CZ286935B6 - Composite material reinforced with glass fibers and process for producing thereof - Google Patents

Abstract

Prodn. of a glass fibre-reinforced composite material comprises a) heating glass fibres with a silane compsn. comprising silane molecules having amine functional gps. and silicone molecules having ethylenically unsatd. functional gps.; b) admixing the treated glass fibres with a polyolefin resin and a fibre bonding agent comprising (i) 0.05-15 wt% polymerisable unsatd. organic cpd. with at least two polymerisable unsaturation gps.; and (ii) 0.05-5 wt% of a vinyl-polymerisable unsatd. hydrolysable silane; and opt. (iii) 0.0025-2.5 wt% free radical generator. The wt. percentages of (i) to (iii) are based on the total wt. of the treated fibres. The free radicals are generated in an amt. sufficient to cause bonding of the treated glass fibres with the resin. The resultant mixt. is exposed to conditions of temp. and pressure to cause the formation of a fibre-reinforced composite materials. The glass fibre reinforced composite material formed as above is also claimed.

Description

Glass-fiber-reinforced composite material and process for its manufacture

Technical field

The present invention relates to a glass fiber reinforced composite material and to a method of making the composite material. In particular, the present invention is directed to a silane treatment of glass fibers by means of which an increase in the impact strength of the composite material thus obtained is promoted.

BACKGROUND OF THE INVENTION

Processes for manufacturing composite materials by reinforcing plastic materials with glass or other fibers are known in the art. Plastic materials that can be reinforced in this way include polyamides, thermoplastic polyesters, thermoset resins, and polyolefins.

Polyolefin matrix composites and glass fiber reinforced composites have poor mechanical properties compared to similar materials used by other types of plastic matrix. These poor mechanical properties can be attributed to poor internal adhesion between the polyolefin matrix and the glass fiber. Polyolefins and especially polypropylene have extremely low polarity and thus their adhesion to other materials is very poor. For example, it is well known in the industry that no paint or sealant will adhere to the polypropylene surface without pretreating the surface.

To date, many attempts have been made to improve these properties in the case of glass fiber reinforced polyolefin materials by modifying the glass fiber surface and / or polyolefin. For example, U.S. Patent No. 4,451,592, which discloses glass fiber treatment with a mixture of aminosilane and a carboxylated polyolefin / latex film-forming material, along with a polyolefin treatment with a carboxylic acid, for example using isophthalic or terephthalic acid. In this process, the acid reacts with the polypropylene chains to graft onto them, while the aminosilane forms a basic group on the surface of the glass fibers. In the subsequent phase when the glass fiber comes into contact with the acid-modified polyolefin, electrostatic bonds of the salt type are formed between the fiber and the olefin, thereby increasing the impact strength of the composite material.

Thus, it is known in the art to incorporate acid-grafted polyolefin copolymers into the polyolefin composition and use of the resulting aminosilane-treated glass fiber polyolefin composition thus obtained to improve the mechanical properties of the composite material. Polypropylene modified in this manner is referred to in the literature as "cupped polypropylene", which is described, for example, in U.S. Patent Nos. 3,416,990 and 3,849,516.

U.S. Pat. No. 4,455,343 describes a process for treating glass fiber strands to be used in reinforced mats for thermoplastic polymers, including polyolefins. In this process, the glass fiber strands are treated with an aqueous mixture comprising a combination of organic silane coupling agents, the first of which is a vinyl grouping agent and the second is a saturated aminosilane coupling agent, wherein the vinyl grouping agent is present in an amount of 60 to 99 % wt. and the aminosilane coupling agent is present in an amount of 40 to 1 wt. based on the total weight of the silane present. The aqueous composition further comprises a thermally stable organic peroxide, a glass fiber lubricant and a nonionic

A surfactant. A film-forming polymer and / or a plasticizer can also be incorporated into the aqueous mixture.

