CN111676596A

CN111676596A - Latex bonded textile fiber structures for architectural applications

Info

Publication number: CN111676596A
Application number: CN201910181725.8A
Authority: CN
Inventors: 亚历山德拉·阿布莱; 安德烈亚斯·赫尔; 米歇尔·卡诺坡
Original assignee: Germany Xintema Co ltd
Current assignee: Germany Xintema Co ltd; Synthomer Deutschland GmbH
Priority date: 2019-03-11
Filing date: 2019-03-11
Publication date: 2020-09-18

Abstract

The present invention relates to a textile fibre structure comprising rayon reinforced with a binder comprising a polymer latex obtained by emulsion polymerization in an aqueous medium of a mixture of ethylenically unsaturated monomers comprising: (a) an aliphatic conjugated diene, (b) an aromatic vinyl compound, (c) an ethylenically unsaturated silane bearing at least one silicon-bonded hydrolyzable group, and (d) an ethylenically unsaturated acid; it also relates to the use of the textile fibre structure in building applications and to the use of the above-mentioned binder for reinforcing textile fibre structures.

Description

Latex bonded textile fiber structures for architectural applications

Technical Field

The present invention relates to a fibrous structure comprising man-made fibres reinforced with a binder comprising a polymer latex, to the use thereof in building applications, and to the use of said binder for reinforcing fibrous structures.

Background

Binder-reinforced fibrous structures are commonly used in construction applications. One example is for roofing felts that include a fibrous structure typically made from organic polymer fibers. The fibrous structure is typically a nonwoven structure of polyester fibers that needs to be reinforced with a binder for the desired application as a roofing felt. According to a method commonly used in the industry, the binder is a two-component system (2K) in which one component comprises a polymer latex and the second component is a cross-linked resin, for example an aminoplast resin such as a urea-formaldehyde resin or a melamine-formaldehyde resin. The two components are combined just prior to application to the fibrous structure, and the coated fibrous structure is subsequently heat cured to provide the roofing felt.

Another example of the use of binder-reinforced fibrous structures in construction applications is exterior insulation systems (EIFS). The fibrous structures used for this application are typically woven glass fiber structures. According to one approach commonly used in the industry, binders for reinforcing fibrous structures include polymer latexes made from monomer compositions containing self-crosslinking monomers, such as N-methylolamide functional ethylenically unsaturated monomers. After the adhesive is applied, the fibrous structure is heat cured to provide the desired mechanical strength and alkali resistance for use in exterior insulation systems.

Common to both examples is that formaldehyde is released upon curing of the binder. The aminoplast resin and the self-crosslinking N-methylolamide groups release formaldehyde upon curing. Formaldehyde has recently been examined by governmental organizations as a potential carcinogenic compound, possibly classified as a hazardous compound. Accordingly, there is a need in the industry for binders for reinforcing fibrous structures that do not release formaldehyde upon curing.

WO 2008/008868 describes a fibre mat for building applications which is bonded by means of a binder comprising a formaldehyde-free resin and a functional silane additive which is not part of the resin. Specifically, it discloses an adhesive comprising a styrene acrylate dispersion in combination with a polyol crosslinker and an aminosilane additive.

US 2011/0214796 relates to adhesives comprising an aqueous dispersion based on styrene butadiene and an epoxy silane. The styrene butadiene latex may contain structural units from other monomers such as ethylenically unsaturated silane monomers. Other suitable co-polymers include N-methylol (meth) acrylamide. There is no disclosure of the use of the mastic as a binder to reinforce fibrous structures or of binder reinforced fibrous structures.

WO 2008/150647 relates to a fibre mat for construction applications, which is bound by an aqueous binder composition comprising a urea-formaldehyde resin and a polymer latex prepared from a monomer mixture comprising styrene, alkyl (meth) acrylate, acrylonitrile and acrylamide. Due to the presence of urea formaldehyde resin, the binder releases formaldehyde upon thermal curing.

WO 2010/019338 discloses glass fibre mats bonded by a binder composition comprising a formaldehyde-free binder which may be selected from acrylic polyols, starch grafted styrene or acrylic modified polyvinyl acetate and reactive hydrophobic additives such as stearyl acrylate, stearylmelamine, epoxidized fatty acid based oils and epoxysilanes.

WO 2016/193646 describes a binder composition for impregnating glass fibre fabrics comprising a silylated acrylic polymer obtained by copolymerising an alkyl (meth) acrylate and an ethylenically unsaturated silane monomer. Conjugated dienes and aromatic vinyl compounds are not mentioned as suitable comonomers. Thus, latex polymers are limited to pure (meth) acrylic polymers.

EP 1114849 relates to a polymer latex obtained by aqueous emulsion polymerization of a monomer mixture comprising a conjugated diene, an aromatic vinyl compound, an ethylenically unsaturated carboxylic acid and a copolymerizable self-crosslinking monomer selected from N-methylol (meth) acrylates. The latex is useful as a binder for textiles, particularly organic polymer fiber nonwovens used in asphalt impregnated roofing felts. The coated fibrous structure exhibits excellent high temperature dimensional stability, which is required for the pitch impregnation process and high temperature processing of the resulting shingle.

WO 02/42344 discloses an aqueous dispersion of core-shell acrylic polymers obtained from one or more acrylic monomers whose corresponding homopolymers have a glass transition temperature (Tg) of less than 0 ℃, one or more acrylic monomers whose corresponding homopolymers have a Tg of greater than 0 ℃, one or more monomers containing at least two ethylenic unsaturates, a vinyl alkoxysilane, and an ethylenically unsaturated carboxylic acid. The aqueous dispersion can be used for impregnation of textiles. No architectural applications are mentioned.

WO 2007/024683 describes a Wet-laid (Wet-laid) chopped strand glass mat for roofing applications that is formed by applying or including at least one coupling agent, for example, as part of a two-part binder composition including a coupling agent. Preferred two-part binders include a combination of urea formaldehyde binders and styrene butadiene binders. Preferred coupling agents are silanes and reactive siloxanes.

It is therefore an object of the present invention to provide a binder composition to reinforce textile fibre structures which, when cured, does not release formaldehyde and does not impair the desired properties of the reinforced fibre structure or even improve properties such as high temperature dimensional stability or alkali resistance. Furthermore, it is an object of the present invention to provide a binder composition which allows for lower curing temperatures and shorter curing times in the preparation of binder reinforced textile fibre structures to reduce energy consumption and increase the output of existing production lines without compromising the desired properties of the reinforced fibre structure.

Disclosure of Invention

These objects are surprisingly achieved by a textile fibre structure for building applications comprising rayon reinforced with a binder comprising a polymer latex obtained by emulsion polymerization in an aqueous medium of an ethylenically unsaturated monomer mixture comprising:

(a) aliphatic conjugated diene

(b) An aromatic vinyl compound; and

(c) an ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group.

According to another aspect, the invention relates to the use of a binder for reinforcing a textile fibre structure, the binder comprising a polymer latex obtained by emulsion polymerisation in an aqueous medium of an ethylenically unsaturated monomer mixture comprising:

(a) aliphatic conjugated diene

(b) An aromatic vinyl compound; and

A further aspect of the invention is the use of the textile fibre structure of the invention in building applications.

Detailed Description

The present invention will now be described in more detail.

Adhesive:

the binder of the present invention comprises a polymer latex obtained by emulsion polymerization in an aqueous medium of an ethylenically unsaturated monomer mixture comprising:

(a) an aliphatic conjugated diene;

(b) an aromatic vinyl compound; and

Owing to the presence of the ethylenically unsaturated silane having at least one silicon-bonded hydrolyzable group, the binder has self-crosslinking properties and therefore does not release harmful constituents such as formaldehyde on crosslinking. Suitable silicon-bonded hydrolysable groups according to the present invention may be alkoxy groups, acyloxy groups, halogen groups or combinations thereof. Preferred hydrolysable groups are alkoxy groups, especially methoxy and ethoxy groups.

