CN101076549A - Polyester binding compositions - Google Patents

Abstract

Disclosed are formaldehyde-free, thermally-curable, alkaline, aqueous binder compositions. The disclosed binder compositions may be cured to substantially water-insoluble thermoset polyester resins, including formaldehyde-free, substantially water-insoluble thermoset polyester resins. Uses of the disclosed binder compositions as binders for non-woven fibers and fiber materials are also disclosed.

Description

Polyester binding compositions

The cross reference of related application

The application requires the rights and interests of U.S. Provisional Application sequence number 60/618441 that proposed on October 13rd, 2004 and the U.S. Provisional Application sequence number 60/700486 that proposed on July 19th, 2005 under 35 U.S.C. § 119 (e), the application is open with reference to quoting these.

Invention field

The present invention relates to the non woven fibre binder composition.Particularly, the present invention relates to non woven fibre thermal curable polyester binder.

Background technology

Fiber insulation product generally comprises the felting glass fibre that combines by solidified thermoset polymerization resol (resole resin).In the manufacturing processed of this product, molten glass flow is drawn into the fiber of different lengths, be blown into then in the forming cavity, in forming cavity, make its almost tissue ground, or, deposit on the mobile travelling belt as felt with different pattern.When fiber transports in forming cavity and still go back heat behind stretched operation, spray with the water-base resin binder solution to fiber.Air can evaporate the most of moisture of resin glue usually by flowing of fibrefelt during the waste heat of glass fibre and the forming operation, thereby the remaining ingredient of the tackiness agent that stays on fiber is viscosity or half viscosity high solid liquid.The fibrefelt that gained applies is commonly referred to as " wet felt ".Then with this owing to cross this felt and the fibrefelt or the wet felt of the coating that forms with compressed state are transported to transition range from forming cavity in forming cavity high speed air communication, at this felt of transition range because the screen resilience of glass fibre and vertical expansion.This vertical expansion is very important in the heat insulation or acoustical insulation products manufacturing process at commercial acceptable glass fibre.Then, the felt that applies is transferred in the curing oven, made hot blast blow over this felt herein and combine securely with cure adhesive and with glass fibre.

Resol is that the mol ratio of phenol and aldehyde is about 1: the resol that 1.1-is about 1: 5.Preferred phenol is about 1 with the ratio of aldehyde: about 1: 3 of 2-.The phenol component of resol can comprise various replacements and unsubstituted phenolic compound.The preferred formaldehyde of aldehyde component of resol, but can comprise so-called aldehyde or aldehyde Equivalent, for example acetal or the hemiacetal sheltered.The specific examples of appropriate aldehyde comprises: formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, furfural and phenyl aldehyde.

Adopt phenol-formaldehyde (PF) resol in the traditional method, and with the phenol-formaldehyde resol (PFU resin) of urea chain extension, and greatly rely on them in the several years in the past and prepare the fiber insulation product tackiness agent.Though these resins are very cheap, and provide the cured fiberglass insulation product of the physicals with expectation, they often have very high free formaldehyde content, and smell special or that dislike has limited their purposes in some applications.In addition, during fiber insulation product is made, exist potential formaldehyde emissions and workman to expose.Therefore, often need to install expensive control device to minimize may exposing of workman's PARA FORMALDEHYDE PRILLS(91,95) discharging with PF and PFU resol as the manufactory of insulating products main binder component, and expensive emission reduction device is installed is handled waste gas, require standard to satisfy specific Maximum Achieveable Control Technology (MACT).The selection of formaldehydeless product or technology comprises: i) add formaldehyde scavenger in tackiness agent, with reduction or removing free formaldehyde, thereby limit its follow-up discharging and/or smell; Ii) make resin reaction continue the long period, to reduce the free formaldehyde content in the rosin products; Or iii) utilize the formaldehyde-free resins prescription.

Use formaldehyde scavenger can cause precipitation, this derives from the soluble adducts of scavenging agent itself and/or scavenging agent and any residual formaldehyde.In addition, the long period that makes resin reaction continue to be enough to reach the target formaldehyde content can make rosin products be accompanied by higher molecular weight.This higher molecular weight resin can lack some and use required performance, and for example thickness very often sticks on the production unit fiberglass products of tackiness agent and application of adhesive.In addition, higher molecular weight PF resol often has higher " tetradimer " content.Tetradimer is the PF dipolymer of the highly crystalline that exists in the resol for preparing under the base catalysis condition, and it often is easy to precipitation.As if easier precipitation during free formaldehyde in removing resin.The Tetradimer precipitation can cause spray nozzle clogging, and causes forming the precipitation that must remove in the resin glue hold-up vessel and in resin itself.

Therefore, as the surrogate of PF and PFU resol, the formaldehyde-free resins prescription receives publicity day by day as the tackiness agent in glass-fiberinsulation and other product manufacturings.

Summary of the invention

Aqueous adhesive composition has been described.On the one hand, this aqueous adhesive composition is formaldehydeless.On the other hand, this aqueous adhesive composition thermal curable.On the other hand, this aqueous adhesive composition has alkaline pH.Also described the aqueous adhesive composition that is used to make fiber product, fiber product comprises that the non woven fibre product for example comprises the fiber product that heat resistance fiber etc. is formed by glass fibre and/or other fibers.Aqueous adhesive composition and use the methods involving of this binder composition can comprise one or several feature described herein or combination of features.

In an illustrative embodiment, that aqueous adhesive composition is solidified into is formaldehydeless, water-fast thermosetting polyester resin basically.In another illustrative embodiment, said composition comprises one or more polyprotonic acid components or its acid anhydrides or the salt derivative that has acid groups, with the multiple polyhydroxy component that has hydroxyl, wherein the pH of binder composition is greater than about 7, and illustrative ground also is less than or equal to about 10.In another illustrative embodiment, said composition comprises one or more polyprotonic acid components and multiple polyhydroxy component, and wherein the ratio of the hydroxyl molar equivalent number that exists on molar equivalent number of the acid groups that exists on the polyprotonic acid component or its acid anhydrides or salt derivative (number ofmolar equivalents) and the multiple polyhydroxy component is about 0.7: between about 1.3: 1 of the 1-.In a kind of variant, the molar equivalent number of the acid groups that exists on the polyprotonic acid component or its acid anhydrides or salt derivative is excessive.In another variant, the hydroxyl molar equivalent number that exists on the multiple polyhydroxy component is excessive.In another variant, the ratio of the hydroxyl molar equivalent number that exists on the molar equivalent number of the acid groups that exists on the polyprotonic acid component or its acid anhydrides or salt derivative and the multiple polyhydroxy component is about 1.3: 1.In another variant, the ratio of the hydroxyl molar equivalent number that exists on the molar equivalent number of the acid groups that exists on the polyprotonic acid component or its acid anhydrides or salt derivative and the multiple polyhydroxy component is about 1: 1.