U.S. Patent 4,481,322 to Godlewski et al., Which is the same as the present PV, discloses compositions for improving the bonding of glass fibers to thermoplastic polymers including polyolefins. This composition independently of the formation of an electrostatic bond of the salt type between the glass fiber and the thermoplastic material, but rather of the formation of a covalent bond between the two materials. It follows that, when used with polypropylene, there is no need to duplicate or otherwise modify the polypropylene. This composition, which is commercially marketed by Union Carbide Corporation under the trade name Ucarsil PC, comprises (a) a polymerizable unsaturated organic compound having at least two polymerizable unsaturated groups;

(b) a vinyl-polymerizable unsaturated hydrolyzable silane; and (c) a free radical generator.

This three-component system will hereinafter be referred to as a "covalent fiber binder". This composition is normally added to the glass fibers and olefin during the bonding operation. (In the form described in the aforementioned U.S. Patent No. 4,481,322, the covalent fiber binder also comprises an inorganic filler and a surfactant. However, in some cases, the surfactant may be omitted and if the covalent fiber binder is used. to produce a composite material based on glass fibers and polyolefin, then these glass fibers act as an inorganic filler, for example, instead of the mica described in the patent.)

The advantages of using this covalent fiber binder have been described in the literature; see, e.g., Godlewski, Organosilicon Chemicals in Mica-filled Polyolefins, 3R ^h Conference on Reinforced Plastics / Composites, SPI, Houston, Texas, February 9, 1983, and Guillet, Chemical Conplint with Silanes in Filled and Reinforced Polyolefins, "Coupling 88 "Conference, London, UK, February 16-17, 1988. As described in these publications, a fiber-polymer covalent bond formed by covalent fiber bonding agents (fiber bonding agent) provides consistent physical and mechanical properties of composites equivalent to those of known from the prior art, which are obtained by the known process, i.e. the properties of the acid-modified polypropylene-based products and amine-treated glass fibers, but the covalent fiber-based composites are much more stable in an environment of severe conditions. After some aging in a humid atmosphere, these glass fiber products of acid-modified polypropylene and amine treated glass fibers exhibit a dramatic reduction in impact toughness, and under similar conditions, products bonded with a covalent fiber binder exhibit little or no change in properties.

Since the covalent fiber binder acts by radical addition reactions between the strong and the polyolefin, it is not necessary to pretreat the glass fiber with an aminosilane. Unfortunately, commercially available glass fibers are usually treated with lubricating compositions which are optimized for use in combination with conventional acid-modified polyolefins. Therefore, in order to obtain optimum properties of these covalent fiber bonding agents in the manufacture of polyolefin-based composites, a glass fiber pretreatment needs to be performed for this process, which increases the ability of the treated fiber to contribute covalently to the polyolefin matrix.

-2GB 286935 B6

SUMMARY OF THE INVENTION

The present invention provides a method of making a fiberglass reinforced composite material in which such pretreatment of fiberglass is incorporated.

The glass fiber reinforced composite material of the present invention comprises a polyolefin matrix, and glass fibers dispersed in a polyolefin matrix, the glass fibers being bound to the polyolefin matrix by the reaction product of a silane composition comprising silane molecules having amine functional groups, and silane molecules having ethylenically unsaturated functional groups, with a fibrous binder comprising (a) from 0.05% to 15% by weight of a silane molecule; % of a polymerizable unsaturated organic compound having at least 2 polymerizable unsaturated groups; % of an unsaturated hydrolyzable silane with vinyl groups capable of polymerization, and optionally further comprising (c) from 0.0025% to 2.5% by weight of a polymer; free radicals providing a weight percent of components (a) to (c) based on the total weight of the treated glass fibers.

Preferably, for the composite material, the reaction product is derived from a silane composition comprising at least one silane having an amine function and an ethylenically unsaturated function in the same molecule.

Said silane composition preferably comprises any fatty ethylenic acylaminoorganosilane compound of formula

Y [N (Y) _c R ^] _x [N (W) R '] _y [N (Y) _b R ² _{2 - b} ] _z (HX) _w in which:

R ¹ and R ¹ are individually selected from the group consisting of divalent alkylene groups having from 2 to 6 carbon atoms inclusive, divalent arylene groups having from 6 to 12 carbon atoms inclusive, divalent substituted arylene groups having from 7 to 20 carbon atoms inclusive, and divalent radicals of formula -C (= O) R ³ -, wherein

R ³ is a divalent alkylene group having 2 to 6 carbon atoms inclusive,

R ² is a monovalent alkyl or aryl group containing 1 to 10 carbon atoms or hydrogen,