Thus, suitable ethylenically unsaturated silanes bearing at least one silicon-bonded hydrolysable group according to the invention may be selected from: gamma- (meth) acryloyloxypropyltrimethoxysilane, gamma- (meth) acryloyloxypropyltriethoxysilane, gamma-methacryloyloxypropylmethyldimethoxysilane, gamma- (meth) acryloyloxypropyldimethylmethoxysilane, gamma- (meth) acryloyloxypropylmethyldiethoxysilane, gamma- (meth) acryloyloxypropyldimethylethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 3- (3-aminopropoxy) -3, 3-dimethyl-1-propenyltrimethoxysilane, poly (meth) acryloyloxypropyltrimethoxysilane, poly (meth) acryloyloxypropyl-dimethylmethoxysilane, poly (meth) acryloyloxypropyl-ethylmethoxysilane, poly (meth), Butenyltriethoxysilane, butenyltrimethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, decyltrimethoxysilane (decosyltriethoxysilane), (meth) acryloyloxyethyltrimethoxysilane, (meth) acryloyloxyethoxyethyltriethoxysilane, (meth) acryloyloxyethoxymethyldimethoxysilane, (meth) acryloyloxyethoxymethyldiethoxysilane, (meth) acryloyloxymethyl-methyltrimethoxysilane, (meth) acryloyloxymethyl-dimethoxysilane, (meth) acryloyloxymethyl-triethoxysilane, (meth) acryloyloxymethyl-methyldiethoxysilane, γ - (meth) acryloyloxypropyltri (methoxyethoxy) silane, 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, decyltrimethoxysilane, (meth) acryloyloxyethyltriethoxysilane, decyltrimethoxysilane, and mixtures thereof, Allylmethyldimethoxysilane (allylmethyldimethoxysilane), vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, vinyldimethylmethoxysilane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, and combinations thereof.

Particularly suitable ethylenically unsaturated silanes bearing at least one silicon-bonded hydrolyzable group are selected from: gamma- (meth) acryloxypropyltrimethoxysilane, gamma- (meth) acryloxypropyltriethoxysilane, gamma- (meth) acryloxypropylmethyldimethoxysilane, gamma- (meth) acryloxypropyldimethylmethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and combinations thereof. Particularly preferred is gamma-methacryloxypropyltrimethoxysilane.

According to the invention, the ethylenically unsaturated monomer mixture may comprise:

(a) 20-60% by weight of at least one aliphatic conjugated diene;

(b)30-70 wt% of at least one aromatic vinyl compound;

(c)0.5 to 5% by weight of at least one ethylenically unsaturated silane having at least one silicon-bonded hydrolysable group;

(d)0.1 to 8% by weight of at least one ethylenically unsaturated acid; and

(e)0 to 20% by weight of at least one other olefinically unsaturated compound than compounds (a) to (d),

the weight percentages are based on the total amount of monomers and add up to 100 wt.%.

In particular, the ethylenically unsaturated monomer mixture may comprise:

(a) 25-45% by weight of at least one aliphatic conjugated diene;

(b) 50-65% by weight of at least one aromatic vinyl compound;

(d)0.1 to 7% by weight of at least one ethylenically unsaturated acid; and

(e)0 to 20% by weight of at least one other olefinically unsaturated compound than compounds (a) to (d).

Suitable conjugated diene monomers for preparing the latex of the present invention include conjugated diene monomers selected from the group consisting of: 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene. 1, 3-butadiene is a preferred conjugated diene according to the present invention. Generally, the amount of conjugated diene monomer is from 20 to 60 weight percent, preferably from 20 to 50 weight percent, more preferably from 25 to 45 weight percent, and most preferably from 30 to 40 weight percent, based on the total weight of the monomers. Thus, the conjugated diene may be present in an amount of at least 20 wt-%, at least 22 wt-%, at least 24 wt-%, at least 26 wt-%, at least 28 wt-%, or at least 30 wt-%, based on the total weight of the ethylenically unsaturated monomers.

Thus, the conjugated diene monomer may be used in an amount of not more than 60 wt%, not more than 58 wt%, not more than 56 wt%, not more than 54 wt%, not more than 52 wt%, not more than 50 wt%, not more than 48 wt%, not more than 46 wt%, not more than 44 wt%, not more than 42 wt%, or not more than 40 wt%.

One skilled in the art will appreciate that any range between any explicitly disclosed lower and upper limit is disclosed herein.

Representative examples of the aromatic vinyl monomer include: styrene, alpha-methylstyrene, p-methylstyrene, tert-butylstyrene and 2-vinyltoluene. Mixtures of one or more aromatic vinyl compounds may also be used. Preferred monomers are styrene and alpha-methylstyrene. The aromatic vinyl compound may be used in an amount of 30 to 70% by weight, preferably 50 to 65% by weight or 50 to 60% by weight, based on the total weight of the ethylenically unsaturated monomers. Thus, the aromatic vinyl compound may be present in an amount of at least 30 wt%, at least 32 wt%, at least 34 wt%, at least 36 wt%, at least 38 wt%, at least 40 wt%, at least 42 wt%, at least 44 wt%, at least 46 wt%, at least 48 wt%, or at least 50 wt%. Likewise, the aromatic vinyl compound may be present in an amount of no more than 70 weight percent, no more than 68 weight percent, no more than 66 weight percent, no more than 64 weight percent, no more than 62 weight percent, or no more than 60 weight percent, based on the total weight of the ethylenically unsaturated monomers. One skilled in the art will appreciate that any range between the explicitly disclosed lower and upper limits is disclosed herein.

Typically, the amount of ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group is from 0.5 to 5 wt%, preferably from 0.5 to 4.5 wt%, more preferably from 1 to 4 wt%, even more preferably from 1 wt% to 3.5 wt% or from 1.0 wt% to 3 wt%, based on the total amount of monomers. Thus, the ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group may be present in an amount of at least 0.5 wt.%, at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.%. Likewise, the ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group may be present in an amount of no more than 5 wt.%, no more than 4.5 wt.%, no more than 4.0 wt.%, no more than 3.5 wt.%, no more than 3.0 wt.%, based on the total weight of ethylenically unsaturated monomers. One skilled in the art will appreciate that any range between the explicitly disclosed lower and upper limits is disclosed herein.

The monomer mixture used for preparing the polymer latex used according to the present invention may comprise other monomers copolymerizable with the monomers defined above. One suitable class of optional comonomers is ethylenically unsaturated acids (d).

Ethylenically unsaturated carboxylic acid monomers suitable for use in the present invention include monocarboxylic acid monomers and dicarboxylic acid monoesters. In the practice of the present invention, it is preferred to use ethylenically unsaturated aliphatic mono-or dicarboxylic acids or anhydrides having from 3 to 5 carbon atoms. Examples of the monocarboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, and examples of the dicarboxylic acid monomer include fumaric acid, itaconic acid, maleic acid, and maleic anhydride. Examples of other suitable ethylenically unsaturated acids include vinyl acetic acid, vinyl lactic acid, vinyl sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfonic acid and their salts.

The use of ethylenically unsaturated acid monomers affects the properties of the polymer dispersion and coatings prepared therefrom. The type and amount of these monomers are thus determined. Typically, the amount of ethylenically unsaturated acid monomer is from 0.1 to 8 wt%, preferably from 1 to 8 wt%, more preferably from 1 to 7 wt%, even more preferably from 1 to 6 wt% or from 1 to 5 wt%, based on the total weight of ethylenically unsaturated monomers. Thus, the ethylenically unsaturated acid monomer can be present in an amount of at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 0.7 wt%, at least 0.9 wt%, at least 1 wt%, at least 1.2 wt%, at least 1.4 wt%, at least 1.6 wt%, at least 1.8 wt%, at least 2 wt%. Likewise, the ethylenically unsaturated acid monomer can be present in an amount of no more than 8 weight percent, no more than 7.5 weight percent, no more than 7 weight percent, no more than 6.5 weight percent, or no more than 6 weight percent, no more than 5.5 weight percent, no more than 5 weight percent, or no more than 4.5 weight percent, based on the total weight of the ethylenically unsaturated monomers. One skilled in the art will appreciate that any range defined by an explicitly disclosed lower limit and an explicitly disclosed upper limit is disclosed herein.