In another illustrative embodiment, said composition comprises one or more polyprotonic acid components as dicarboxylic acid, include but not limited to derivative that unsaturated aliphatic dicarboxylic acid, radical of saturated aliphatic dicarboxylic acid, aromatic dicarboxylic acid, unsaturated cyclic dicarboxylic acid, saturated cyclic dicarboxylic acid, their hydroxyl replace etc., and their salt and anhydride ester derivs.In another illustrative embodiment, said composition comprises that one or more are as tricarboxylic polyprotonic acid component, include but not limited to derivative that unsaturated aliphatic tricarboxylic acid, radical of saturated aliphatic tricarboxylic acid, aromatic tricarboxylic acid, unsaturated cyclic tricarboxylic acid, saturated cyclic tricarboxylic acid, their hydroxyl replace etc., and their salt and anhydride ester derivs.In another illustrative embodiment, said composition comprises one or more polyprotonic acid component and their salt and anhydride ester derivs as tetracarboxylic acid, five yuan of polycarboxylic acids such as carboxylic acid, and their combination.Certainly any of these polyprotonic acid all can not necessarily be substituted, and for example uses replacements such as hydroxyl, halogen, alkyl, alkoxyl group.Aspect an illustrative, said composition is an alkaline compositions, and wherein one or more polyprotonic acid components neutralize by adding alkali, or wherein adopt some salt of one or more polyprotonic acid components.In another illustrative embodiment, said composition comprises by adding one or more polyprotonic acid components of alkali neutral or salt, for example succsinic acid, citric acid or fumaric acid etc.In another illustrative embodiment, the polyprotonic acid component is with for example amine such as ammoniacal liquor neutral toxilic acid.In another illustrative embodiment, the polyprotonic acid component is the ammonium salt of maleate.

In another illustrative embodiment, the polyvinyl acetate that described multiple polyhydroxy component is partial hydrolysis for example ELVANOL (from DuPont Packaging and IndustrialPolymers, Wilmington, Delaware, USA is purchased), with intact hydrolyzed poly vinyl acetate for example MOWIOL (from Clariant, Clear Lake, Texas, USA is purchased) mixture.The polyvinyl acetate and/or the complete hydrolysis polyvinyl acetate that for example certainly can comprise the partial hydrolysis of CELVOL (from Celanese, Calvert City, Kentucky, USA is purchased) here in the binder composition of describing.

In another illustrative embodiment, said composition also comprises catalyzer, and for example acid or acid/salt comprise inorganic and organic acid, and their salt.The illustrative organic acid comprises sulfonic acid and salt thereof, for example tosic acid, paratoluenesulfonic acid ammonium salt, naphthalene disulfonic acid ammonium etc.It should be understood that this catalyzer can improve the ester formation speed of binder composition setting up period described herein.In another illustrative embodiment, said composition also comprises silicon-containing compound, for example silyl ether and alkyl silyl ether, and they can be not necessarily by for example replacements such as halogen, alkoxyl group, amino.On the one hand, silicon-containing compound is the amino silicon-containing compound that replaces, and includes but not limited to γ-An Jibingjisanyiyangjiguiwan.It should be understood that binder composition setting up period that silicon-containing compound is described herein can play the effect of coupling agent.

In another illustrative embodiment, the processing fiber has been described, comprise the method for non woven fibre.Aspect an illustrative, this method comprises makes fiber contact with the thermal curable aqueous adhesive composition that comprises one or more polyprotonic acid components and multiple polyhydroxy component described herein, wherein the pH of binder composition is greater than about 7, and also be less than or equal to illustrative approximately 10, and be enough to solidify under the elevated temperature of this binder composition this thermal curable aqueous adhesive composition of heating to form ester.On the one hand, this polyester is water insoluble basically.On the other hand, this polyester is a thermosetting resin.

In another illustrative embodiment, glass fiber product has been described.This glass fiber product comprises by heating and has been coated in the composition that the thermal curable aqueous adhesive composition described herein on the fiber of non woven fibre felt for example obtains.On the one hand, the pH of this binder composition is greater than about 7, and illustrative ground also is less than or equal to about 10.In one embodiment, this binder composition comprises one or more polyprotonic acid components described herein and multiple polyhydroxy component.

Describe in detail

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition has been described.This binder composition comprises one or more polyprotonic acid components or its acid anhydrides or salt derivative that has acid groups and the multiple polyhydroxy component that has hydroxyl, and wherein the pH of this binder composition is greater than about 7, and illustrative ground also is less than or equal to about 10.Said composition can be used as the tackiness agent of non woven fibre, the tackiness agent of the glass fibre in for example making as insulating products.In one embodiment, discovery can be quickened or when improving the catalyzer of chemical reaction velocity when not existing, the short period of time heating formaldehydeless alkaline aqueous adhesive composition that comprises one or more polyprotonic acid components and multiple polyhydroxy component described herein has prepared water-fast basically thermosetting polyester resin.Therefore, find that one or more polyprotonic acid components can not exist under the alkaline aqueous conditions of catalyzer,, form thermosetting polyester resin with multiple polyhydroxy component reaction.

In an illustrative embodiment, this formaldehydeless thermal curable alkalescence aqueous adhesive composition is unreacted basically on being applied to such as the base material of non woven fibre sample the time.In case heating, this tackiness agent is dried and finishes thermofixation.Should be understood that described drying and thermofixation can be successively, same period or take place simultaneously.Term " thermal curable " is meant structure or the metamorphosis in the aqueous binder that is enough to change the non woven fibre character that has applied the significant quantity tackiness agent that takes place by heating; The covalent reaction that these change including but not necessarily limited to binder ingredients comprises crosslinkedly, and binder ingredients is to the adhesion of the improvement of base material, and the hydrogen bonding of binder ingredients.