W is either hydrogen or -C (= O) R ⁴ -, wherein R ⁴ is a monovalent hydrocarbon group containing 8 to 24 carbon atoms and containing at least one double bond,

Y is selected from the group consisting of hydrogen, -C (= O) R ⁴ -, wherein R ⁴ is as defined above, R ² and -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) a, wherein R ² is as defined above R ⁵ is a double alkylene group containing 2 to 6 carbon atoms inclusive,

-3 CZ 286935 B6

R ⁶ and R ⁷ are individually alkyl or aryl groups having 1 to 6 carbon atoms inclusive, and

R ⁶ may also be a moiety containing silicon, where the oxygen atom is directly bonded to a silicon atom of R ⁶ in the silicon-containing and has a value of 0, 1 or 2, b is 0, 1 or 2, c has a value of 0 or 1, x and y have values such that x + y = 1 to 30, provided that x is at least 1, z is 0 or 1

X is a halogen atom or an esterhydroxyl or anhydride group, w having a value of 0 to the sum of x + y + z provided that w does not exceed the total number of nitrogen atoms in the free amine form, provided that at least one

Y is -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) and and at least one other Y is -C (= O) R ⁴ -, and if x = 1, y = 0 and z = 0, then c = 1.

The above silane composition preferably comprises a compound:

[CH ₃ (CH ₂ CH = CH) ₃ (CH ₂ ) 7 CO] [NCH ₂ CH ₂ NH] [CH ₂ CH ₂ CH ₂ Si (OMe) ₃ ] ₂ in which Me represents a methyl group.

According to another preferred embodiment, the reaction product is derived from the silane composition comprising a first silane having an amine functional group and a second silane having an ethylenically unsaturated functional group.

Preferably, the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, 1,2-bis- (trimethoxysilylpropyl) ethanediamine, and isomers thereof, and trimethoxysilylpropylsubstituted is more preferred, the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane and gamma-amine propyltrimethoxysilane.

Further preferably, according to this embodiment, said second silane is vinyl silane.

-4GB 286935 B6

The present invention also relates to a process for the production of a glass fiber-reinforced composite material as defined above, which comprises:

- treat the glass fibers with a silane composition comprising silane molecules having amine functional groups and silane molecules having ethylenically unsaturated functional groups,

- the treated glass fibers are mixed with a polyolefin resin and a fiber binder comprising (a) from 0.05% to 15% by weight of a polymerizable unsaturated organic compound having at least 2 polymerizable unsaturated groups and (b) from 0.05% to 5% by weight unsaturated hydrolyzable silane with polymerizable vinyl groups, wherein the weight% of components (a) and (b) are based on the total weight of the treated glass fibers,

- free radicals are formed in the resulting mixture or added to the mixture in sufficient amounts to form the bonded treated glass fibers with the polyolefin resin,

and the resulting mixture of glass fibers of the polyolefin resin and the fibrous binder is exposed to a temperature and pressure sufficient to induce formation of the fiber-reinforced composite material.

In a preferred embodiment of the process, the free radical-providing substance is added as part of the fibrous binder in an amount of 0.0025% by weight to 2.5% by weight, based on the total weight of the treated glass fibers.

According to another preferred embodiment, the silane mixture comprises at least one silane having amine functionalities and ethylenically unsaturated functional groups in the same molecule.

In carrying out the process of the invention, it is preferred that the silane mixture used contains any one fatty ethylenic acylaminoorganosilane compound of the general formula

Y [N (Y) _c R ₂ J _x [N (W) R ¹ ] y [N (Y) _b R ² 2 _b ] _x (HX) _w in which:

R ¹ and R ¹ are individually selected from the group consisting of divalent alkylene groups containing from 2 to 6 carbon atoms inclusive, divalent arylene groups containing from 6 to 12 carbon atoms inclusive, divalent substituted arylene groups containing from 7 to 20 carbon atoms inclusive, and divalent groups of the formula -C (= O) R ³ -, wherein

R ³ is a divalent alkylene group having 2 to 6 carbon atoms inclusive,

R ² is a monovalent alkyl or aryl group containing 1 to 10 carbon atoms or hydrogen,

