives, such as, boron-containing compound, non- Ion or cationic lubricant, antistatic additive and/or to pH be by final coating composition regulation 4.5 ± 0.5 and thus control the weak organic acid of hydrolysis dynamics of silane alkoxy groups group.

The invention still further relates to a kind of glass fibre being coated with sizing material defined above and comprise this glass fibers The glass fibre reinforced composion of dimension.In a preferred embodiment, glass fibre reinforced composion tool Have selected from unsaturated polyester resin, vinyl ester resin, polyurethane resin or undersaturated polyester-type poly- Matrix in urethane hybrid resin.For such matrix, the dialkoxy silicane in glass fiber size can With selected from epoxy silane and/or (methyl) acryloxy silane；Described film former can be selected from polyester, polyester Base film former, vinyl esters and/or epoxy film former.In alternate embodiments, described matrix can To be epoxy resin.Suitably dialkoxy silicane can be epoxy silane；Described film former can be epoxy Film former.

Composite according to the present invention goes for manufacturing air vane；Propeller generator housing；Pipeline； Container, preferably pressure vessel；The crossbeam of pultrusion；Shell (profile)；Mechanical elements； Spring leaf；Shellproof element；Filament winding parts；Boats and ships and naval vessels, automobile and air transport, building, Parts in power generator, motion, field of civil engineering.

Unless otherwise noted, the weight % value of all components is relative to the active solid thing weight of described component Amount is measured.

Accompanying drawing explanation

In order to be more fully understood by the essence of the present invention, carry out described in detail below, wherein with reference to combining accompanying drawing:

Fig. 1 shows what the UD glass fibre reinforced composion to prior art with according to the present invention was measured The figure of short beam test (SBT) result；

Fig. 2 shows and the 0 ° of glass fibre (GF) using various matrixes is strengthened opening of composite implementation Power-tension force (R0.1)-testing fatigue result: cycle-index during fracture and (a) maximum load and (b) The relation of maximum strain.

Detailed description of the invention

The present invention proposes a kind of silylation sizing material with complete innovation form, and it is for as in composite The glass fibre of reinforcing agent, relative at present can the glass fibre bought of market, this glass fibre produces more For excellent performance.On the one hand when the most all of silylation sizing material is designed to, with the surface of glass fibre Reaction, when on the other hand mutually carrying out reacting the network to form crosslinking at fiber peripheral, the present invention carries on the back completely From this approach and limit between (in some embodiments, practically even eliminate) neighbouring silane chain Cross-linking reaction.This is the dialkoxy by using at least 15 weight % in an amount of from total silane coupler The silane changed rather than major part (whole) as described in the prior art use tri-alkoxy Silane realize.

The alkoxy grp of alkoxy silane, when contacting with aqueous medium, is hydrolyzed into hydroxyl to form silanol.When Being employed the surface with glass fibre when contacting, the hydroxyl condensation of this silanol coupling agent is on the surface of glass. Trialkoxy silane also will be reacted to form-Si-O-Si-network with neighbouring trialkoxy silane.In the present invention In the dialkoxy silicane that uses with the amount of at least 15 weight % of total silane coupler can not be with neighbouring two Alkoxy silane forms substantial amounts of cross-linked network, and will be from the table of glass fibre as substantial amounts of hair Area linear extend out.By measuring the dissolubility of sizing material, the interchain between neighbouring silanol can be evaluated and hand over Connection degree.Employing toluene soxhlet extraction method measures the glass fibre after applying glue in weight m before₀With at it After weight m₁.This dissolubility is expressed as (m with the form of percentage ratio₀-m₁)/m₀.Preferably in the present invention Framework in dissolubility in toluene between 30～98%, preferably between 50～95%.

Based on total silane coupler, the sizing material of the present invention comprises the dialkoxylated silicon of at least 15 weight % Alkane.Concentration is cross-linked in order to reduce-the Si-O-Si-of the sizing material on fiberglass surfacing even further, this The silane coupler of bright sizing material can comprise the dialkoxylated silane coupler of at least 20 weight %, Remaining silane coupler is the silane of tri-alkoxy.Preferably at least 35 weight %, preferably at least 60 weights Amount %, more preferably at least 75 weight %, the silane coupler of most preferably at least 95 weight % should be by dioxane Epoxide.The sizing composition not having trialkoxy silane with only comprising dialkoxy silicane can also obtain Obtain excellent performance.