Optionally, the ethylenically unsaturated monomers used in the free-radical emulsion polymerization to form the polymer latex used according to the invention may comprise other ethylenically unsaturated monomers than the monomers a) to d) described above. These other monomers may be selected from: alkyl or hydroxyalkyl esters of (meth) acrylic acid, vinyl esters, unsaturated nitriles and amides of ethylenically unsaturated acids.

Nitrile monomers useful in the present invention include polymerizable unsaturated aliphatic nitrile monomers containing a linear or branched arrangement of 2 to 4 carbon atoms, which may be substituted with acetyl or other nitrile groups. These nitrile monomers include acrylonitrile, methacrylonitrile and fumaronitrile, with acrylonitrile being most preferred. These nitrile monomers may be present in amounts of up to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 12% by weight, and even more preferably from 1 to 12% by weight, based on the total weight of the ethylenically unsaturated monomers.

Vinyl ester monomers that may be used according to the present invention include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl 2-ethylhexanoate, vinyl stearate, and vinyl versatate (versatic acid). The most preferred vinyl ester monomer for use in the present invention is vinyl acetate. In general, the vinyl ester monomer may be present in the emulsion polymerization used to prepare the polymer latex of the present invention in an amount of from 0 to 20 weight percent, preferably from 0 to 15 weight percent, more preferably from 0 to 10 weight percent or from 0 to 5 weight percent, based on the total weight of ethylenically unsaturated monomers.

The (meth) acrylates which can be used according to the invention include: n-, iso-, or tert-alkyl esters of acrylic acid or (meth) acrylic acid, wherein the alkyl group has 1 to 20 carbon atoms, the reaction product of methacrylic acid with a glycidyl ester of a neo acid (neo acid), such as versatic acid, neodecanoic acid, or pivalic acid, and hydroxyalkyl (meth) acrylate and alkoxyalkyl (meth) acrylate monomers.

In general, the preferred alkyl esters of (meth) acrylic acid may be selected from C (meth) acrylic acid₁-C₁₀Alkyl esters, preferably C1-C10 alkyl (meth) acrylates. Examples of such acrylate monomers include: n-butyl acrylate, sec-butyl acrylate, ethyl acrylate, hexyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, methyl methacrylate, butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, and hexadecyl methacrylate. Generally, the amount of alkyl (meth) acrylate monomer present in the polymer phase depends on the monomers selected, but is generally from 0 to 20% by weight, preferably from 0 to 15% by weight, more preferably from 0 to 10% by weight, even more preferably from 0 to 8% by weight or from 0 to 5% by weight, based on the total amount of ethylenically unsaturated monomers. The lower limit of the content of the alkyl (meth) acrylate may be 0.5 wt%, or 1.0 wt%, or 1.5 wt%, or 2.0 wt%. It is most preferred if the monomer composition does not contain alkyl esters of (meth) acrylic acid.

Hydroxyalkyl (meth) acrylate monomers useful in preparing the polymer latex according to the present invention include: hydroxyalkyl acrylate and methacrylate monomers based on ethylene oxide, propylene oxide and higher alkylene oxides or mixtures thereof. Examples are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate. Generally, the amount of hydroxyalkyl (meth) acrylate monomer present in the polymer phase depends on the monomers selected, but typically ranges from 0 to 15 wt.%, preferably from 0 to 10 wt.%, based on the total weight of ethylenically unsaturated monomers. It is most preferred if the monomer composition does not contain hydroxyalkyl (meth) acrylate monomers.

Alkoxyalkyl (meth) acrylate monomers useful in the present invention include methoxyethyl methacrylate, ethoxyethyl methacrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, butoxyethyl methacrylate, methoxybutyl acrylate, and methoxyethoxyethyl acrylate. Preferred alkoxyalkyl (meth) acrylate monomers are ethoxyethyl acrylate and methoxyethyl acrylate. Generally, the amount of the alkoxyethyl alkyl (meth) acrylate monomer present in the polymeric phase depends on the monomer chosen, but typically ranges from 0 to 15% by weight, preferably from 0 to 10% by weight, based on the total weight of the ethylenically unsaturated monomers. It is most preferred if the monomer composition does not contain an alkoxyalkyl (meth) acrylate monomer.

Amides of ethylenically unsaturated acids that may be used to prepare the polymer latex used in accordance with the present invention include acrylamide, methacrylamide and diacetone acrylamide. Preferred amide monomers are methacrylamide and acrylamide. Typically, the amount of amide of ethylenically unsaturated acid is from 0 to 10 wt%, preferably from 0.5 to 5 wt%, even more preferably from 0.5 to 4 wt% or from 1 to 3.5 wt%, most preferably from 1 to 3 wt%, based on the total weight of ethylenically unsaturated monomers.

The rayon fiber can have a ratio of the longest measurable dimension to the shortest measurable dimension of greater than 5: 1. Preferably, the ratio of the rayon of the present invention is 10:1, more preferably 20:1 or more, and more preferably 50:1 or more. Thus, coatings and binders for agglomerating nearly spherical particles are not within the scope of the invention. In one embodiment where the textile fibers are present as a woven web, with the binder applied at the intersections, the preferred ratio of individual rayon fibers can be significantly greater than 500: 1.

According to the invention, the longest dimension is preferably more than 100nm in length, more preferably more than 200nm in length, more preferably more than 500nm in length, more preferably more than 1 micron in length. Coating and curing of the nanorod material is not a preferred embodiment.

According to the present invention, the rayon may comprise: organic polymeric rayon, which may include polyesters such as hydroxyl-functionalized polyesters or polyethylene terephthalate, polyether esters, polyurethanes, polybutylene terephthalate, hydroxyl-functionalized polyolefins, such as (meth) acrylic-g-propylene, polyvinyl alcohol or its acetals or ketals, nylon 6, nylon 66, polyethylene, polypropylene, polyarylene sulfide, polydietherketone, graphitic carbon, especially activated fibrous carbon, glassy carbon fibers, graphite-epoxy mixtures, fullerenic carbon, acrylic fibers, modacrylic fibers, aramid or kevlar fibers, nomex fibers, spandex fibers, polyacrylonitrile, chemically modified polycarbonate fibers, chemically treated vinylidene (vinylidine) fibers, chemically treated vinyon or saran PVC fibers, synthetic polyisoprene, or combinations thereof.

Natural fibers in man-made form; also included among the artificial fibers according to the term of the present invention are artificial fibers including artificial cellulose fibers, artificial cellulose acetates, artificial cellulose triacetates, artificial alginic acid fibers, polylactone fibers, casein fibers (polycasein fibers), polycycloglobulin fibers, polyurea, polylactic acid fibers, or artificial fibers produced by polymerizing polypeptides, amino acids to form carboxylic amide bonds.

Suitable inorganic staple fibers according to the present invention may include mineral staple inorganic fibers such as ceramic fibers, basalt fibers, asbestos fibers, slag wool, asbestos, refractory ceramic fibers such as kaowool.

According to the invention, the rayon preferably comprises polyester, preferably hydroxy-functionalized polyester or glass fiber. A preferred example of a fiber glass is alkaline earth silicate wool (alkali earth silicate wool) with CaO and MgO additives, particularly preferred is alkali-resistant E-glass comprising additional alumina, or containing zirconia and Na₂AR-glass with O replacing CaO. Less preferred fiber glasses are C-glass, A-glass, borosilicate D-glass, E-CR-glass, R-glass, S-vitreous quartz and S-2-glass. The fibers may be amorphous or crystalline. In case the man-made fibers are glass fibers, the amount of silica is preferably more than 40 wt.%, more preferably more than 50 wt.%%, most preferably greater than 55% by weight. In the case of rayon comprising a hydroxy-functional polyester, the amount of hydroxy-functional polyester is preferably greater than 70 weight percent, more preferably greater than 80 weight percent, and most preferably greater than 90 weight percent.