W is either hydrogen or -C (= O) R ⁴ -, wherein R ⁴ is a monovalent hydrocarbon group containing 8 to 24 carbon atoms and containing at least one double bond,

-5 CZ 286935 B6

Y is selected from the group consisting of hydrogen, -C (= O) R ⁴ -, wherein R ⁴ is as defined above, R ² and -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) a, wherein R ⁵ is divalent C 2 -C 6 alkylene, inclusive,

R ⁶ and R ⁷ are individually alkyl or aryl groups having 1 to 6 carbon atoms inclusive, and

R ⁶ may also be a moiety containing silicon, where the oxygen atom is directly bonded to a silicon atom of R ⁶ in the silicon-containing and has a value of 0, 1 or 2, b is 0, 1 or 2, c has a value of 0 or 1, x and y have values such that x + y - 1 to 30, provided that x is at least 1,

X is a halogen atom or an esterhydroxyl or anhydride group, w having a value of 0 to the sum of x + y + z provided that w does not exceed the total number of nitrogen atoms in the free amine form, provided that at least one

Y is -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) and and at least one other Y is -C (= O) R ⁴ -, and if x = 1, y = 0 and z = 0, then c = 1.

This silane composition preferably contains a compound of the formula:

[CH ₃ (CH ₂ CH = CH) ₃ (CH ₂ ) ₇ CO] [NCH ₂ CH ₂ NH] [CH ₂ CH ₂ CH ₂ Si (OMe) ₃ ] ₂ in which Me represents a methyl group.

According to one preferred embodiment of the process, the silane composition comprises a first silane having an amine functional group and a second silane having an ethylenically unsaturated functional group. According to an even more preferred embodiment, the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, 1,2-bis- (trimethoxysilylpropyl) ethanediamine, and isomers thereof, and trimethoxysilylpropyentubstituent the first silane is at least one silane selected from gamma-aminopropyltriethoxysilane and gamma-amine propyltrimethoxysilane.

-6GB 286935 B6

Most preferably, said second strong is vinylsilane, in particular at least one silane selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane.

In another preferred embodiment, the fibrous binder further comprises a maximum of about 2.5% by weight of the glass fiber surfactant, comprising (i) a siloxane containing at least one silicon-linked alkyl group of at least 12 carbon atoms, or (ii) a polyoxyalkylene compound having one or more polyoxyalkylene blocks, each bound to one end of a siloxane block, an alkyl group having at least 12 carbon atoms or an alkenyl group, and bound to the other end to an alkoxy, siloxane block, or hydroxy group.

According to a further preferred embodiment of the present invention said fibrous bonding composition further comprises at most about 15% by weight of the inert support, based on the weight of the glass fiber. The inert carrier preferably comprises at least one of porous silica, silicates, alumina, aluminosilicate, and polymeric material.

According to a further preferred embodiment of the process according to the invention, the glass fibers are treated with an amount of silane equal to 0.01 to 1% by weight of the glass fiber.

According to a further preferred embodiment of the process, the glass fibers are treated with a lubricating bath containing from 0.1 to 2% by weight of silane. Preferably, the lubricating bath further comprises a film-forming material. Preferably, the film-forming material comprises at least one of polyvinyl acetate, acrylate, polyolefin, polyester, phenol-formaldehyde resin, urea, polyurethane, epoxy resin, and phenoxy resin. It is also preferred that the film-forming material comprises at least one epoxy resin. Said film-forming material preferably comprises 1 to 20% by weight of a lubricating bath.

According to the invention, it is further preferred that the aforementioned polyolefin resin is polypropylene.

It is also preferred that in the fiber binder the polymerizable unsaturated organic compound having at least two polymerizable unsaturated groups is selected from the group consisting of polyvinyl alcohol tri-, tetra- and pentaacrylates, pentaerythritol, methylopropane and dipentaerythritol, and tri-, tetra- and pentamethacrylate of pentaerythritol, methylolpropane and dipentaerythritol.

It is also preferred that the unsaturated hydrolyzable silane with vinyl polymerization groups is selected from the group consisting of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltrichlorosilane, vinyltrichlorosilane, vinyltrichlorosilane, vinyltrichlorosilane, vinyltrichlorosilane, -propinyltrichlorosilane.