Term used herein " formaldehydeless " is meant that aqueous adhesive composition is substantially free of formaldehyde, and/or does not emit formaldehyde basically when dry and/or curing; With composition weight meter, the general formaldehyde that maybe can discharge that exists in formaldehydeless composition is lower than about 1ppm.

The pH value that term used herein " alkalescence " is meant solution is greater than about 7, and illustrative ground also is less than or equal to about 10.

Term used herein " water-based " comprises water and includes but not limited to the mixture that alcohol, ether, amine, polar aprotic solvent etc. are formed by water and other water-miscible solvents basically.

Term used herein " glass yarn ", " non woven fibre " and " glass fibre " are meant the heat resistance fiber that is fit to bear elevated temperature, for example mineral fibre, Kevlar, ceramic fiber, steel fiber, carbon fiber, polyimide fiber, some trevira, regenerated fiber and glass fibre.For purposes of illustration, this fiber is exposed to about unaffected basically under the temperature more than 120 ℃.

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition comprises that one or more have the polyprotonic acid component of acid groups, or their acid anhydrides or salt derivative.On the one hand, described one or more polyprotonic acid components have enough non-volatilities, make its maintenance can be used for the maximized of reacting with polyhydroxy component.The polyprotonic acid component can replace with other chemical functional groups.Certainly should select other functional groups so that they to vibrin preparation or form influence minimum.As an illustration, the polyprotonic acid component can be a for example toxilic acid of dicarboxylic acid.Other suitable polyprotonic acid components include but not limited to equisetic acid, hexanodioic acid, nonane diacid, the ethylene-dimalonic acid dihydride, the butane tricarboxylic acid, chlorendic acid, citraconic acid, citric acid, Dicyclopentadiene (DCPD)-toxilic acid adducts, diethylene triaminepentaacetic acid(DTPA), the adducts of kautschin and toxilic acid, interior methylene radical chlordene phthalic acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), complete maleinization (maleated) rosin, the maleinization tall oil fatty acid, fumaric acid, pentanedioic acid, m-phthalic acid, methylene-succinic acid, be oxidizing to the right maleinization rosin of alcohol with Potassium peroxide with carboxylic acid, oxysuccinic acid, methylfumaric acid, introduce the dihydroxyphenyl propane or the Bisphenol F of 3-4 carboxyl by KOLBE-Schmidt reaction and carbon dioxide reaction, oxalic acid, phthalic acid, poly(lactic acid), sebacic acid, succsinic acid, tartrate, terephthalic acid, tetrabromophthalate, tetrachlorophthalic acid, tetrahydrophthalic acid, 1,2, the 4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid etc., with their acid anhydrides and salt, and their combination.

In an illustrative embodiment, the acid groups of the polyprotonic acid component of formaldehydeless thermal curable alkalescence aqueous adhesive composition neutralizes with alkali before its hydroxyl reaction with multiple polyhydroxy component forms vibrin, thereby changes into hydrochlorate group (acid salt groups).Should be understood that fully neutralization, promptly about 100% with the equivalent basic calculation, can eliminate in polyester forms before titration or the part and any demand of the acid groups in the polyprotonic acid component, but can estimate that incomplete neutralization will can not suppress polyester formation." alkali " used herein refers to be enough to promote under the condition that polyester forms volatilization or nonvolatile alkali basically.As an illustration, alkali can be for example ammoniacal liquor of volatile alkali; As selection, alkali can be for example yellow soda ash of non-volatile alkali, and considers for example other non-volatile alkali of sodium hydroxide, potassium hydroxide etc.Neutralization can the polyprotonic acid component with carry out before multiple polyhydroxy component mixes or after mixing.

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition comprises the multiple polyhydroxy component that has hydroxyl.On the one hand, this multiple polyhydroxy component has enough non-volatilities, so that its maintenance can be used for the maximized with the polyprotonic acid component reaction.This multiple polyhydroxy component illustrative ground can be the polyvinyl acetate ester mixture of polyvinyl alcohol mixture, partial hydrolysis, the polyvinyl acetate ester mixture of complete hydrolysis, or the mixture of partial hydrolysis and complete hydrolysis polyvinyl acetate.As an illustration, when partial hydrolysis polyvinyl acetate during as the component of described multiple polyhydroxy component, can adopt the polyvinyl acetate of 87-89% hydrolysis, for example the DuPont ELVANOL 51-05 of the about 22000-26000Da of molecular weight, the about 5.0-6.0 centipoise of viscosity.Other partial hydrolysis polyvinyl acetate that can be used for preparing above-described binder composition include but not limited to the polyvinyl acetate of the 87-89% hydrolysis that molecular weight and viscosity are different with ELVANOL51-05, for example DuPont ELVANOL51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 52-22, ELVANOL 50-26, ELVANOL 50-42; And the polyvinyl acetate of molecular weight, viscosity and/or degree of hydrolysis and the hydrolysis of ELVANOL 51-05 distinct portions, for example DuPontELVANOL 51-03 (86-89% hydrolysis), ELVANOL 70-14 (95.0-97.0% hydrolysis), ELVANOL 70-27 (95.5-96.5% hydrolysis), ELVANOL 60-30 (90-93% hydrolysis).Other partial hydrolysis polyvinyl acetate that can be used for preparing above-described binder composition include but not limited to Clariant MOWIOL 15-79, MOWIOL 3-83, MOWIOL4-88, MOWIOL 5-88, MOWIOL 8-88, MOWIOL 18-88, MOWIOL23-88, MOWIOL 26-88, MOWIOL 40-88, MOWIOL 47-88 and MOWIOL 30-92, and Celanese CELVOL 203, CELVOL 205, CELVOL 502, CELVOL 504, CELVOL 513, CELVOL 523, CELVOL523TV, CELVOL 530, CELVOL 540, CELVOL 540TV, CELVOL418, CELVOL 425 and CELVOL 443.Also can attempt adopting the same or similar partial hydrolysis polyvinyl acetate that obtains from other suppliers.