Although outside the scope of the present invention, the skilled person will appreciate that the binders described herein may be used to treat natural fibres that have been purified, chemically or thermally treated or production treated. Such as sisal, hemp, Solka-

Powdered cellulose, cellulose xanthate, or any natural fiber treated by the viscose process or by-products thereof, such as lignin fiber, or any product obtained by treating a biomass-containing fiber with a paper pulp, or saponifying acetate. Unmodified natural fibers, such as silk, cotton, or jute fibers, may be cured with a binder. Alternatively, the binder may cure animal by-product based fibers, such as collagen or keratin. In particular fibers with hydroxyl and/or carboxyl functionality can be brought to uncured strength (green strength) by addition of divalent metal ions, which otherwise may require chemical modification.

Or any one or more of the above organic man-made fibers, man-made forms of natural fibers, or inorganic man-made fibers, may be present as a mixed fiber.

Alternatively or additionally, an adhesive may be applied to the fibers at their ends to provide them as a thermally stable matrix in a "carpet-like configuration," and then cured to produce a surface of long free-flowing fibrous material extending perpendicularly from the substrate on one or both sides of the substrate.

Alternatively or additionally, individual fibers may be uniformly oriented and bundled using the binder of the present invention to at least partially cure the partially oriented fiber groups to achieve improved micro-elasticity in the composite.

In accordance with the present invention, the binder is compatible with certain fibers as a concentric coating during melt extrusion. In certain embodiments, the binder may be used as a temporary binder to coalesce the metal and/or mixed metal oxide fleece prior to rapid sintering. This is not the case in the preferred embodiment. Without wishing to be bound by theory, in fiber chemistry, since there are no bond-forming groups on the surface of the rayon (e.g., noble metal rayon), covalent bond formation with silicone in the binder polymer is not possible, and the primary means of surface adhesion is physisorption, in which case, one skilled in the art will appreciate that the preferred embodiment of the coated fiber is a uniform mat (uniform mat) with substantially no gaps between the binder and the filamentary material to prevent the binder from peeling or debonding from the rayon surface upon dry curing.

According to one embodiment of the present invention, which is particularly useful for bonding nonwoven structures of organic polymeric fibers, can be advantageously used in roofing material (rooming) applications, wherein the ethylenically unsaturated monomer mixture used to prepare the polymer latex comprises:

(a) 25-35% by weight of at least one aliphatic conjugated diene, preferably butadiene;

(b) 55-65% by weight of at least one aromatic vinyl compound, preferably styrene;

(c)0.5 to 5% by weight of at least one ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group, preferably gamma-methacryloxypropyltrimethoxysilane;

(d)0.1 to 6 wt% of at least one ethylenically unsaturated acid, preferably a combination of acrylic acid and itaconic acid;

(e1)1 to 15% by weight of at least one ethylenically unsaturated nitrile, preferably acrylonitrile; and

(e2) from 0.5 to 5% by weight of at least one amide of an ethylenically unsaturated acid, preferably methacrylamide,

preferably, the first and second electrodes are formed of a metal,

(a) 28-32% by weight of at least one aliphatic conjugated diene, preferably butadiene;

(b) 57-63% by weight of at least one aromatic vinyl compound, preferably styrene;

(c)1 to 4% by weight of at least one ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group, preferably gamma-methacryloxypropyltrimethoxysilane;

(d)0.1 to 5 wt% of at least one ethylenically unsaturated acid, preferably a combination of acrylic acid and itaconic acid;

(e1)3 to 10% by weight of at least one ethylenically unsaturated nitrile, preferably acrylonitrile; and

(e2)0.5 to 3% by weight of at least one amide of an ethylenically unsaturated acid, preferably methacrylamide.

According to one embodiment of the present invention, said embodiment is particularly suitable for bonding woven structures of glass fibers that can be advantageously used in external insulation systems for exterior walls, wherein the ethylenically unsaturated monomer mixture used for preparing the polymer latex comprises:

(a) 35-45% by weight of at least one aliphatic conjugated diene, preferably butadiene;

(b) 50-60% by weight of at least one aromatic vinyl compound, preferably styrene;

(e1)0 to 10% by weight of at least one ethylenically unsaturated nitrile, preferably acrylonitrile; and

preferably, the first and second electrodes are formed of a metal,

(a) 38-42% by weight of at least one aliphatic conjugated diene, preferably butadiene;

(b) 47-57% by weight of at least one aromatic vinyl compound, preferably styrene;

(d)0.1 to 5 wt% of at least one ethylenically unsaturated acid, preferably a combination of acrylic acid and itaconic acid; and

Preferably, the monomer mixture is free of ethylenically unsaturated nitriles.

In general, the polymer latex composition of the present invention can be prepared by polymerization methods known in the art, and in particular, by known latex emulsion polymerization methods, including latex polymerization with a seed (seed latex) and latex polymerization without a seed latex. Representative methods include us patent No. 4,478,974; U.S. Pat. No. 4,751,111; us patent No. 4,968,740; us patent No. 3,563,946; us patent No. 3,575,913; and those described in DE-A-1905256. These methods are applicable to the polymerization of the above monomers. The seed latex used is preferably based on carboxylated styrene copolymers, as exemplified in WO2017164726A 1. Preferably, no acrylate-based ex situ seed is used. The method of introducing the monomers and other ingredients, such as polymerization aids, is not particularly critical. The polymerization is then carried out under conventional conditions until the desired conversion of the monomers to polymer is achieved. Crosslinking agents and well-known auxiliaries for latex polymerization, such as initiators, surfactants, bases, buffers and emulsifiers, can be used as needed.

The process for preparing the above-described polymer latices can be carried out at temperatures of from 0 to 130 ℃, preferably from 60 to 130 ℃, particularly preferably from 60 to 100 ℃ and very particularly preferably from 75 to 100 ℃ in the absence or presence of one or more emulsifiers and one or more initiators, for example preferably sodium or ammonium persulphate. Temperature includes all values and sub-values therebetween, including, inter alia, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, and 125 ℃.

The manner in which the monomers are introduced into the reaction mixture is not particularly limited. Thus, the emulsion polymerization according to the invention can be carried out, for example, in a batchwise, pseudo-batchwise or continuous mode of monomer feed. SBR-based polymers can also be prepared in which the styrene and butadiene groups are present in "blocks", i.e., [ p (sty) -b-p (1,3-BD) ] -g-MEMO with small amounts of other monomers between the block forms.

Initiators that may be used in the practice of the present invention include water-soluble and/or oil-soluble initiators effective for polymerization purposes. Representative initiators are well known in the art and include, for example: azo compounds (e.g., AIBN, AMBN, and cyanovaleric acid), inorganic peroxy compounds, such as hydrogen peroxide, sodium peroxydisulfate, potassium and ammonium peroxydisulfate, peroxycarbonates, and peroxyborates, and organic peroxy compounds, such as alkyl hydroperoxides, dialkyl peroxides, acyl hydroperoxides, and diacyl peroxides, and esters, such as t-butyl perbenzoate, and combinations of inorganic and organic initiators. Most preferred are inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate.

The initiator is used in an amount sufficient to initiate polymerization at the desired rate. In general, an amount of from 0.05 to 5% by weight, preferably from 0.1 to 4% by weight, of initiator, based on the weight of the total polymer, is sufficient. The amount of initiator is most preferably from 0.1 to 3% by weight, based on the total weight of the polymer. The amount of initiator includes all values and sub-values therebetween, including especially 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 and 4.5 weight percent based on the total weight of the polymer.

The inorganic peroxy compounds and organic peroxy compounds described above can be used alone or in combination with one or more suitable reducing agents well known in the art. Examples of reducing agents of this type which may be mentioned are sulfur dioxide, alkali metal hydrogen sulfates, alkali metal and ammonium hydrogen sulfites, thiosulfates and dithionites, and also hydroxylamine hydrochloride, hydrazine sulfate, iron (II) sulfate, cuprous naphthoate, glucose, sulfonic acid compounds such as sodium methanesulfonate, amine compounds such as dimethylaniline, and ascorbic acid. The amount of the reducing agent is preferably 0.03 to 10 parts by weight per part by weight of the polymerization initiator.