Preferably dialkoxy silicane is dimethoxysilane, diethoxy silane and (ethoxymethyl) epoxide silicon Alkane.Dialkoxy silicane can be silicon ester, vinyl silanes, epoxy silane, isocynate silane.Two Alkoxy silane can also include beta-unsaturated esters alkoxy silane, such as, (methyl) acryloxy silane, Condition is dialkoxylated and the total amount of the beta-unsaturated esters silane of tri-alkoxy is formed as silane coupler At least 20 weight %；And also amino silane can be comprised, condition is dialkoxylated and tri-alkoxy The total amount of amino silane be formed as 5 weight % less than silane coupler.It is applicable to the dioxane of the present invention The example of TMOS includes:

(i) epoxy-silane, such as, γ-glycidoxypropyl dimethoxysilane,_γ-epoxy third Epoxide propyl-methyl diethoxy silane；

(ii) vinyl-silane, such as, vinyl methyl dimethoxysilane, vinyl methyl diethoxy Base silane；

(iii) (methyl) acryloxy-silane, such as, γ-(methyl) acryloxypropyl diformazan TMOS, γ-(methyl) acryloxypropyl diethoxy silane, ((methyl) acryloxy first Base) metil-dimethoxysilane；

(iv) amino-silane, such as, γ-aminopropyltriethoxy diethoxy silane, N-β-(aminoethyl)-γ- Aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-methyl dimethoxysilane, N-β -(aminoethyl)-gamma-amino isobutyl methyl dimethoxy-silane, γ-aminopropyltriethoxy dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl-methyldiethoxysilane；

(v) mercapto-silane, such as, 3-mercapto hydroxypropyl methyl dimethoxysilane.

These dialkoxy silicanes easily from SHIN ETSU company with article number KBE402, KBM-502, KBE-502, KBM-602 are commercially available；From MOMENTIVE company with article number Silquest Wetlink78 or Coatosil2287 and A-2171 is commercially available.

Document WO2006007169, US2006204763, EP2053078 or WO2004110948 Dialkoxylated silane is accurately mentioned outside the silane list of substantial amounts of tri-alkoxy, but not Have and considered that it was applied in earnest, if there being it to apply, then the most up to for silane total amount the most at least The amount of 15 weight %.

Trialkoxy silane can exist less than 85 weight % amounts of silane coupler total amount, and with two The silane coupler that alkoxy silane forms the sizing material according to the present invention together is all.Trialkoxy silane is permissible Selected from according to trialkoxy silane usual in the prior art of application-specific, condition is to form whole silane Coupling agent dialkoxylated-and the summation of silane of tri-alkoxy include the unsaturation of at least 20 weight % Ester alkoxy silane, the amino silane of preferably more than 5 weight %.Except latter two silane in detail below Outside description, it is suitable for oversize with the series of the silane of the possible tri-alkoxy of dialkoxylated silane use So that can not be exhaustive, and it be well-known to those skilled in the art, and can from about dialkoxy Identical company of the relevant company of SiClx alkane be readily obtained (see, for example, WO2006007169, US2006204763, EP2053078 or WO2004110948).Use limitation in the composition The silane of tri-alkoxy so that the interface between the surface and coupling agent of fiber produces limitation -Sl-O-Si-cross-links.But, in most cases, it is preferable to even relative to the silane in the presence of compositions The gross weight of connection agent, is reduced to the amount of the silane of tri-alkoxy, less than 80 weight %, not surpass Crossing 65 weight %, more preferably no more than 25 weight %, override is less than 5 weight %.The present invention's In particular implementation, described sizing composition does not comprise the silane of tri-alkoxy.

The sizing composition of the present invention must include containing at least 20 weight %, preferably at least 25 weight %, More preferably at least 45 weight %, the silane of the beta-unsaturated esters alkoxy silane of most preferably at least 75 weight % is even Join agent, and it even can include the beta-unsaturated esters alkoxy silane of at least 95 weight %, wherein said Weight % is to measure relative to the gross activity solids weight of silane based coupling agents.At the present composition The beta-unsaturated esters alkoxy silane of middle use can be dialkoxylated or tri-alkoxy.Specifically, Beta-unsaturated esters silane preferably includes selected from (methyl) acrylate, fumarate, sorbate, cinnamic acid Part in ester, maleate, itaconate, citraconate, aconitate, the most described beta-unsaturated esters Silane is (methyl) acrylate or sorbate.More precisely, described beta-unsaturated esters silane preferably has Below formula:

R"-CH=(CR')-(C=O)-O-(CH₂)_m-Si(R)_n(OR)_3-n

Wherein R can be-H ,-CH₃、-C₂H₅, wherein R' can be-H ,-CH₃、-CH₂-COOR, wherein R " can be-H ,-CH=CH₂,-COOH, phenyl, CH₃-CH=CH-,-COOR, wherein m is 0～8, preferably 2～4, more preferably m=3, and n=0～2, preferably 0 or 1.Particularly preferred insatiable hunger Include containing (methyl) the acryloxy dialkoxy silicane with lower part and three alcoxyls with ester alkoxy silane Base silane:

(methyl) acryloxy dialkoxy silicane, such as, γ-(methyl) acryloxypropyl two Methoxy-silane, γ-(methyl) acryloxypropyl-diethoxy silane, ((methyl) acryloxy Methyl)-methyl dimethoxysilane；

(methyl) acryloxytrialkoxysilane, such as, γ-(methyl) acryloxypropyl trimethoxy Base silane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloyloxymethyl three second TMOS；

(methyl) acryloxy monoalkoxysilane, such as, (methyl) acryloxypropyl-dimethyl Ethoxysilane, (methyl) acryloxypropyl dimethyl methoxy silane.