As an illustration, when complete hydrolysis polyvinyl acetate during, can adopt the Clariant MOWIOL 4-98 of the about 27000Da of molecular weight as the component of described multiple polyhydroxy component.Other complete hydrolysis polyvinyl acetate that can attempt adopting include but not limited to DuPont ELVANOL70-03 (98.0-98.8% hydrolysis), ELVANOL 70-04 (98.0-98.8% hydrolysis), ELVANOL 70-06 (98.5-99.2% hydrolysis), ELVANOL 90-50 (99.0-99.8% hydrolysis), ELVANOL 70-20 (98.5-99.2% hydrolysis), ELVANOL 70-30 (98.5-99.2% hydrolysis), ELVANOL 71-30 (99.0-99.8% hydrolysis), ELVANOL70-62 (98.4-99.8% hydrolysis), ELVANOL 70-63 (98.5-99.2% hydrolysis), ELVANOL 70-75 (98.5-99.2% hydrolysis), Clariant MOWIOL 3-98, MOWIOL 6-98, MOWIOL 10-98, MOWIOL 20-98, MOWIOL 56-98, MOWIOL 28-99 and Celanese CELVOL 103, CELVOL 107, CELVOL305, CELVOL 310, CELVOL 325, CELVOL 325LA and CELVOL 350, and the same or similar complete hydrolysis polyvinyl acetate that obtains from other suppliers.

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition comprises and contains silicone couplet (for example organic silicone oil).Many silicone couplets that contain can obtain from Dow-Corning Corporation, Petrarch Systems and General Electric Company.As an illustration, contain silicone couplet and comprise compound such as silyl ether and alkyl silyl ether, they all can be not necessarily by for example replacements such as halogen, alkoxyl group, amino.On the one hand, silicon-containing compound is the amino silane that replaces, for example γ-An Jibingjisanyiyangjiguiwan (Dow SILQUEST A-1101; Dow Chemical; Midland, MI; USA).On the other hand, silicon-containing compound is γ-Huan Yangbingyangbingjisanjiayangjiguiwan (DowSILQUEST A-187).When in an illustrative embodiment, adopting, generally account for about 2.0% (weight) of the about 0.2%-of adhesive solids such as the above-mentioned content of silicone couplet in binder composition that contains.

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition comprises that also the polyester that can improve binder composition setting up period described herein forms the catalyzer of speed.As an illustration, this catalyzer can be an ammonium salt, for example paratoluenesulfonic acid ammonium salt or naphthalene disulfonic acid ammonium.Other appropriate catalyst include but not limited to ammonium sulfate, ammonium chloride, sulfuric acid, lactic acid, lead acetate, sodium acetate, lime acetate, zinc acetate, organo-tin compound, titanium ester, ANTIMONY TRIOXIDE SB 203 99.8 PCT, germanium salt, sodium hypophosphite, sodium phosphite, methylsulfonic acid and tosic acid, and their mixture.Be also noted that if comprise an acidic catalyst in the binder composition, just need to regulate the pH of said composition to realize alkalescence.

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition also comprises and is designed for one or more additives that increase the mobile of binder composition and/or postpone the agglomerative speed that binder composition may carry out.As an illustration, additive can be such as the polypropylene glycol of glycerine, dextrin, replacement and the compound of TriMethylolPropane(TMP).

In an illustrative embodiment, formaldehydeless thermal curable alkalescence aqueous adhesive composition can by mix be neutralized or in the presence of multiple polyhydroxy component second polyhydroxy component of the aqueous solution, about 10-30 weight % of first polyhydroxy component of the aqueous solution, about 10-30 weight % of the polyprotonic acid component of the about 10-50 weight of original position neutral % the aqueous solution and contain silicone couplet and prepare.On the one hand, binder composition also can comprise the aqueous solution of the catalyzer that can improve setting up period polyester formation speed.On the other hand, binder composition also can comprise and is designed for the additive that increases the mobile of binder composition and/or postpone the agglomerative speed that binder composition may carry out.By changing polyprotonic acid component, multiple polyhydroxy component, containing silicone couplet, and composition, their starting point concentration and the solution ratio of mixture of the additive of nonessential catalyzer and increase flowability, the binder solution composition that can prepare wide region, wherein the pH of binder composition is alkaline, as an illustration, greater than about 7 to being less than or equal in about 10 the scope.Certainly, because alkaline formaldehyde-free binder compositions described herein adopts common manufacturing process and cure parameter, thereby can adopt existing manufacturing installation in the glass fibre manufactory, therefore very useful.

Following examples further describe specific embodiments.These embodiment only are used for illustrative use, and never in any form the present invention or notion of the present invention are limited in any specific physical structure.For example, though in following examples 1 to 8 in the polyprotonic acid component in the molar equivalent number of acid groups or its acid anhydrides or salt derivative and the multiple polyhydroxy component ratio of the molar equivalent number of hydroxyl be about 1.3: 1, and be about 1: 1 among the embodiment 11, but should be understood that in the distortion of embodiment described herein, this ratio can change in the scope that does not influence described essence of the present invention, for example is included in about 0.7: about 1.3: 1 interior ratio of scope of 1-.In addition, though following examples comprise that the toxilic acid ammonium is as the polyprotonic acid component, MOWIOL 4-98 and ELVANOL 51-05 are as described multiple polyhydroxy component, but should be understood that in the distortion of the embodiment of describing herein, can adopt as the component of selecting and not influence described essence of the present invention, for example comprise with the ammonium salt of different dicarboxylic acid as the different mixtures of polyprotonic acid component that adopts in the composition described herein and polyvinyl acetate complete hydrolysis and/or partial hydrolysis as the described multiple polyhydroxy component that adopts in the composition described herein.