Suitable surfactants or emulsifiers for stabilizing the latex particles include those conventional surfactants used in polymerization processes. A surfactant or surfactants may be added to the aqueous phase and/or the monomer phase. An effective amount of surfactant in the seed process is an amount selected to support stabilization of the particles as a colloid, minimize contact between the particles, and prevent coagulation. During non-seeding, an effective amount of surfactant is that amount selected to affect particle size. The surfactant may be anionic, nonionic, cationic, amphoteric or zwitterionic in nature, most preferably an anionic or nonionic surfactant, or a combination thereof.

Representative surfactants include saturated and ethylenically unsaturated sulfonic acids or salts thereof, including, for example, unsaturated hydrocarbon sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid and salts thereof; aromatic hydrocarbon acids such as p-styrenesulfonic acid, isopropenylbenzenesulfonic acid and vinyloxybenzenesulfonic acid and salts thereof; sulfoalkyl esters of acrylic and methacrylic acid, such as sulfoethyl and sulfopropyl methacrylate and salts thereof, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof; alkylated diphenyl ether disulfonates, sodium dodecylbenzenesulfonate and sodium sulfosuccinate lauryl esters, ethoxylated alkylphenols and ethoxylated alcohols; fatty alcohol (poly) ether sulfates.

The type and amount of surfactant will generally depend on the number of particles, the size and composition of the particles. In general, the surfactant is used in an amount of 0 to 10, preferably 0 to 5, more preferably 0 to 3 parts by weight, based on the total weight of the monomers. The amount of surfactant includes all values and sub-values therebetween, including especially 0, 0.1, 0.5, 1,2, 3, 4,5, 6, 7, 8,9 and 10 parts by weight based on the total weight of the monomers. According to one embodiment of the invention, the polymerization is carried out without the use of a surfactant.

In addition to the surfactants mentioned above, various protective colloids can be used. Suitable colloids include polyols, such as partially acetylated polyvinyl alcohol, casein, hydroxyethyl starch, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol and gum arabic. Preferred protective colloids are carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose.

Furthermore, the polymerization of the monomer mixture can be carried out in the presence of a degraded polysaccharide (also known as dextrin). Any degraded starch may be used. When used, degraded starches having a dextrose equivalent DE of 15 to 70, measured according to ISO 5377(1981-12-15), are preferred. The term "polysaccharide" includes polysaccharides and oligosaccharides. Suitable examples are glucose syrups, commercially available from e.g. Cargill Deutschland GmbH, Krefeld, Germany or Roquette, lestem, France, and other alternatives to degraded polysaccharides which can be used according to the invention.

In general, these protective colloids are used in amounts of from 0 to 10 parts by weight, preferably from 0 to 5 parts by weight, more preferably from 0 to 2 parts by weight, based on the total weight of the monomers. The amount of protective colloid includes all values and sub-values therebetween, including in particular 1,2, 3, 4,5, 6, 7, 8 and 9 parts by weight, based on the total weight of the monomers.

Other auxiliary agents which are frequently used in conventional emulsion polymerization processes may also be used as needed for preparing the polymer latex of the present invention. These further adjuvants include, but are not limited to, pH adjusters, buffer substances, chelating agents, chain transfer agents and shortstopping agents.

Non-limiting examples of suitable buffering substances are, for example, alkali metal carbonates and bicarbonates, phosphates and pyrophosphates. Examples of suitable chelating agents may be alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or hydroxy-2-ethylenediaminetriacetic acid (hetta). The amount of buffer substance and chelating agent is generally from 0.001 to 1% by weight, based on the total amount of monomers.

Chain transfer agents may be used to control the average molecular weight of the polymer chains formed during emulsion polymerization. Non-limiting examples of suitable chain transfer agents are organosulfur compounds, such as thioesters, such as alkylthio esters, e.g., ethyl thioacetate, propyl thioacetate, ethyl thiopropionate, lauryl thiopropionate, methyl thiobutyrate, propyl thiobutyrate; alkylthioglycolates, e.g. butylthioglycolate, hexylthioglycolate, laurylthioglycolate, 2-ethylhexylthioglycolate, isooctylthioglycolateEsters and thiopropionates, and the like; dithiols (e.g., 1, 2-ethane-dithiol) and alkyl ethers (e.g., 2-mercaptoethyl ether). Alternatively or additionally, 2-mercaptoethanol, 3-mercaptopropionic acid and C may be used₁-C₁₂Alkyl mercaptans, of which n-dodecyl mercaptan and t-dodecyl mercaptan are preferred. If present, the amount of chain transfer agent is generally from 0.05 to 3.0% by weight, preferably from 0.2 to 2.0% by weight, based on the total amount of monomers.

Furthermore, it may be beneficial to incorporate partial neutralization into the polymerization process. Those skilled in the art will appreciate that by appropriate selection of this parameter, the necessary control can be achieved.

Various other additives and ingredients may be added to prepare the latex composition of the invention. These additives include, for example: buffers, defoamers, wetting agents, thickeners, plasticizers, fillers, pigments, dispersants, optical brighteners, crosslinking agents, antioxidants, hydrophobing agents and metal chelating agents. Known defoamers include silicone oils and acetylene glycols. Commonly known wetting agents include alkylphenol ethoxylates, alkali metal dialkyl sulfosuccinates, acetylene glycols, and alkali metal alkyl sulfates. Typical thickeners include polyacrylates, polyacrylamides, xanthan gums, modified celluloses or particulate thickeners such as silica and clays. Typical plasticizers include mineral oil, liquid polybutene, liquid polyacrylate and lanolin. Preferably, no high molecular weight plasticizer is used, more preferably no plasticizer is used. Zinc oxide, titanium dioxide, aluminum trihydroxide (also known as aluminum trihydroxide), calcium carbonate and clay are commonly used fillers. The hydrophobic agent may be an aliphatic compound such as a C8-22 fatty acid, a C8-22 fatty acid amide, a C8-22 fatty acid ester with a C1-8 monohydric alcohol, a C8-22 fatty acid ester of ethylene glycol, a C8-22 fatty acid ester of polyethylene glycol, a C8-22 fatty acid ester of polyalkylene glycol, a C8-22 fatty acid ester of glycerol, a C8-22 fatty acid ester of monoethanolamine, diethanolamine or triethanolamine, and a C8-22 fatty acid ester of a monosaccharide. Preferably no fatty compounds are used in the formation of the binder. The filler may or may not be used as a flame retardant component. The filler may or may not act as a pigment; colorants, dyes and pigments may be present instead of or in addition to the filler. Preferably, no non-reinforcing filler is present in the rayon reinforced with the binder.

It will be appreciated by those skilled in the art that in order to produce an effective cure between the fibers, it is preferred that the binder coated rayon be not subsequently coated prior to the use of the silicone curing step.

The binder used to strengthen the textile fibre structure of the invention may contain further components, such as co-binders and cross-linking agents, as long as these further components do not release formaldehyde upon curing. The binder used according to the invention is therefore preferably free of any formaldehyde resin. It is particularly preferred if the adhesive does not contain any additional resin component.

In order to optimize the properties of the adhesives used in the present invention, additional components may be present. For example, the adhesive may comprise at least one organosilane crosslinking agent, such as a monomeric epoxy functional silane or a reaction product thereof. The at least one organosilane crosslinking agent can comprise at least one organic group having one or more pendant functional groups reactive with the active hydrogen-containing functional groups of the monomer (if present), wherein preferably each reactive functional group of the organosilane crosslinking agent is independently selected from the group consisting of epoxy, isocyanate, amino, thiol, halogen, ureido, sulfonic acid, carboxylic acid, and anhydride. Wherein the at least one organosilane crosslinking agent further comprises at least one hydrolysable group capable of forming a silanol group, the at least one hydrolysable group preferably being selected from alkoxy, acyloxy or halogen. A suitable compound is a 3-glycidoxypropyl (3-glycidoxypropyl) functionalized alkoxysilane. Preferably, however, the adhesive does not contain an epoxy functional silane.