It is further preferred that in the fiber binder the free radical providing agent is selected from the group consisting of dicumyl peroxide, lauryl peroxide, azobisisobutyronitrile, benzoyl peroxide, tertiary butyl perbenzoate, di (tertiary butyl) peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5- di (tert-butyl peroxy) hexane, tertiary butyl hydroperoxide and isopropyl percarbonate.

-7EN 286935 B6

It is also preferred in the process of the present invention that the fibrous binder is added in powder form formed by absorbing the liquid constituents of the fibrous binder onto a porous inert support.

In carrying out the process of this invention, the glass fiber is pretreated with a silane composition having both amine functionalities and ethylenically unsaturated functionalities. The silane mixture may comprise at least one silane having an amine function and an ethylenically unsaturated function in the same molecule. Alternatively, the silane mixture may comprise a first silane having an amine functional group and a second silane having an ethylenically unsaturated functional group.

Preferred silanes having an amine functional group and an ethylenically unsaturated functional group on the same molecule are those described in U.S. Patent Nos. 4,584,138 and 4,668,716. These silanes are fatty ethonoid acylaminoorganosilane compounds represented by the general formula

Y [N (Y) _c R ₂ ^] _x N (W) R ¹ ] y [N (Y) _b R ² 2 _b ] _x (HX) _w , in which:

R ¹ and R ¹ are individually selected from the group consisting of divalent alkylene groups containing from 2 to 6 carbon atoms inclusive, divalent arylene groups containing from 6 to 12 carbon atoms inclusive, divalent substituted arylene groups containing from 7 to 20 carbon atoms inclusive, and divalent radicals of formula -C (= O) R ³ -, wherein

R ³ is a divalent alkylene group containing from 2 to 6 carbon atoms;

R ² is a monovalent alkyl or aryl group containing 1 to 10 carbon atoms or hydrogen,

W is either hydrogen or -C (= O) R ⁴ -, wherein R ⁴ is a monovalent hydrocarbon group containing 8 to 24 carbon atoms and containing at least one double bond,

Y is selected from the group consisting of hydrogen, -C (= O) R ⁴ -, wherein R ⁴ is as defined above, R ² and -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) a, wherein R ⁵ is divalent C 2 -C 6 alkylene, inclusive,

R ⁶ and R ⁷ are individually alkyl or aryl groups having 1 to 6 carbon atoms inclusive, and

R ⁶ may also be a moiety containing silicon, where the oxygen atom is directly bonded to a silicon atom of R ⁶ in the silicon-containing and has a value of 0, 1, or 2, b is 0, 1 or 2; c is 0 or 1 , x and y have values such that x + y = 1 to 30, provided that x is at least 1,

X is a halogen atom or an esterhydroxyl or anhydride group,

W6 has a value of 0 to the sum of x + y + z provided that w does not exceed the total number of nitrogen atoms in the free amine form, provided that at least one

Y is -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) and and at least one other Y is -C (= O) R ⁴ -, and when x = 1, y = 0 and z = 0 , then c = 1.

Among these silanes, substances which are synthesized in such a way as to contain 2 silicon atoms in a substantial proportion of the silane molecules are preferred because, as described in the aforementioned U.S. Patent 4,668,716, such silanes have superior properties. Linolenylamidsilanes with a bis-silane structure are particularly preferred, with [(MeO) ₃ SiCH ₂ CH ₂ CH ₂ ] ₂ [NHCH ₂ CH ₂ NH] and [CH ₃ (CH ₂ CH = CH) ₃ (CH ₂ ) being particularly preferred ₁₇ O] [NCH ₂ CH ₂ NH] [CH ₂ NH] [CH ₂ CH ₂ CH ₂ Si (OMe) ₃ ] ₂ wherein Me represents a methyl group, i.e. a mixture of isomers. A preferred commercially available difunctional silane composition is that available under the tradename Y-9708 from Union Carbide Corporation.