Embodiment 1

In 14.2% solution (9.8g) of the MOWIOL 4-98 of the 69g that at room temperature stirs, add 70g 30.6% toxilic acid ammonium solution (being equivalent to 16.6g toxilic acid solid), 20g15% tosic acid ammonium solution (3g), 0.6g SILQUEST A-1101 silane and 41g soft water successively, prepare about 200g solution.The pH of this solution is 7.0, form by about 32.6% MOWIOL4-98,55.3% toxilic acid, 10% paratoluenesulfonic acid ammonium salt and 2% SILQUEST A-110 silane (as the relative percentage of total dissolved solidss), and contain the 15% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 2

To the MOWIOL 4-98 (80% that at room temperature stirs, 9.0g) and ELVANOL51-05 (20%, 2.2g) 79g 14.3% mixing solutions in add 79g 30.6% toxilic acid ammonium solution (being equivalent to 18.8g toxilic acid solid) and 43g soft water successively, prepare about 200g solution.The pH of this solution is 7.28, is made up of about 30% MOWIOL 4-98,7.3% ELVANOL51-05 and 62.6% toxilic acid (as the relative percentage of total dissolved solidss), and contains the 15% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 3

To the MOWIOL 4-98 (95% that at room temperature stirs, 5.3g) and ELVANOL 51-05 (5%, 0.28g) 39g 14.3% mixing solutions in add 40g 30.6% toxilic acid ammonium solution (being equivalent to 9.5g toxilic acid solid) and 21g soft water successively, prepare about 100g solution.This solution is made up of about 35.1% MOWIOL 4-98,1.9% ELVANOL 51-05 and 63.0% toxilic acid (as the relative percentage of total dissolved solidss), and contains the 15% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 4

In 3.1g 14.5% ELVANOL 51-05 (0.45g) solution that at room temperature stirs, add 54g 14.2% MOWIOL 4-98 solution (7.7g), 58g 30.6% toxilic acid ammonium solution (being equivalent to 13.8g toxilic acid solid), 1.7g maleation (maleinized) soya-bean oil, 2.2g 80% corn syrup solution (1.8g), 22.5g 20% ammoniumsulphate soln (4.5g), 0.6gSILQUEST A-1101 silane, 58g soft water and 36.5g 19% ammonia solution successively, prepare about 237g solution.The pH of this solution is 10.49, form by about 25.2% MOWIOL 4-98,1.5%ELVANOL 51-05,45.2% toxilic acid, 5.6% maleation soya-bean oil, 5.9% maize treacle, 14.7% ammonium sulfate and 2.0% SILQUEST A-1101 silane (as the relative percentage of total dissolved solidss), and contain the 13% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 5

In 3.3g 14.5% ELVANOL 51-05 (0.48g) solution that at room temperature stirs, add 57g 14.2% MOWIOL 4-98 solution (8.1g), 62g 30.6% toxilic acid ammonium solution (being equivalent to 14.7g toxilic acid solid), 1.7g maleation soya-bean oil, 23g 20% ammoniumsulphate soln (4.6g), 0.6g SILQUEST A-1101 silane, 53g soft water and 13.2g 19% ammonia solution successively, prepare about 214g solution.The pH of this solution is 9.90, form by about 26.8% MOWIOL4-98,1.6% ELVANOL 51-05,48.7% toxilic acid, 5.6% maleation soya-bean oil, 15.2% ammonium sulfate and 2.0% SILQUEST A-1101 silane (as the relative percentage of total dissolved solidss), and contain the 14% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 6

In 3.5g 14.5% ELVANOL 51-05 (0.51g) solution that at room temperature stirs, add 61g 14.2% MOWIOL 4-98 solution (8.7g), 66g 30.6% toxilic acid ammonium solution (being equivalent to 15.7g toxilic acid solid), 23g 20% ammoniumsulphate soln (4.6g), 0.6gSILQUEST A-1101 silane and 46g soft water successively, prepare about 200g solution.The pH value of this solution is 7.60, form by about 28.9% MOWIOL 4-98,1.7% ELVANOL 51-05,52.1% toxilic acid, 15.3% ammonium sulfate and 2.0% SILQUEST A-1101 silane (as the relative percentage of total dissolved solidss), and contain the 15% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 7

In 4.0g 14.5% ELVANOL 51-05 (0.58g) solution that at room temperature stirs, add 67g 14.2% MOWIOL 4-98 solution (9.5g), 74g 30.6% toxilic acid ammonium solution (being equivalent to 17.6g toxilic acid solid), 7.5g 20% ammoniumsulphate soln (1.5g), 0.6gSILQUEST A-1101 silane and 47g soft water successively, prepare about 200g solution.This solution is made up of about 31.9% MOWIOL 4-98,1.9% ELVANOL 51-05,59.1% toxilic acid, 5.0% ammonium sulfate and 2.0% SILQUEST A-1101 silane (as the relative percentage of total dissolved solidss), and contains the 15% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 8

In 4.0g 14.5% ELVANOL 51-05 (0.58g) solution that at room temperature stirs, add 68g 14.2% MOWIOL 4-98 solution (9.7g), 75g 30.6% toxilic acid ammonium solution (being equivalent to 17.8g toxilic acid solid), 7.5g 20% ammoniumsulphate soln (1.5g), 0.06gSILQUEST A-1101 silane and 45g soft water successively, prepare about 200g solution.This solution is made up of about 32.7% MOWIOL 4-98,1.9% ELVANOL 51-05,60.0% toxilic acid, 5.1% ammonium sulfate and 0.2% SILQUEST A-1101 silane (as the relative percentage of total dissolved solidss), and contains the 15% dissolved solid (as the per-cent of solution gross weight) of having an appointment.

Embodiment 9

Solidify the general method of the binder composition of embodiment 1 to 8

In order to estimate the aqueous adhesive composition under the thermofixation condition, the every kind of binder composition for preparing among the embodiment 1 to 8 got the 1g sample and placed on one or more independently aluminium sheets.Then every kind of binder composition is placed under one or more conventional baking/conditions of cure of preheating oven, prepare corresponding solidified adhesive sample, for example: following 0.5 hour of following 0.5 hour of 300  (149 ℃) and 350  (177 ℃).Various conditions of cure are shown in table 1.

Embodiment 10

Test/the evaluation of the solidified adhesive sample of embodiment 9

Measure dried snappiness, wet tenacity and the wet metal adhesion power of every kind of solidified adhesive sample of embodiment 9 preparations in the following manner: (a) do snappiness with soft or crisp expression; (b) wet tenacity is with weak or strong representation; (c) wet metal adhesion power is with tight or pine expression.It is definite by the anti-breaking degree of solidified adhesive sample (generally existing with the film that adheres on the aluminium sheet) when the crooked metal sheet to do snappiness.Wet tenacity with add 10mL water and at room temperature place one night after fixing adhesive sample seem that solidified degree (be kept perfectly and resist the trend of fracture to represent by it) is definite.Wet metal adhesion power is determined with the degree that surface of aluminum plate keeps directly contacting with the adhesive sample of immersion after fixing at one night in water.Also measure the outward appearance of solidified adhesive sample.These test-results are shown in table 1.