Alternatively or in addition, at least some silanol-containing groups may be grafted in situ to the polymerized latex to form a core-shell structure, either before termination/residual monomer stripping, or at the end of polymerization, where trace amounts of monomer are still present in the polymer latex, or after the exotherm peak. Such grafts may comprise ethylenically unsaturated silanes bearing at least one silicon-bonded hydrolysable group. This type of grafting can be carried out by using an oxidizing agent to effect a grafting reaction between the ethylenically unsaturated groups of the siloxane and the pendant or terminal chain unsaturated groups of the SBR polymer. However, for ease of manufacture, it is preferred that the adhesive be free of such grafted functional silanes, and that the adhesive comprising the polymer latex be free of other silicone compounds as curing additives not originally present in the polymer chain.

Where strong adhesion between the fiber and the binder is a priority, the glass fiber or silica fiber may be pretreated with monomeric alkoxysilane and then subjected to a curing step to silanize the glass fiber prior to application of the binder. This embodiment is less preferred.

While not within the scope of the present invention, those skilled in the art will appreciate that while known in the art are concerned with oxidizing agents, (X) SBR-based polymers, and any of the following: in the technique of grafting polymers of ethylenically unsaturated siloxanes, amine-functional siloxanes, glycidyl-functional siloxanes, carboxylic acid-functional siloxanes or hydroxyl-functional siloxanes, silylation of the polymers can also be omitted during copolymerization of SBR-or XSBR-based polymers and including siloxane-containing groups after termination and before or after removal of (X) SBR-based polymer from the polymerization tank, and/or before or after the residual monomer stripping step, and/or before or after resuspension of (X) SBR-based polymer. The disadvantage of this process is that it is a multi-step process and has the following difficulties: non-selective grafting, unwanted side reactions, high reaction initiation temperatures, and the possibility of requiring other catalysts not desired in the final composition.

In one embodiment, an acid or base catalyst may also be present that reduces the activation energy of the hydrolysis or silanol condensation reaction. The catalyst promotes initial hydrolysis before the binder dries. As disclosed in US6313253B1, effective catalysts may be acetic acid, mineral acids, lewis acids, tin-based catalysts, alkali or alkaline earth metal compounds and chelating promoters thereof.

In another embodimentIn embodiments, light curing may be used to create silane bonds from the siloxane. Typically, photoinitiators are used in combination with UV radiation, with or without aprotic solvents, to effect curing of the matted fibers or webs (the fiber mat or mesh) at room temperature. The photocuring step is generally carried out in an inert or sub-aerobic atmosphere to prevent inhibition of photocuring, for example

819, preferably monochromatic light having a wavelength of 360nm to 380 nm. Such embodiments are believed to fully cure at the end of the exothermic release.

Suitable surface tensions for the adhesive of the invention may range from 20 to 52mN/m, preferably from 23 to 45mN/m, more preferably from 25 to 42mN/m, most preferably from 28 to 38mN/m, as measured according to ISO 1409 at 23 ℃. As understood by those skilled in the art, the appropriate surface tension can be adjusted by adding appropriate amounts of surfactants and/or wetting agents to adjust the desired surface tension. Preferred surfactants or wetting agents are sodium dioctyl sulfosuccinate, sodium dinonyl sulfosuccinate and ethoxylated mixtures of linear C9-C11 alcohols. In addition, the dialkyl sulfosuccinates useful in the present invention are the ammonium and alkali metal salts, especially the sodium and potassium salts, of dialkyl sulfosuccinates.

In the context of the present invention, a nonwoven fabric is defined in ISO standard 9092 and CEN EN 29092 as a sheet of fibers, continuous filaments or chopped yarns of any nature or origin, which are formed into a network by any means and bonded together in any manner, except woven or knitted. The felt obtained by wet milling is not a nonwoven fabric.

The wet laid webs are non-woven fibers, provided that they contain at least 50% of man-made fibers having an aspect ratio equal to or greater than 300 or fibers of non-plant origin, or at least 30% of man-made fibers having an aspect ratio equal to or greater than 600, and 0.40g/cm³The maximum apparent density of (c).

Composite structures are considered nonwovens provided that they are composed of at least 50% by mass of a nonwoven as defined above, or if the nonwoven component plays a "general role".

The nonwoven fabric fibrous structure of the present invention may be suitable for use as a coated backing layer (sarking), roofing material, and a primary backing for sealing membranes.

Suitable nonwoven fabrics may be made from spunbond nonwoven fabrics or webs of staple fibers.

Spunbond nonwovens can be made by randomly depositing freshly melt spun filaments. They consist of endless (endless) synthetic fibres made of a melt-spinnable polymeric material, for example a polyester, in particular a partially aromatic polyester of wholly aromatic polyester. The staple fiber web may be formed by a carding, air-laying or wet-laying process, followed by stacking of the webs by parallel laying, cross laying and perpendicular laying processes.

In both cases, the nonwoven fabric is bonded by the adhesive of the present invention to provide sufficient mechanical stability, e.g., good puncture strength and good tensile strength, e.g., in processes such as asphalting or paving. In addition, high thermal stability and high thermal dimensional stability are required, for example during asphalting, or when radiation heating applications are being performed. In contrast to prior art adhesives, according to the present invention, the addition of reactive thermosetting resins such as resins that release formaldehyde upon curing is not required and is preferably avoided.

In addition to chemical bonding, the mechanical stability can be further improved by reinforcing fibers, such as glass fibers, or by composites which are incorporated into spunbonded fabrics and staple fiber webs by knitting or stitch bonding (stitch bond) techniques, or by using bicomponent fibers or else using starches which are compatible with the polymer latices of the invention, for example native starches (so-called native starches) and modified starches (for example cationic or anionic or starch derivatives (so-called chemically modified starches)).

Examples of such membranes can be found in GB-A-1,517,595, EP-A-160,609, EP-A-176,847, DE-A-3,347,280, US-A-4,472,086, US-A-4,504,539, EP-A-0,281,643, EP 2231917B 1, EP-A-333,602 and EPA-A-395,548.

Another object is an EIFS or ETICS system based on a woven glass fiber structure. However, other glass netting systems (ETICS ═ exterior wall insulation), glass scrims, knit scrims, fiberglass mats, and glass mats may also be reinforced with the binder of the present invention.

Alternatively or additionally, the reinforcing fiber structure may comprise a fabric, typically but not limited to fiberglass threads (yarns and rovings) or filaments derived from any Tex series, where Tex is a unit of yarn weight. Glass fabric in this description is to be understood as a glass mesh structure (woven), a glass scrim system or a glass mat (non-woven), particularly suitable as a core grid for mortar and mortar reinforcement, mortar layer reinforcement for supporting an inlay pattern, or any other type of glass fiber reinforcement system. Applications also include fiberglass wallpaper (which may be woven and non-woven).

Common features of these glass fabrics are the use of the binder of the present invention, resulting in woven pattern stability, excellent alkali resistance, ease of use by construction workers, greater resistance to mishandling, protection from aggressive environmental influences, and fiber bonding.

The process of coating the fibers with the polymer latex can be performed for different target coating weights. Coating weight is defined as the ratio of the total weight of the primary binder (bone binder) to the total weight of the dry solid fibers, which may be individually coated fibers or in a coated web configuration. The skilled person will appreciate that the optimum amount is a compromise between the mechanical properties and/or alkali resistance of the impregnated and cured fibre and the cost of the binder to achieve an effective cured textile fibre structure. The coating weight value may be higher than 1.0[ wt% dry/dry ], higher than 2.0%, higher than 3.0%, higher than 4.0%, higher than 6.0%, higher than 8.0%, higher than 10.0%, higher than 12.0%, higher than 14.0%, higher than 16.0%, higher than 17.0%, higher than 18.0%, higher than 19.0%, higher than 20.0%, higher than 21.0%, higher than 22.0%, higher than 24.0%, higher than 26.0%, higher than 28.0%, higher than 30.0%, higher than 35.0%, higher than 40.0%, or higher than 50.0% [ wt% dry/dry ], or even larger amounts. Coating weight values may be less than 100.0% [ wt% dry/dry ], less than 50.0%, less than 45.0%, less than 40%, less than 35%, less than 30.0%, less than 28.0%, less than 26.0%, less than 24.0%, less than 22.0%, less than 21.0%, less than 20.0%, less than 19.0%, less than 18.0%, less than 17.0%, less than 16.0%, less than 14.0%, less than 12.0%, less than 10.0%, less than 8.0%, less than 6.0%, less than 4.0%, less than 3.0%, less than 2.0%, less than 1.0%, or less than lower loads. The coating weight may include all values and sub-values therebetween.