No matter it is dialkoxylated or tri-alkoxy, beta-unsaturated esters present in the sizing composition Alkoxy silane is conducive to improving by the wettability of resin wetted fiber, and described resin is such as unsaturated polyester (UP) Resin, vinyl ester resin, polyurethane resin and undersaturated PAUR hybrid resin.? The matrix flowed during dipping moistening fiber surface well, obtains good to consequent composite Mechanical performance it is critical that.The undersaturated olefinic double bond activated by ester functional group is improve so Resin and fiberglass surfacing between adhesion.By the good wettability of resin wetted fiber with not The unique combination forming covalent bond between saturated ester alkoxy silane and matrix significantly increases composite Mechanical performance and its hydrolytic resistance.

The sizing material of the present invention can use amino silane as coupling agent, but the most limited amount.Amino Silane is not to be exceeded 5 weight % of silane coupler solids, preferably smaller than 3 weight %, is more preferably less than 2 weight %, wherein said weight % is to measure relative to the gross activity solids weight of silane based coupling agents 's.In a preferred embodiment, silane based coupling agents mixture is not containing amino silane.Amino silane Amount should be retained as low, anti-with the epoxide group of other silane or film former to limit amino group Should, this can result in covalent bond between undesirable fiber.Suitably amino dialkoxy silicane or three alkane The example of TMOS includes:

Amino dialkoxy silicane, such as, γ-aminopropyltriethoxy diethoxy silane, N-β-(aminoethyl)-γ -aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-methyl dimethoxysilane, N- β-(aminoethyl)-gamma-amino isobutyl methyl dimethoxy-silane, γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-methyldiethoxysilane；And/or

Amino-trialkoxy silane, such as, gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy Silane, N-β-(aminoethyl)-γ-aminopropyl trimethoxy-silane, N-β-(aminoethyl)-γ-aminopropyl three ethoxy Base silane, diethylidene triamido-propyl trimethoxy silicane, double-(_γ-Trimethoxy-silylpropyl) Amine, N-phenyl-γ-aminopropyltrimethoxysilane, gamma-amino-3,3-dimethylbutyl trimethoxy silane, γ- Ammobutyltriethoxysilane, poly-azepine amide silane (polyazamide silane).

The sizing composition of the present invention advantageously comprises at least one epoxy silane, in order to improve glass fibre with The compatibility of epoxy resin, has thus been significantly expanded the scope of the particularly suitable matrix of described sizing composition. If existed in the composition, then one or more during epoxy silane is preferably chosen from following material:

(i) epoxy-dialkoxy silicane, such as, γ-glycidoxypropyl dimethoxysilane, γ- Glycidoxypropyl group-methyldiethoxysilane；Or

(ii) epoxy-trialkoxy silane, such as, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane, γ-epoxy third Epoxide propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl Triethoxy-Silane, β-(3,4-epoxy Cyclohexyl) ethyl trimethoxy silane, 5,6-epoxyhexyl-triethoxysilane.

Epoxy silane preferably with at least 10 weight %, preferably at least 20 weight %, more preferably at least 67% Amount, and the amount of 80% of can being up to is present in silane coupler, condition is the silicon of at least 15 weight % Alkane is dialkoxylated, and the silane of at least 20 weight % is acryloxy silane.

The total amount of the silane coupler existed in the composition preferably comprises gross activity compositions (i.e., not Including water and any hydrolysis volatile byproducts) 2～30 weight %, more preferably 4～20 weight %, optimum Select 8～18 weight %.Except beta-unsaturated esters alkoxy silane and amino silane, silane coupler can comprise Other silane, such as, vinyl-silane, mercapto-silane etc., both can be dialkoxylated, also It can be tri-alkoxy.The existence of epoxy silane is preferred.

Film former interacts with silane coupler, and interacts with matrix during the dipping of fiber. Therefore, film former have to be compatible with the matrix that will use.Film former protection glass fibre is in processing (example As, braiding, knitting, edge are sewed) period is not destroyed, and promotes the compatible of matrix and fiber.Film forming It is unnecessary that agent and silane coupler form any (or not being the most a large amount of) covalent bond.The most preferred Do not form covalent bond with silane or form little covalent bond so that it can be in the dipping phase of fibre structure Between dissolve in the base.The film forming of trace is identified in the toluene extract according to the sizing material of the present invention Agent, which imply that it dissolves in matrix.Preferably film former includes epoxy resin, saturated or undersaturated Polyester resin, vinyl esters or phenolic resin.Such film former is sold with emulsion, and such as by As DSM N. V. provides with trade name Neoxil or by Hexion-Momentive company with trade name Epi-Rez provides.Gross weight based on active compound (that is, does not include the most generally being supplied in membrane The weight of the solvent used in emulsion), preferably film former is to comprise 40～80 weight %, more preferably 50～70 Weight %, the amount of most preferably 60～65 weight % exists.Film former can comprise one-component or film former Mixture.The example of film former being suitable for includes one or more in following material:

Based on bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin, cresol novolac The epoxy resin latex of any one of resin；

Epoxy ester resin emulsion；

Epoxy polyurethane resin emulsion；

Polyester emulsion；

Vinyl esters ((methyl) acrylate epoxy resin) emulsion；

Polyurethane polyureas ester group dispersion.