Embodiment 11

To 35.7 gallons (about 321 pounds of stirring at room, 145.7kg) (about 48.2 pounds of 15% MOWIOL 4-98 solution, 21.9kg) in add 1.9 gallons (about 17 pounds successively, 7.7kg) (about 2.5 pounds of 14.5%ELVANOL 51-05,1.1kg) solution, 39.2 gallons (about 353 pounds, 160.3kg) (about 86.5 pounds of 24.5% toxilic acid ammonium solutions, 39.3kg), (about 195 pounds of 125g SILQUEST A-187 silane (about 0.27 pound) and 23.3 gallons of soft water, 88.5kg), prepare about 100 gallons (about 887 pounds, 402.7kg) solution.This solution is made up of about 35.2% MOWIOL 4-98,1.8% ELVANOL 51-05,63.0% toxilic acid and 0.2% SILQUEST A-187 silane (as the relative percentage of total dissolved solidss), and contains the 15.5% dissolved solid (as the per-cent of solution gross weight) of having an appointment.The solution stirring several minutes is transferred to the tackiness agent pump then, and it is used to use ordinary method to make fiber insulation product herein, is commonly referred to the product of " amber blanket " especially for formation, though this tackiness agent is not given the amber color.This method general description is in patent US 5318990, here with reference to quoting this patent.The specification of prepared solidified blanket product is that density and 1.5 inches (3.8cm) of 3/4 pound every square feet (the every square meter of 3.66kg) are thick.Oven temperature is set in about 450  (232 ℃) and is used for solidifying.The product outward appearance of taking out from baking oven is a white and finely bonding.After collecting several volumes test solidified materials, before baking oven, smash felt, and also collect uncured material and be used for test.

Embodiment 12

Test/the evaluation of the curing blanket of embodiment 11

Discharging, thickness recovery, dust, tensile strength, peeling strength, bonding strength, water-intake rate and the hot surface performance of the uncured blanket (uncured product) of the solidified blanket (solidified product) of preparation or moulding the results are shown in table 2 to 5 among the mensuration embodiment 11.The actual conditions that carries out these tests is as follows:

Emission testing-general

According to ASTM D5116 (" Standard Guide for Small-ScaleEnvironmental Chamber Determinations of Organic Emission fromIndoor Materials/Products "), the State of Washington IAQSpecification in United States Environmental ProtectionAgency (USEPA) and in January, 1994, the discharging of the total volatile organic compound (TVOC) of monitoring insulating products (solidified product), formaldehyde, whole selected aldehyde.Collection exposes the emissions data during 1 week, and every kind of potential pollutant is measured the air concentration of gained.Based on the requirement of the State of Washington, with the prediction of computer monitoring air concentration, it comprises loading (loading) and ASHARE Standard 62-1999 ventilation condition in the standard chamber.Product loads based at 32m ³Use 28.1m in the room ²The standard wall.

The aldehyde of emission testing-selection

At volume 0.0855m ³The minienvironment chamber in detect insulating products, analysis to measure is carried out in chemistry discharging.Measure the discharging that the aldehyde of selecting comprises formaldehyde according to ASTM D5197 (" Standard Test Method forDetermination of Formaldehyde and Other Carbonyl Compounds inAir (Active Sampler Methodology) ") with high speed liquid chromatography method (HPLC).With having 2, the solid adsorbent tube of 4-dinitrophenyl hydrazine (DNPH) is collected formaldehyde and other Low-Molecular-Weight Carbonyl Compounds in the environment chamber atmosphere.DNPH reagent in the tube and the reaction of the carbonyl compound of collection form stable hydrazone derivative and are retained in the tube.Go out hydrazone derivative with HPLC level acetonitrile wash-out from tube.Use anti-phase high speed liquid chromatography (HPLC) to detect the lower molecular weight aldehyde hydrazone derivative of analyzing aliquot sample with UV.Measure the absorption of derivative at the 360nm place.The multiple spot calibration curve that use is obtained by the hydrazone derivative standardized solution is measured the mass-basis response at gained peak.Standard air volume based on 45L is collected, but the quantization level of measurement report to 0.2 μ g.

Emission testing-volatile organic compounds (VOC)

VOC measures and adopts the gas-chromatography with mass spectrometric detection to carry out (GC/MS).Chamber atmosphere is collected on the solid adsorbent, its then pyrolysis be drawn onto among the GC/MS.The technological improvement that sorbent material collection technique, separation and check and analysis method are proposed by USEPA and other investigators.This technology is deferred to USEPA Method 1P-1B, generally can be used for the C of boiling point between 35 ℃-250 ℃ ₅-C ₁₆Organic chemicals.Standard air volume based on 18L is collected, but the quantization level of measurement report to 0.4 μ g.Separate and detect single VOC by GC/MS.Total VOC measures by adding and carrying out by all single VOC responses of mass spectrograph acquisition and with respect to toluene correction total mass.

Emission testing-air concentration is measured

The ER for emission rate of formaldehyde, total aldehyde and TVOC is used for computer exposure model, to measure the potential air concentration of pollutent.Computer model adopts the measurement ER for emission rate in the measured week to change, and determines that the air concentration that will take place thus changes.This model measurement carries out based on following hypothesis: the air of open Office Area is breathed the horizontal zone thorough mixing at shared spatial in the buildings; Envrionment conditions keeps 50% relative humidity and 73  (23 ℃); Other sources that do not have these pollutents; In this space, there is not reception sources (sinks) or potential source of release again for these pollutents.To the Indoor Air Exposure Model of USEPA, Version 2.0 carries out specific modification, to be applicable to this product and interested chemical.Ventilation and occupancy parameter are provided by ASHARE Standard 62-1999.

Peeling strength

The peeling strength of solidified blanket is according to ASTM C686, and " Parting Strength ofMineral Fiber Batt and Blanket Type Insulation " measures.