When the silane composition comprises a first silane having an amine functional group and a second silane having an ethylenically unsaturated functional group, the aminosilanes ("A" and "Y" symbols following the chemical names of the compounds below are the trade names, by which these products are sold by Union Carbide Corporation);

gamma-aminopropyltriethoxysilane (Al 100), gamma-aminopropyltrimethoxysilane (Al 110), bis (trimethoxysilylpropyl) amine (Y-9492), 1,2-bis (trimethoxysilylpropyl) ethanediamine, and their isomers and trimethoxysilylpropyl-substituted 130-diethylentriamine, gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane are particularly preferred.

Preferred ethylenically unsaturated silanes are vinyl silanes, for example, vinyltrimethoxysilane (A-1771), vinyltriethoxysilane (A-1731), vinyltris (2-methoxyethoxy) silane (A-1722) and gamma-methacryloxypropyltrimethoxysilane (A-1774).

Although the covalent fiber binder does not necessarily contain a surfactant, it is preferred that the fiber binder contains a maximum of about 2.5% by weight based on the weight of the glass fiber of a surfactant comprising (i) a siloxane containing at least one alkyl group bonded to a silicon having at least 12 carbon atoms;

or

(Ii) a polyoxyalkylene compound having at least one polyoxyalkylene block bonded at one end thereof to a siloxane block, a alkyl group containing at least 12 carbon atoms or an alkenyl group, and bonded at its other end to an alkoxy group, a siloxane block or a hydroxy group.

The fibrous binder may also preferably contain a maximum of about 15% by weight, based on the weight of the glass fiber, of an inert inorganic carrier, with preferred inorganic carriers including porous silica, silicates, alumina, aluminosilicates and polymeric materials.

The amount of silane that should be applied to the glass fibers in this process is similar to that used in the prior art processes described above, and the optimum amount for each individual silane mixture and glass fibers can be readily determined by routine empirical testing. It is generally recommended to use an amount of silane of 0.01 to 1% by weight based on the amount of glass fibers. When the silane mixture comprises a first silane having an amine function and a second silane having an ethylenically unsaturated functional group, the molar ratio of the first silane to the second silane may vary over a wide range, but is usually in the range of 1: 9 to 9: 1. The optimal ratio for any particular mixture can be readily determined by routine empirical methods. Although in quite a small proportion the aminosilane can act as a catalyst, it is generally recommended that the silane mixture contain a small proportion of aminosilane and a large proportion of unsaturated silane.

As is conventional in the present invention, the silane composition may be in the form of a lubricant bath containing components other than silanes. Preferably, such a lubricating bath may contain from 0.1 to 2% by weight of silane. Typically, such a lubricating bath also comprises a film-forming agent, for example at least one of polyvinyl acetate, acrylate, polyolefin, polyester, phenoxy resin, phenol-formaldehyde resin, urea resin, polyurethane resin, and epoxy resin. Preferred film forming materials for use in this process of the invention are epoxy resins because the epoxy resins react with aminosilanes, and this addition reaction can bring additional advantages in increasing the impact strength of the composite material. Preferably, the film-forming material constitutes 1 to 20% by weight of the lubricating bath.

The deposition of the silane mixture on the glass fibers can be carried out by any conventional method known to those skilled in the art. Thus, the glass fiber to be treated may be in the form of continuous strands of glass fibers, continuous glass fibers, flame retardants, mats, fabrics or chopped strands. The silane mixture can be applied to the glass fibers directly after forming the fibers by means of a roller applicator. Alternatively, the silane mixture may be applied by spraying or dipping the glass fibers into the silane mixture either at the time of the glass fiber formation or after drying the glass fiber.

As already mentioned, the silane composition may be incorporated into a lubricating bath containing other ingredients such as film-forming materials. Alternatively, the silane mixture and the commonly used lubricating bath may be applied separately to the glass fibers, such as by means of a twin-cylinder applicator or two separate applicator systems for spraying, dipping or subsequent treatment of the glass fibers after drying. However, it should be noted in this context that the properties of some combinations of silanes and said other components of the lubricating bath may vary depending on whether they are applied together from one lubricating bath or separately. Some lubricating baths are not merely mixtures, so substantial interactions can occur between silane and other bath components, especially in film-forming materials. In particular, aminosilanes are added to the preferred epoxy resins used in the lubricating bath. The same is true for isocyanates

-106 286935 B6 Formal prepolymers and formaldehyde resins. If any of these film-forming materials is used with aminosilanes in a lubricating bath, then the rate of addition of silanes and film-forming materials may affect the properties of the final composite materials. In the following examples, it will be shown that the effect of the film-forming material is important and varies in concentration, showing that there is a specific optimum concentration for each particular film-forming material, depending on the type of material.