Film former preferably comprises bisphenol A based epoxy resin emulsion, itself and one or more in above-mentioned emulsion Emulsion premixing is to improve by the wettability of particular substrate moistening.Epoxy resin is combined through with ester film former Improve the wettability of matrix moistening fiber surface flowed and the compatibility between the two and expand with The number of types of the matrix that described sizing material is compatible.

Can also come modified by adding the typical additive that can increase interface extension and/or fracture propagation energy Film former, this causes being improved particularly the fatigue resistance with such fibre-reinforced composite.For The example of the modifying agent of film former dissolves in any elastomer of liquid film former, example before being included in its emulsifying As, from Emerald performance materials company (Emerald Performance Materials) available carboxylic Base end-blocking butadiene acrylonitrile copolymer (CTBN), the dienite (CTB) of carboxy blocking, The butadiene-acrylonitrile polymer (ETBN) of epoxy radicals end-blocking, the butadiene-acrylonitrile of ethenyl blocking Polymer (VTB)；Or it is pre-dispersed in ring from Kaneka company with what Kane Ace MX grade obtained Core shell rubber particles in epoxy resins.

Film former can comprise one or more surfactants, such as, the poly-ethoxy of Octylphenoxy further Base ethanol (from the Triton X-100 of associating carbon compound company), ethylene oxide/propylene oxide block are altogether Polymers (from the Pluronic P103 of BASF), ethylene oxide/propylene oxide block copolymer (from The Pluronic F77 of BASF), ethylene oxide/propylene oxide block copolymer is (from BASF Pluronic10R5), the block copolymer (Pluronic from BASF of ethylene oxide and propylene oxide L101), polyox-yethylene-polyoxypropylene block copolymer (from the Pluronic P105 of BASF) or Person's ethylene oxide/propylene oxide copolymer (from BASF).Preferably, film former resin emulsion contains Two or more surfactants.Surfactant can be with 7～25 weights in film former resin emulsion The amount of amount % exists, and most preferably exists with the amount of 10～20 weight %.

The sizing composition of the present invention can comprise multiple additives, it include boron-containing compound, nonionic or Person's cationic lubricant, antistatic additive and weak acid.

Boron-containing compound such as borate is counted as the catalyst of various reaction.First they be considered to be catalyzed alkane The hydrolysis of TMOS, it is by forming silanol thus necessary with fiberglass surfacing formation covalent bond 's.Secondly, they are also believed to catalytic thermal thermosetting resin during manufacturing fibre-reinforced composite material component Curing reaction.The most eurypalynous boron salt can be used in the present invention.The example of boron-containing compound includes oxygen Change boron, sodium tetraborate, potassium metaborate, dipotassium tetraborate, ammonium hydrogen borate, ammonium tetrafluoroborate, butyl tetrafluoro boron Acid ammonium, Tetrafluoroboric acid calcium, lithium fluoroborate, potassium tetrafluoroborate, sodium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, Tetraethyl ammonium tetrafluoroborate and Tetrafluoroboric acid zinc.Ammonium tetrafluoroborate is most preferred.Based on active compound Gross weight, ammonium tetrafluoroborate is preferably with 0.2～8 weight %, preferably 0.5～5 weight %, more preferably 1～5 Weight %, the amount of most preferably 1.2～2.5 weight % exists.

Lubricant reduces the abrasion between filament and the generation of fine hair.Its existence is necessary to the process of fiber 's.Lubricant can be nonionic, cationic or anionic.Cationic lubricant, and Especially non-ionic lubricant is preferred.Suitably non-ionic lubricant is polyalkylene glycol fatty Acid and ester thereof.It is, for example possible to use PEG200, PEG300, PEG400, PEG600, and institute State ester and comprise monoleate, dioleate, monolaurate, dilaurate, monostearate and two Stearate.They can be from such as public affairs such as Ke Ningsi (Cognis), BASF, Ou Lian (Oleon) Department obtains.The example of cationic lubricant includes polyethyleneimine polyamide salt.Preferably lubricant is PEG400 monoleate.Gross weight based on active compound, described lubricant can be to comprise 5～32 Weight %, preferably 10～25 weight %, the amount of more preferably 15～25 weight % exists.Non-ionic lubricant Preferably represent current most of lubricant, solids weight based on described compositions, described lubricant Amount comprises 0～30 weight % solidss, more preferably 10～25 weight % solidss.If there is cationic Lubricant, then cationic lubricant is preferably to comprise 0～2 weight % solidss, preferably 0.8～1.2 weight % The amount of solids exists.

As shown in its name, antistatic additive is moving and friction insulating glass fibre during preventing from managing at which The accumulation of electric charge during dimension.The example of antistatic additive includes quaternary ammonium, tetraethylammonium chloride, lithium chloride, polyethylene Imines condensation substance, antistatic additive is preferably with 0～5 weight % solidss, preferably 0.5～1.5 weight % solidss Amount be present in described compositions.