Tensile strength

The tensile strength of profiled part is according to closed test method KRD-161, and " TensileStrength-Dogbone method " measures.Carry out on the batten that this test is downcut on by profiled part, this profiled part is by hot-forming uncured insulating products preparation.Regulation among dog bone batten specification such as the ASTM D638, " Standard Test Method for Tensile Properties ofPlastics ".The pinblock speed of 2 inch per minute clocks (5.1cm/min) is all adopted in all tests.

Bonding strength

The interfacial bonding strength of profiled part adopts closed test method KRD-162, and " BondStrength of Molded Media Products (High Density) " carries out.(the moulding batten of 5.1cm * 5.1cm) is adhered to 2 inches * 2 inches and (on the wooden unit of 5.1cm * 5.1cm), and places the anchor clamps that apply vertical power to specimen surface with 2 inches * 2 inches of sectional areas.The pinblock speed of 12 inch per minute clocks (30.5cm/min) is all adopted in all tests.

Thickness recovery

Adopt ASTM C167, " Thickness and Density of Blanket of BattThermal Insulations " do not have packing and the test of upset thickness on the solidified blanket.

The dust test

Closed test method K-102 is adopted in the dust test, and " Packaged Fiber Glass DustTest, Batt Method " carries out on the solidified blanket.On strainer, collect and emit the dust of falling into the dust collection box, by difference definite amount of dust of weighing from the solidified blanket sample (carpet veneer) of picked at random.

Water-intake rate

ASTM C1104 is adopted in water-intake rate (% weight) test, and " Test Method forDetermining the Water Vapor Absorption of Unfaced Mineral FiberInsulation " carries out on the solidified blanket.

The hot surface performance

The hot surface performance test adopts ASTM C411, and " Test Method for Hot SurfacePerformance of High Temperature Thermal Insulation " carries out on the solidified blanket.

The solidified adhesive sample test-results of table 1: embodiment 9

Embodiment numbers embodiment and describes (% solid composition)	Solidification value	Do snappiness	Wet tenacity	Wet metal adhesion power	COOH/ OH ratio	Outward appearance
							1 PVA 1/AM/ATS/SILQUEST (32.6％∶55.3％∶10％∶2％)	149℃	Soft	A little less than	Pine	1.3∶1	Pale brown look
2 PVA 1/PVA 2/AM (30％∶7.3％∶62.6％)	149℃ 177℃	Soft	Weak	Degree of tightness	1.3∶1	The milk yellow yellow
							3 PVA 1/PVA 2/AM (35.1％∶1.9％∶63.0％)	149℃ 177℃	Crisp	Strong	Song Song	1.3∶1	Pale brown look pale brown look
4 PVA 1/PVA 2/AM/AS/CS/MSO/SILQUEST (25.2％∶1.5％∶45.2％∶14.7％∶5.9％∶5.6％∶2％)	149℃ 177℃	Crisp softness	Strong	Tense-lax	1.3∶1	The brown brown
							5 PVA 1/PVA 2/AM/AS/MSO/SILQUEST (26.8％∶1.6％∶48.7％∶15.2％∶5.6％∶2％)	149℃ 177℃	-softness	Strong and weak	Degree of tightness	1.3∶1	Pale brown look brown
6 PVA 1/PVA 2/AM/AS/SILQUEST (28.9％∶1.7％∶52.1％∶15.3％∶2％)	149℃ 177℃	Crisp	Strong	Song Song	1.3∶1	Opaque brown
							7 PVA 1/PVA 2/AM/AS/SILQUEST (31.9％∶1.9％∶59.1％∶5％∶2％)	149℃ 177℃	Soft crisp	Strong	Degree of tightness	1.3∶1	The milk yellow darkorange
8 PVA 1/PVA 2/AM/AS/SILQUEST (32.7％∶1.9％∶60.0％∶5.1％∶0.2％)	149℃ 177℃	Crisp softness	Strong	Degree of tightness	1.3∶1	Shallow milk yellow is orange

PVA ₁=MOWIOL 4-98 (polyvinyl acetate of 98% hydrolysis)

PVA ₂=ELVANOL 51-05 (polyvinyl acetate of 87-89% hydrolysis)

AM=toxilic acid ammonium

The ATS=paratoluenesulfonic acid ammonium salt

AS=ammonium sulfate

SILQUEST=gamma-amino propyl triethoxy (A-1101) silane

The CS=maize treacle

MSO=maleation soya-bean oil

The test-results of the solidified blanket sample of table 2. embodiment 11: total VOC emission factor

Exposure duration (hour)	VOC(μg/m 2)/hr	VOC air concentration (the μ g/m of expectation 3)
			4	77.5	85
8	61.8	68
			24	18.3	21
48	12.5	14
			72	8.3	9
96	5.7	6

The test-results of the solidified blanket sample of table 3. embodiment 11: total aldehyde emission factor

Exposure duration (hour)	Total aldehyde (μ g/m 2)/hr	Total aldehyde air concentration (μ g/m of expectation 3)
			4	0	0
8	0	0
			24	0	0
48	0	0
			72	0	0
96	0	0

The test-results of the solidified blanket sample of table 4. embodiment 11: total formaldehyde emissions factor

Exposure duration (hour)	Total formaldehyde (μ g/m 2)/hr	Total formaldehyde air concentration (μ g/m of expectation 3)
			4	0	0
8	0	0
			24	0	0
48	0	0
			72	0	0
96	0	0

The test-results of the solidified blanket sample of table 5. embodiment 11:

Thickness recovery, dust, strength property, water-intake rate and hot surface performance

Test			Test-results
Thickness recovery (dead, cm)			3.28±0.46 (3.8cm.nom)
				Thickness recovery (drop, cm)			3.78±0.56 (3.8cm.nom)
				Dust (mg)			37.9±4.1
				Tensile strength (kg/cm width)
Machine direction			0.23±0.05
				Intersect with machine direction			0.14±0.03
Add up to			0.18±0.07
Peeling strength (g/g)
				Machine direction			219±46
Intersect with machine direction			170±49
				Add up to			194±53
				Bonding strength (kg/m 2)			32.2±4.4
Water-intake rate			5.6±0.7
The hot surface performance			By

Though top description and/or enumerated certain embodiments of the present invention can be imagined to have a large amount of variant of the present invention and improvement.Therefore, the invention is not restricted to the specific embodiments above describing and/or enumerate.