The invention will now be illustrated by the following examples.

Examples

Determination of physical parameters:

the dispersions were characterized by measuring the Total Solids Content (TSC), pH, glass transition temperature and viscosity (Brookfield LVT).

Determination of the Total Solids Content (TSC):

the determination of the total solids content is based on gravimetric analysis. 1-2g of the dispersion were weighed on an analytical balance and placed in a tarred aluminum pan. The trays were stored in a circulating air oven at 120 ℃ for 1 hour until a constant mass was reached. After cooling to room temperature (23 ℃), the final weight was measured again. The solids content was calculated as follows:

m_initialInitial weight, m_{Finally, the product is processed}Dry basis weight

Determination of pH:

the pH value is determined in accordance with DIN ISO 976. After 2-point calibration with buffer solution, the electrode of the Schott CG 840pH meter was immersed in the dispersion at 23 ℃ and the constant value on the display was recorded as pH value.

Measurement of viscosity:

the viscosity was measured with a Brookfield LVT viscometer at 23 ℃. About 220ml of liquid (without air bubbles) was charged into a 250ml beaker and the spindle (spindle) of the viscometer was immersed until the mark was reached. The viscometer is then turned on and values are recorded after about 1 minute until they are constant. The viscosity range determines the selection and speed of rotation of the rotor and the coefficients for calculating the recorded values of viscosity. Information about the rotor and rpm is shown in parentheses in table 1.

Measurement of surface tension:

surface tension was measured according to ISO 1409 at 23 ℃.

Measurement of glass transition temperature:

glass transition temperatures were measured according to ASTM D3418-08. Tmg is the midpoint temperature measured at a heating rate of 20 deg.C/min.

The following abbreviations are used in the examples:

AA ═ acrylic acid

IA ═ itaconic acid

2-HEA ═ 2-hydroxyethyl acrylate

MAAm ═ methacrylamide

B ═ butadiene

S ═ styrene

Seed of carboxylated styrene copolymer (including the weight of acrylic acid residue)

ACN ═ Acrylonitrile

tDDM ═ t-dodecyl mercaptan

Na₄Tetrasodium salt of EDTA ═ ethylenediaminetetraacetic acid

NaPS sodium peroxodisulfate

Memo ═ gamma-methacryloxypropyltrimethoxysilane

Emu SAS ═ C14-C17 secondary alkyl sodium sulfonate

EMU SDBS sodium dodecyl benzene sulfonate

TSC-Total solids content

Tmg ═ glass transition temperature, midpoint temperature

Thermal Dimensional Stability (TDS)

Hereinafter, all parts and percentages are by weight unless otherwise indicated.

Example 1

The polymer latex composition is prepared by radical polymerization combining an initial charge (initial charge) and a feed (feed). Stainless steel pressure high pressure purging nitrogenThe seed in the initial charge and a complexing agent (0.03 parts by weight of Na based on 100 parts by weight of the monomer containing the seed latex) were added to the autoclave₄EDTA, 0.1 parts by weight of emulsifier, itaconic acid (if used), and water (about 65 parts by weight)). After heating the initial charge to 85 ℃, the polymerization was initiated by starting the NaPS feed. The monomer addition (except methacrylamide and itaconic acid) was started 5 minutes after the NaPS feed and continued for 6 hours. Addition of methanol acrylamide and additional emulsifier was started after 60 minutes and continued for 5 hours. After this, post-activation with NaPS was started to reduce residual monomer for 2 hours, and then the phase was maintained at 85 ℃ for 1 hour. Residual monomers were removed by vacuum distillation at 60 ℃. Cooling the reaction mixture to room temperature; the pH was adjusted to 6.7 by using aqueous sodium hydroxide solution, 0.5 parts by weight of Wingstay L-type antioxidant (60% dispersion in water) and (according to table 1)0.4 parts of a sodium dialkyl sulfosuccinate-based wetting agent were added. The total solids content was adjusted to 50% and sieved through a sieve (90 μm). The properties of the latex prepared are summarized in table 1.

For comparison to represent the industry standard described in the background section, commercial XSBR latex containing N-methylol (meth) acrylamide residues available as Litex SBV 600 from Synthomerdeutschland GmbH was used in the comparative examples. In the latex of the invention, N-methylolmethacrylamide was replaced by γ -methacryloxypropyltrimethoxysilane and the glass temperature was adjusted by the monomer composition to approach that of Litex SBV 600 at 31 ℃.

Impregnation of non-woven fabric for roofing felt:

the latex is used to impregnate a non-woven fabric comprising a bituminous roofing felt.

The latex was diluted with deionized water to a TSC of 8 wt%. Using a catalyst having a viscosity of 158g/m²Gram weight polyester spunbond nonwoven impregnation samples (32 × 40cm) were impregnated using a laboratory scale grid machine of HVF 350 type (3 bar, 1.5 m/min) supplied by Mathis AG, switzerland, achieving a coating weight of 20 wt%, dry/dry the coated fabric was dried on a tentering frame (pre-stretched 1kP) at a temperature of 200 ℃ for 10 minutesA clock.

In the case of combining the Litex SBV 600 with a melamine formaldehyde resin, 93pph of latex was mixed with 7pph of madurat SMW 818(Ineos Melamines GmbH), diluted with deionized water to 8 wt% TSC and stirred at room temperature for 20 minutes.

Testing the thermal dimensional stability of the fabric according to DIN 18192 (paragraph 5.7); the elongation and shrinkage are summarized in table 2.

Table 2: comparative example

As can be seen from a comparison between the examples of the present invention and the comparative examples, the binders of the present invention achieve the same level of thermal dimensional stability when cured without formaldehyde emission as the 2-pack (2K) binder system, which uses a urea formaldehyde crosslinker in addition to the latex containing N-methylolmethacrylamide. TDS elongation is better improved for many of the binders of the present invention. The thermal dimensional stability is significantly improved when the adhesive of the present invention is used as compared to 1-pack (1K) commercial adhesives.

Example 2

The polymer latex composition is prepared by radical polymerization combining an initial charge and a charge. To a nitrogen purged stainless steel pressure autoclave were added the seed in the initial charge and a complexing agent (0.03 parts by weight of Na based on 100 parts by weight of the monomer containing the seed latex)₄EDTA, 0.1 parts by weight of emulsifier, itaconic acid and water (about 65 parts by weight)). After heating the initial charge to 85 ℃, the polymerization was initiated by starting the NaPS feed. The addition of monomers (except methacrylamide and itaconic acid) was started 5 minutes after the sodium peroxodisulfate feed and continued for 6 hours. Addition of methanol acrylamide and additional emulsifier was started after 60 minutes and continued for 5 hours. Thereafter, post-activation with NaPS was initiated toThe residual monomer was reduced for 2 hours and then kept in phase at 85 ℃ for 1 hour. Residual monomers were removed by vacuum distillation at 60 ℃. Cooling the reaction mixture to room temperature; the pH was adjusted to 6.7 by using aqueous sodium hydroxide solution, 0.5 parts by weight of Wingstay L-type antioxidant (60% dispersion in water) and 0.4 parts of a sodium dialkyl sulfosuccinate-based wetting agent were added. The total solids content was adjusted to 50% and sieved through a sieve (90 μm). The properties of the latex prepared are summarized in table 3.