Sizing composition according to the present invention can comprise at least one a small amount of weak organic acid further so that Contribute to silane hydrolysis and by final coating composition regulation to pH be 4.5 ± 0.5.The regulation of pH has Help reduce the speed of silane condensation, and give to put on sizing material the enough time of glass fibre.Described Sizing composition should preferably comprise the such weak organic acid less than 2 weight %.The most described organic acid It is acetic acid.Owing to acetic acid is volatile, so the solids weight percent not being calculated as in described compositions Content.

By various components: silane coupler, film former and additive are mixed in water to form aqueous coupling Agent compositions.Solid contents in water is typically not greater than 10 weight %, and especially, this content can wrap Containing 2～9 weight %, preferably 3～8 weight %, more preferably 4～7 weight %.By those skilled in the art institute Known method, generally by running the fiber pulled out from sleeve pipe to being continuously supplied aqueous coupling agent On coating roll, waterborne compositions can be applied to the surface of glass fibre.Then fibril aggregation is become a branch of Or several bundle, Shu great little is only limited by the size of sleeve pipe.Glass fiber bundle in composite generally wraps Include 800～8000 monofilament.Then glass fiber bundle is wrapped on spool and is stored in for be dried and In the controlled air that silane coupler is condensed on fiberglass surfacing and temperature.Selectively, Can be by fibre bundle cutting short-forming fiber line, it is embedded into further in thermoplastic matrix and can pass through note to be formed Molded extrusion and processed glass fiber reinforcement granule.

May then pass through braiding, edge is sewed, knitting continuous bundle processes continuous print glass fiber bundle further, To form the fabric of the reinforcing agent being used as composite.By such as works such as resin transfer mouldings (RTM) Skill, by which floor tissue layer stacks, and then impregnates with polymeric matrix.In another technology, the glass being dried Glass fabric can be by such as calendering (calendering) by pre-preg, and can pre-by monolayer Dipping fabric layer (the most unidirectional) stacking with formed can pass through compression forming, vacuum-bag process, The laminate that autoclave molding etc. are strengthened.Selectively, by such as the technology of filament wound or pultrusion, Polymeric matrix direct impregnation glass fiber bundle can be used.In view of the viscosity that they are the highest, thermoplastic poly Compound matrix may need the intermediate steps for dipping, and such as, powder infusion, fiber are mixed into.Some Thermoplastic matrix can as thermosetting polymer in-situ polymerization, such as at reaction injection molding (RIM) In.

Any polymer can serve as the matrix of the composite according to the present invention.Especially, described matrix can To be the thermosetting resins such as such as epoxy resin, unsaturated polyester (UP), vinyl esters, polyurethane.Epoxy resin It is particularly preferred.Selectively, described matrix can be thermoplastic polymer, such as, polypropylene (PP), Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethers ether copper (PEEK), Polyetherimide (PEI), linear polyester (PU), Merlon (PC), polystyrene and Its copolymer and terpolymer.The sizing composition epoxy resin of the present invention creates and is adopted as epoxy The sizing material of resin particular design and the suitable mechanical performance of the mechanical performance that obtains.Use undersaturated resin, this Dramatically increasing, in some cases, with the machine obtained with epoxy resin of the sizing material permission mechanical performance of invention The mechanical performance (with reference to Fig. 1) that tool performance is suitable.

According to the concrete polymer as matrix, the composition of sizing material can be optimized.Such as, if matrix is not In saturated polyester resin, vinyl ester resin, polyurethane resin or unsaturated polyester ester polyurethane hybrid resin One, then dialkoxy silicane is preferably (methyl) acryloxy silane and/or epoxy silane, and described Film former is preferably polyester base film former, it is also possible that or comprise epoxy film former.If matrix is Epoxy resin, then dialkoxy silicane is preferably epoxy silane, and described film former is preferably epoxy film forming Agent.

Fibre reinforced composites are especially sensitive to the mechanical strain of three types:

The elongation strain of a direction applying that () is vertical with the direction of fiber, it can be by as at ISO527/ Defined in 1, execute on unidirectional fibre-reinforced sample with the direction in 90 ° of the direction relative to fiber Add extension test to measure；

B () is parallel to the shear strain of fiber, it can be characterized by short beam test (SBT), institute State short beam test (SBT) and be applied to the three-point bend test on specific short sample, and as at ISO Defined in l4130；And

C () repeatability strain (tired), it can pass through tired as defined in ISO l3003:2003 Labor test characterizes, the repetition three that described testing fatigue is implemented under continuous print strain or continuous print stress value Point bending or extension test.

Fig. 1 represent to use be coated with 0.52 weight % sizing material (dried active solids) according to the present invention Glass fibre, and use various matrix: the one-way glass of epoxy amine, vinyl esters and unsaturated polyester (UP) Fibre reinforced composites (see the Lycoperdon polymorphum Vitt post in the embodiment 1 and Fig. 1 in table 1)；Be coated with spy Surely it is designed for the same glass fiber bought from market of the business sizing material of performance application, and uses epoxy Resin carries out short beam as the one-way glass fibre reinforced composites (the white post with reference in Fig. 1) of matrix The result of test (SBT).It can be seen that, the iotaberglass-epoxy amine of the sizing material with invention is combined The SBT result (Lycoperdon polymorphum Vitt post) of Materials Measurement is the highest by 6% with compared with the sizing material (white post) of prior art, This is close to 5% measurement error in this test.This result demonstrate the sizing material of the present invention can substitute for from The special sizing material of epoxy resin being commercially available is used together with epoxy resin, and does not lose with being coated with this The shear strength of the composite of the glass fiber reinforcement of sizing material.