Claims (38)

1. heat-setting aqueous adhesive composition, it comprises:

(a) have the polyprotonic acid component of acid groups, or its acid anhydrides or salt derivative; With

(b) multiple polyhydroxy component with hydroxyl;

The pH of wherein said binder composition is greater than about 7.

2. the binder composition of claim 1, wherein the pH of binder composition greater than about 7 to being less than or equal in about 10 the scope.

3. the binder composition of claim 1, wherein the ratio of the molar equivalent number of the described hydroxyl on the molar equivalent number of the described acid groups on the polyprotonic acid component or its acid anhydrides or salt derivative and the described multiple polyhydroxy component is about 0.7: in about 1.3: 1 scopes of 1-.

4. the binder composition of claim 1, about 1: 1 of the ratio of the described acid groups on the wherein said polyprotonic acid component or the molar equivalent number of its acid anhydrides or salt derivative and the molar equivalent number of the described hydroxyl of described multiple polyhydroxy component.

5. the binder composition of claim 1 also comprises one or more additives, and described additive can increase the flowability of binder composition.

6. the binder composition of claim 1, wherein thermofixation has prepared water-fast basically thermosetting polyester resin or its salt.

7. the binder composition of claim 1, wherein said polyprotonic acid component is selected from derivative, their salt and the acid anhydrides that unsaturated aliphatic polycarboxylic acid, radical of saturated aliphatic polycarboxylic acid, aromatic polycarboxylic acid, unsaturated cyclic polycarboxylic acid, saturated cyclic polycarboxylic acid, their hydroxyl replace, and their combination.

8. the binder composition of claim 1 also comprises ammonia or its salt.

9. the binder composition of claim 1, wherein said polyprotonic acid component is aliphatic polycarboxylic acid's a ammonium salt.

10. the binder composition of claim 1, wherein said polyprotonic acid component is the ammonium salt of unsaturated aliphatic polycarboxylic acid.

11. the binder composition of claim 1, at least two kinds of wherein said multiple polyhydroxy component is polymerized polyalcohol.

12. the binder composition of claim 11, wherein said polymerized polyalcohol are selected from polyalkylene polyvalent alcohol and poly-alkylene group polyvalent alcohol independently of one another.

13. the binder composition of claim 11, wherein said polymerized polyalcohol are selected from polyvinyl acetate, the polyvinyl acetate of complete hydrolysis, the polyvinyl alcohol of partial hydrolysis, and their mixture.

14. the binder composition of claim 1 also comprises catalyzer, described catalyzer can improve ester and form speed.

15. the binder composition of claim 14, wherein said catalyzer are sulfuric acid or sulfonic acid, or their salt or derivative.

16. the binder composition of claim 1 also comprises silicon-containing compound.

17. the binder composition of claim 1 also comprises the amino silicon-containing compound that replaces.

18. the binder composition of claim 16, wherein said silicon-containing compound is a silyl ether.

19. the binder composition of claim 16, wherein said silicon-containing compound is selected from γ-An Jibingjisanyiyangjiguiwan, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, and their mixture.

20. a thermal curable aqueous adhesive composition, it comprises:

(a) ammonium salt of dicarboxylic acid; With

(b) multiple polyhydroxy component with hydroxyl.

21. the binder composition of claim 20, wherein the pH of binder composition is greater than about 7.

22. the binder composition of claim 20, wherein the pH of binder composition greater than about 7 to being less than or equal in about 10 the scope.

23. the binder composition of claim 20 also comprises one or more additives, described additive can increase the flowability of binder composition.

24. the binder composition of claim 20, wherein said dicarboxylic acid is a toxilic acid.

25. the binder composition of claim 20, the mixture of the polyvinyl acetate that wherein said multiple polyhydroxy component is partial hydrolysis and the polyvinyl acetate of complete hydrolysis.

26. the binder composition of claim 20, wherein the ratio of the equivalents of the molar equivalent number of hydroxy-acid group on the dicarboxylic acid and salt thereof and the hydroxyl on the multiple polyhydroxy component is about 0.7: between about 1.3: 1 of the 1-.

27. the binder composition of claim 20, wherein the ratio of the equivalents of the hydroxyl on the molar equivalent number of hydroxy-acid group on the dicarboxylic acid and salt thereof and the multiple polyhydroxy component is about 1: 1.

28. the binder composition of claim 20, wherein the ratio of the equivalents of the hydroxyl on the molar equivalent number of hydroxy-acid group on the dicarboxylic acid and salt thereof and the multiple polyhydroxy component is about 1.3: 1.

29. a thermal curable aqueous adhesive composition, it comprises:

(a) have the polyprotonic acid component of acid groups, or its acid anhydrides or salt derivative; With

(b) mixture of the polyvinyl acetate of the polyvinyl acetate of partial hydrolysis and complete hydrolysis.

30. the binder composition of claim 29, wherein the pH of binder composition is greater than about 7.

31. the binder composition of claim 29, wherein the pH of binder composition greater than about 7 to being less than or equal in about 10 the scope.

32. the method for a binder fibre, this method may further comprise the steps:

(a) any one thermal curable aqueous adhesive composition of described fiber and aforesaid right requirement is contacted; With

(b) be enough to solidify the described thermal curable aqueous adhesive composition that adds the described fiber of thermo-contact under the temperature of this aqueous adhesive composition.

33. the method for claim 32, wherein said fiber is a non woven fibre.

34. the method for claim 32, wherein thermofixation has prepared water-fast basically thermosetting polyester resin or its salt.

35. a composition that comprises the glass fibre that contacts with heat curable adhesive composition, wherein said heat curable adhesive composition contain polyprotonic acid component or its acid anhydrides or salt derivative and the multiple polyhydroxy component with hydroxyl with acid groups.

36. a composition that comprises the glass fibre that contacts with heat curable adhesive composition, wherein said heat curable adhesive composition contains polyprotonic acid component or its acid anhydrides or salt derivative and the multiple polyhydroxy component with hydroxyl with acid groups.

37. a glass fiber product, it contains by heating and has applied any one the composition of fiber production of thermal curable aqueous adhesive composition of claim 1 to 31, and wherein said fiber comprises glass fibre.

38. the glass fiber product of claim 37, wherein said fiber package is contained in the non woven fibre felt, and this glass fiber product is a fiber insulation product.