Table 3: properties of the latex prepared

Latex emulsion	2
		AA	2.5
IA	1.0
		B	39.0
MAAm	1.0
		S	53.0
S seed	1.0
		Memo	2.5
tDDM	0.5
		Emu SAS	0.8
NaPS	1.05
		Surface tension [ mN/m]	36.7
Viscosity (rotor 2, 60rmp) [ mPas ]]	36.7
		Tmg DSC[℃]	9

For comparison to represent the industry standard as described in the background section, commercial XSBR latex containing N-methylolacrylamide residues available as Litex S10656 from SynthomerDeschland GmbH was used in the comparative examples. In the latex of the present invention, gamma-methacryloxypropyltrimethoxysilane was used in place of N-methylolacrylamide, and the glass temperature was adjusted by the monomer composition to approach that of Litex S10656 at 5 ℃.

Table 4: viscosity of the product

Blocking test:

a polymer film having a film thickness of 0.5mm was prepared by drying at a temperature of 40 ℃ and then drying at 150 ℃ for 5 minutes. Test pieces of 2X 2cm were cut and placed in a Fixo test unit from Atlas: the film was loaded with 5kg and held at 50 ℃ for 1 hour. After cooling to room temperature (23 ℃), the caking behaviour was evaluated: 1, no adhesion and easy separation; 6-complete adhesion and no separation.

Table 5:

test according to DIN 13496 or ETAG 004-alkali resistance:

the latex was used to impregnate glass fibers of EIFS, and the residual tensile/alkali resistance (residual tensile/alkali resistance) was determined. The latex was diluted to 45 wt% TSC with deionized water prior to impregnation. Impregnation was performed using a woven open mesh (open mess) fiberglass structure (11 threads per 50mm in the warp direction and 10 threads in the weft direction). Test specimens of dimensions 32X 40cm were impregnated with latex by using a laboratory-sized HVF 350 model (0.95 bar, 0.5 m/min) Foula machine supplied by Mathis AG, Switzerland. The coating weight is 15-20 wt% dry/dry of the final impregnated web weight. If not mentioned in a different way in the table, the coated glass web was dried on a tenter frame at a temperature of 150 ℃ for 5 minutes.

The mechanical properties of the impregnated webs were determined according to DIN 13496 or ETAG 004. The tensile strength of the test piece before and after the chemical treatment was measured in the warp and weft directions. The residual tensile strength is calculated in% by the ratio after and before the chemical treatment.

Table 6:

ETAG 004 measurements-change in curing temperature:

the residual stretch after aging under standard drying conditions was set to 100 (2 minutes at 80 ℃ C. and then 5 minutes at 140 ℃ C.). The residual stretch after aging was calculated as a percentage of the residual stretch cured under standard conditions at varying drying temperatures (step 1: 2 min at 80 ℃ C., step 2: 5 min at 140 ℃ C.).

Table 7:

as can be seen from the comparison between the inventive binder and the comparative binder, the inventive binder provides lower viscosity, improved alkali resistance at the same TSC, and can be cured to a sufficient level at lower temperatures and in a shorter time without releasing formaldehyde compared to the formaldehyde release standard. Thus, when the binder of the present invention is employed, handling and processing efficiency can be improved, resulting in an enhanced product.

Claims

1. A textile fibrous structure comprising rayon reinforced with a binder, said binder comprising a polymer latex obtained by emulsion polymerization in an aqueous medium of an ethylenically unsaturated monomer mixture, said ethylenically unsaturated monomer mixture comprising:

(a) an aliphatic conjugated diene;

(b) an aromatic vinyl compound;

(c) an ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group; and

(d) from 0.1 to 8% by weight, based on the total weight of the ethylenically unsaturated monomers, of at least one ethylenically unsaturated acid.

2. The textile fibrous structure of claim 1, wherein the binder is free of formaldehyde-releasing components, and/or wherein the polymer latex is the sole binder.

3. The textile fibrous structure according to any of the preceding claims, wherein the ethylenically unsaturated monomer mixture comprises:

(a) 20-60% by weight of at least one aliphatic conjugated diene;

(b)30-70 wt% of at least one aromatic vinyl compound;

(c)0.5 to 5% by weight of at least one ethylenically unsaturated silane having at least one silicon-bonded hydrolysable group; and

the weight percentages being based on the total amount of monomers and adding up to 100% by weight,

preferably, the ethylenically unsaturated monomer mixture comprises:

(a) 25-45% by weight of at least one aliphatic conjugated diene;

(b) 50-65% by weight of at least one aromatic vinyl compound;

(d)0.1 to 7% by weight of at least one ethylenically unsaturated acid; and

(e)0 to 20% by weight of at least one other olefinically unsaturated compound than compounds (a) to (d);

and/or wherein:

(a) the conjugated diene is selected from the group consisting of 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, isoprene, and combinations thereof; and/or

(b) The aromatic vinyl compound is at least one selected from the group consisting of styrene, alpha-methylstyrene, p-methylstyrene, t-butylstyrene, 2-vinyltoluene, and combinations thereof; and/or

(c) The ethylenically unsaturated silane bearing at least one silicon-bonded hydrolysable group is selected from the group consisting of gamma- (meth) acryloxypropyltrimethoxysilane, gamma- (meth) acryloxypropyltriethoxysilane, gamma- (meth) acryloxypropylmethyldimethoxysilane, gamma- (meth) acryloxypropyldimethylmethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and combinations thereof; and/or

(d) The ethylenically unsaturated acid is selected from at least one of (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinyl acetic acid, vinyl lactic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamido methyl propane sulfonic acid, and combinations thereof; and/or

(e) The ethylenically unsaturated monomers other than monomers a) to d) are selected from at least one of alkyl or hydroxyalkyl (meth) acrylates, unsaturated nitriles, vinyl esters of carboxylic acids, amides of ethylenically unsaturated acids and vinyl compounds containing sulfonate, sulfonic acid and/or amide groups.

4. The textile fibre structure according to any one of the preceding claims, wherein:

the artificial fibers are selected from organic polymer fibers and glass fibers,

wherein preferably the organic polymer fibres are selected from fibres comprising polyesters, polyetheresters, polyurethanes, polybutylene terephthalate, hydroxy-functionalised polyolefins such as (meth) acrylic-g-propylene, polyvinyl alcohol or acetals or ketals thereof, nylon 6, nylon 66, polyethylene, polypropylene, polyarylene sulphides, polydietherketone, graphitic carbon, especially activated fibrous carbon, glassy carbon fibres, graphite-epoxy mixtures, fullerene-type carbon, acrylic fibres, modacrylic fibres, aramid or kevlar fibres, nomex fibres, spandex fibres, polyacrylonitrile, chemically modified polycarbonate fibres, chemically treated vinylidene fibres, chemically treated vinyon or saran PVC fibres, artificial polyisoprene or combinations thereof.

5. The textile fibrous structure according to any of the preceding claims wherein the fibrous structure is selected from the group consisting of a nonwoven structure and a woven structure.

6. Use of the textile fibre structure according to any of the preceding claims in architectural applications.

7. The textile fibre structure according to any one of the preceding claims, wherein said fibres are organic polymer fibres, preferably polyester fibres, and said textile structure is a non-woven structure.

8. The textile fibrous structure of claim 7, wherein the ethylenically unsaturated monomer mixture comprises:

(d)0.1 to 6 weight percent of at least one ethylenically unsaturated acid, preferably acrylic acid, itaconic acid, or combinations thereof;

(e2)0.5 to 5% by weight of at least one amide of an ethylenically unsaturated acid, preferably (meth) acrylamide.

9. Use of the textile fibre structure of claim 7 or 8 in roofing material applications.

10. The textile fibre structure according to any one of claims 1-5, wherein said fibres are glass fibres, preferably glass fibres comprising a size, and said textile structure is a woven structure.

11. The textile fibrous structure of claim 10 wherein the ethylenically unsaturated monomer mixture comprises:

12. Use of the textile fibre structure according to claim 10 or 11 in an exterior insulation system (EIFS).

13. Use of a binder as defined in any one of claims 1 to 3, 8 and 11 for reinforcing a textile fibre structure.

14. Use according to claim 13, wherein the surface tension of the adhesive is 20-52mN/m, preferably 23-45mN/m, more preferably 25-42mN/m, most preferably 28-38mN/m, measured according to ISO 1409 at 23 ℃.

15. Use according to claim 13 or 14, wherein the textile fibre structure is as defined in any one of claims 4,5, 7 and 10.