When vinyl ester resin is used as matrix, the increase of SBT performance is fabulous, the increase of 15% The shearing resistance of vinyl ester composites is improved to identical with the shearing resistance level of epoxy composite material. With unsaturated polyester (UP) as matrix, compare the glass fibre being coated with the sizing material according to the present invention, SBT performance Increase the most surprising, than the composite with the glass fiber reinforcement of prior art SBT performance increase Add increase by 25%, as listed in Table 1.

Table 1. is according to the composition of the sizing material of the present invention

Fig. 2 represents that employing is coated with the sizing material glass fibre according to the present invention (sees in table 1, Fig. 2 Black circles, is called " vinyl esters-GF INV ") and use be designed for high-performance asphalt mixtures modified by epoxy resin Fat application, the commercially available glass fibre after applying glue (sees the white circle in Fig. 2, quilt Referred to as " vinyl esters-GF PA ") the testing fatigue result that the vinyl esters matrix strengthened is measured.Right Epoxy resin-matrix composite material for the identical glass fiber reinforcement of the vinyl esters of prior art is carried out Identical test (with reference to the white triangles shape in Fig. 2, be called " EP-GF PA ").Fig. 2 (a) Represent cycle-index and the function relation figure of maximum tensile stress when rupturing, and Fig. 2 (b) represents broken The function relation figure that when splitting, cycle-index strains with maximum tension.It can be seen that with Fig. 1 in report SBT Result is the same, can bear according to the fatigue behaviour of the vinyl ester composites of the glass fiber reinforcement of the present invention Ratio is currently used for the epoxy resin composite material of the performance application such as glass fiber reinforcement in air vane Fatigue behaviour (compares black circles (=INV) and white triangles shape (=EP-GF PA)).With existing The fatigue resistance of the vinyl ester composites of technology is compared, according to the vinyl ester composites of the present invention The raising of fatigue resistance (black circles) be surprising, before rupturing, cycle-index adds One to two order of magnitude, is particularly significant under high capacity (or strain) level.These results are by glass Fibre-reinforced vinyl ester composites increases to the qualified high-performance for exposure to fatigue stress should With such as the optional material group of air vane, hull etc..

Although be not to understand in detail comparing the definite composition of the proprietary sizing material used in test, but base In the publication in past, can reliably be concluded that all of sizing material major part that compares is different from this The sample of invention, this is because coupling agent is based on trialkoxy silane, as known to from document, And contrary with the sample of the present invention, these coupling agents do not comprise substantial amounts of dialkoxy silicane and acryloyl-oxy The combination (seeing table 1) of base silane.Combination between glass fibre and silane coupler should be in theory Increase along with the increase of number of the alkoxyl on the silicon atom being connected to silane, because the alkane of three hydrolysis Epoxide has higher interaction than only two groups and generates the possibility of combination with glass surface Property.Borate cocatalyst can promote the reactivity of silane and glass surface, and compensates dialkoxylated The relatively low interaction probability of silane.

Glass fibre relatively is to be commercially used for the application together with epoxy resin, it is hereby assumed that they comprise Most epoxy film former and epoxy silane coupling agent may be comprised.So that to according to the present invention's The mechanical properties results that the sizing material of embodiment is measured may compare with to the mechanical properties results measured by comparative example, Determine to use epoxy film former and epoxy silane in film former.According in the sizing composition of the present invention There is epoxy resin, also have and make they advantages more compatible with epoxy resin and undersaturated resin.

As explained above, the sizing material of hydrolysis being applied to each filament, each filament is in sizing composition and glass fibers The bundle of thousand of filaments it is gathered into immediately before dimension reaction completely.Being dried when when filament tight bunchy There is condensation reaction in period.When using traditional sizing composition based on trialkoxy silane coupling agent, silicon The hydroxyl of the hydrolysis of alcohol reacts with glass fibre, with the hydroxyl of the adjacent silanol chain being attached to same glass fiber Reaction, but also with the hydroxyl reaction of the adjacent silanol chain being attached to different glass fiber, therefore general in bundle Each fiber covalently flocks together.When aliging to produce unidirectional layout with another bundle ensuing by bundle Time, the described fiber whole cross section in the vertical plane of machine direction is not evenly distributed, but poly- The integrated respective bundle separated by cavity.When by thermoplastic resin-impregnated fibers, liquid resin is minimum through resistance, The i.e. path of high osmosis between bundle, and when buildup of pressure, its fiber in each bundle it Between permeate.If two adjacent fibers are combined with each other by-Si-O-Si-key, then resin can not arrive covalency The region of two glass fibre in key range.If there is many fiber combining in bundle, then will significantly Reducing by the zone of fiber of resin wetted of degree.

By comprising different amounts of dialkoxy silicane in sizing composition, the crosslinking water of sizing material can be regulated Flat.Have concluded that: when the silane coupler of at least 15% is dialkoxy silicane, it can be observed that Significantly effect.In the case of using epoxy silane, it is necessary to consider the amount of amino silane.Have observed that amino The amount of silane should be less than 5 weight % of the total solid matters weight of silane coupler.

Seeming contradiction, PRELIMINARY RESULTS shows: by using dialkoxy silicane coupling agent to replace three alkane Part or all of TMOS coupling agent, is not subject to according to the corrosion resistance of the composite of the present invention Adverse influence.This is considered as owing to fiber surface is by the more preferable wettability of resin wetted, its by fiber from Caustic shields ,-Si-O-Si-the network of crosslinking as formed on the fiber surface of prior art mean by Fiber is as described caustic shields.

These uncommon results owing to the more thorough wettability of fiber surface during impregnating at matrix, this High-dissolvability owing to sizing material so that during dipping fiber is separated from each other in bundle, thus increases significantly The permeability that is added in bundle and improve the compatibility between sizing material and various matrix, it is handed at various matrixes Strong combination is formed during connection.The sizing material of the present invention allows to be extended to surpass by the range of polymers being used for performance application Go out the epoxy resin of the most single selection.One of recurrent weakness of fibre-reinforced composite is limited Fatigue resistance.The sizing material of the present invention considerably improves the fatigue resistance of the composite of glass fiber reinforcement, It is make them particularly suitable for use in the application that circulation is exposed to stress and strain.Such as, span reaches 60 meters long Degree and the blade of longer wind power generating set, beg due to the rotation of himself and the change of wind speed very much Ask and obtain fatigability.Similarly, all structure member such as pipeline, wave and tide energies being exposed to current turn Parallel operation, hull etc. must have high fatigue resistance.In traffic and transport field, spring leaf yes cycle Property beg the example that obtains.These application merely comprise the composite according to the present invention possible application non-thoroughly Inventory to the greatest extent.Other application many are possible, such as, and container, preferably pressure vessel；The horizontal stroke of pultrusion Beam；Shell；Any mechanical elements；Shellproof element；Filament winding parts；Automobile and air transport, Parts in building, energy generator, motion, field of civil engineering.Those skilled in the art will stand I.e. recognize that the very good mechanical properties of the composite of the present invention can be best utilized.

Claims (15)

1. a sizing composition for the enhancing glass fibre in composite, described size composition Thing comprises:

A () silane based coupling agents mixture, the amount of described silane based coupling agents mixture is relative to not including The composition total weight of water and hydrolysis volatile byproducts is 2～30 weight %；

B () film former, the amount of described film former is relative to not including supplying institute in the emulsion of described film former The composition total weight of the weight of the solvent used is 40～80 weight %；

(c) additive,

It is characterized in that, described silane based coupling agents mixture comprises:

At least one dialkoxy silicane of (d) at least 15 weight %；With

E at least one of () at least 20 weight % comprises the insatiable hunger of the olefinic double bond activated by ester functional group With ester silane,

Wherein, except as otherwise noted, described weight % is the total solid matters weight relative to silane based coupling agents Measure.

Sizing composition the most according to claim 1, wherein, described beta-unsaturated esters silane includes choosing From (methyl) acrylate, fumarate, sorbate, cinnamate, maleate, itaconate, Part in citraconate, aconitate.

Sizing composition the most according to claim 1, wherein, described beta-unsaturated esters silane have as Lower chemical formula:

R "-CH=(CR')-(C=O)-O-(CH₂)_m-Si(R)_n(OR)_3-n

Wherein R can be-H ,-CH₃、-C₂H₅, wherein R' can be-H ,-CH₃、-CH₂-COOR, wherein R " can be-H ,-CH=CH₂,-COOH, phenyl, CH₃-CH=CH-,-COOR and wherein m It is 0～8.

Sizing composition the most according to claim 1, wherein, described film former is selected from following material In the mixture of one or more:

I () is based on bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin, cresol-novolak ring The epoxy resin latex of any one of epoxy resins；

(ii) epoxy ester resin emulsion；

(iii) polyester emulsion；

(iv) polyurethane polyureas ester group dispersion.

Sizing composition the most according to claim 1, wherein, described silane based coupling agents mixture Comprising the dialkoxy silicane of at least 20 weight %, wherein said weight % is relative to silane based coupling agents Total solid matters weight measure, and the one that wherein said dialkoxy silicane is in following material Or multiple:

(i) dialkoxy-epoxy-silane, selected from γ-glycidoxypropyl dimethoxysilane, γ- Glycidoxypropyl group-methyldiethoxysilane；

(ii) dialkoxy-vinyl-silane, selected from vinyl methyl dimethoxysilane, vinyl first Base diethoxy silane；

(iii) dialkoxy-(methyl) acryloxy-silane, selected from γ-(methyl) acryloxypropyl first Base dimethoxysilane, γ-(methyl) acryloxypropyl diethoxy silane, ((methyl) acryloyl Epoxide methyl) metil-dimethoxysilane；

(iv) dialkoxy-amino-silane, selected from γ-aminopropyltriethoxy diethoxy silane, N-β-(ammonia Ethyl)-γ-aminopropyl-methyl dimethoxysilane, N-β-(aminoethyl)-gamma-amino isobutyl methyl dimethoxy -silane, γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-methyl diethoxy silicon Alkane；

(v) dialkoxy-mercapto-silane.

Sizing composition the most according to claim 1, wherein, of described beta-unsaturated esters silane Point or entirely dialkoxy silicane.

Sizing composition the most according to claim 1, wherein, described silane based coupling agents mixture Comprising (methyl) acryloxy silane of at least 25 weight %, wherein said weight % is relative to silylation The total solid matters weight of coupling agent is measured, and wherein said beta-unsaturated esters silane is selected from following material In (methyl) acryloxy silane:

(i) (methyl) acryloyl group dialkoxy silicane；

(ii) (methyl) acryloyl group trialkoxy silane；And/or

(iii) (methyl) acryloyl group monoalkoxysilane.

Sizing composition the most according to claim 1, wherein, described silane based coupling agents comprises not More than the amino silane of 5 weight %, wherein said weight % is the total solid matters relative to silane based coupling agents Weight is measured, and one or more that described amino silane is in following material:

I () amino dialkoxy silicane, selected from γ-aminopropyltriethoxy diethoxy silane, N-β-(ammonia second Base)-γ-aminopropyltriethoxy dimethoxysilane, Ν-β-(aminoethyl)-γ-aminopropyl-methyl dimethoxysilane, N-β-(aminoethyl)-gamma-amino isobutyl methyl dimethoxy-silane, γ-aminopropyltriethoxy dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl-methyldiethoxysilane；And/or

(ii) amino-trialkoxy silane, selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy Base silane, N-β-(aminoethyl)-γ-aminopropyl-trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyl three second TMOS, diethylidene three aminopropyl trimethoxysilane, double-(γ-trimethoxy-silylpropyl) Amine, N-phenyl-γ-aminopropyltrimethoxysilane, gamma-amino-3,3-dimethylbutyl trimethoxy silane, γ- Ammobutyltriethoxysilane, the poly-azepine amide of silanization.

Sizing composition the most according to claim 1, wherein, described silane based coupling agents at least wraps Containing epoxy silane, in an amount of from least the 20% of the total solid matters weight of silane based coupling agents, and described epoxy One or more in following material of silane:

(i) epoxy-dialkoxy silicane, selected from γ-glycidoxypropyl dimethoxysilane, γ- Glycidoxypropyl group-methyldiethoxysilane；Or

(ii) epoxy-trialkoxy silane, selected from β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ- Glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane, γ-epoxy the third oxygen Base propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl Triethoxy-Silane, β-(3,4-epoxide ring Hexyl) ethyl trimethoxy silane, 5,6-epoxyhexyl-triethoxysilane.

Sizing composition the most according to claim 1, wherein, described additive comprises following material In one or more:

I () boron-containing compound, it selects free boric acid, boron oxide, sodium tetraborate, potassium metaborate, four boron Acid potassium, ammonium hydrogen borate, ammonium tetrafluoroborate, butyl ammonium tetrafluoroborate, Tetrafluoroboric acid calcium, lithium fluoroborate, four Potassium borofluoride, sodium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl ammonium tetrafluoroborate and Tetrafluoroboric acid The group that zinc is formed；

(ii) non-ionic lubricant, including: the fatty-acid monoester of Polyethylene Glycol, described nonionic moistens Lubrication prescription exists with the amount of 0～30 weight % solidss；

(iii) cationic lubricant, deposits with the amount of 0～2 weight % solidss in described sizing composition ?；

(iv) antistatic additive, exists with the amount of 0～5 weight % solidss；

V final coating composition regulation is the weak organic acid of 4.5 ± 0.5 to pH by (), and described In sizing composition, the amount with 0～2 weight % exists.

11. be coated with according to the sizing composition according to any one of claim 1-10 as composite wood The glass fibre of the enhancing in material.

12. glass fibre reinforced composions, it is characterised in that described glass fibre reinforced composion bag Include glass fibre according to claim 11.

13. glass fibre reinforced composions according to claim 12, wherein, matrix is insatiable hunger With polyester resin, vinyl ester resin, polyurethane resin or undersaturated PAUR compound tree One in fat, and wherein

I () described dialkoxy silicane is selected from (methyl) acryloxy silane and/or epoxy silane,

(ii) described film former is selected from polyester base film former, vinyl esters and/or epoxy film former.

14. glass fibre reinforced composions according to claim 12, wherein, matrix is epoxy Resin, and wherein

I () described dialkoxy silicane is selected from epoxy silane,

(ii) described film former is selected from epoxy film former.

15. according to the glass fibre reinforced composion according to any one of claim 12-14, wherein, Described glass fibre reinforced composion is the parts of windmill；Pipeline；Container；The crossbeam of pultrusion；Outward Shell；Mechanical elements；Spring leaf；Shellproof element；Filament winding parts；Boats and ships and naval vessels, automobile and Parts in air transport, building, power generator, motion, field of civil engineering.