Whether or not the silane composition is in the form of a lubricating bath, the composition may comprise water or organic solvents. Where silane is to be included in the aqueous mixture, it should be added to the water and not vice versa. In addition, when the silane is to be incorporated into an aqueous lubricating bath containing other components, it is desirable that the silane be separately hydrolyzed and then added to the remaining components of the lubricating bath.

Although various polyolefins such as polyethylene and ethylene-propylene copolymers may be used in the process of the present invention, the preferred polyolefin resin is polypropylene.

The details of the covalent fiber bonding compositions used in this invention are fully contained in the aforementioned U.S. Patent No. 4,481,322 (Godlewski), the entire contents of which are herein incorporated by reference and, therefore, these compositions will not be described in detail herein. The covalent fiber binder composition comprises a polymerizable unsaturated organic compound having at least two polymerizable unsaturated groups, the compound being one or more of the poly (vinyl alcohol) tri-, tetra- or pentaacrylates, pentaerythritol, methylolpropane, dipentaerythritol, or tri-, tetra- or pentamethacrylates, pentaerythritol, methylolpropane or dipentaerythritol.

The vinylpolymerized unsaturated hydrolyzable silane is preferably at least one silane selected from the group consisting of gamma-methacrylopropyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltrichlorosilane, gamma-acryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane.

The free radical generator is preferably at least one selected from the group consisting of dicumyl peroxide, lauryl peroxide, azobisisobutyronitrile, benzoyl peroxide, tertiary butyl perbenzoate, di (tertiary butyl) peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, tertiary butyl hydroperoxide and isopropyl percarbonate. Alternatively, free radicals may be generated by heat or shear treatment on a plastic processing device (e.g., in extruders used to mix polyolefin and glass fiber), thereby reducing or eliminating the need for the addition of a chemical free radical generator.

DETAILED DESCRIPTION OF THE INVENTION

The process and the composite material of the present invention will be explained in more detail below with reference to specific examples, which are illustrative only and are not intended to limit the scope of the invention in any way. All parts and proportions are by weight unless otherwise indicated. The abbreviations and notations used in these examples are as follows:

LOI - loss of annealing at 540 ° C after 2 hours

LOI outside + LOI inside

Migration index = ------------------ 2 x medium LOI

Wherein the symbols "outside" and "inside" mean the inner and outer surfaces of the mold cake as described in Example 1, part B.

Tensile properties - were determined according to ISO R 527-67 using Type I specimens at 23 ° C and a pulling speed of 50 millimeters per minute.

Charpy notch impact test - Determined according to ISO 179-82 using non-notched specimens.

Thermal deflection temperature (HDT) - determined according to ISO 75-74 using samples of 110 x 10x4 millimeters at a deflection of 0.32 millimeters at 1820 MPa after pre-treatment for 3 minutes at 150 ° C, with pre-treatment necessary to ensure reproducible results.

In the following examples, two different annealing loss tests were used. The first, which is indicated as the "loss on ignition of glass fibers" is determined by the annealing of the glass fibers themselves and simply determines the lubrication of the glass fiber. The second, referred to as the "composite annealing loss" (composite LOI), is determined by the annealing of the final composite material, but this major weight loss is due to the burn-out of the polyolefin base of the composite material. In this way, the composite LOI is used to determine the proportion of polyolefin and glass fiber in the composite material.

Example 1

This example illustrates a process of the invention in which the silane mixture comprises one silane having both amine and vinyl functional groups.

A. Preparation of the lubricating bath

50 grams of linolenylamidosilane was added with stirring to 2500 grams of distilled water and the resulting mixture was allowed to hydrolyze for 30 minutes at pH 6. After addition of the silane, the pH was adjusted to this value with dilute acetic acid.

Separately, 150 grams of self-dispersible epoxy resin (Epikote 255, sold by Shell Oil Company) diluted with 7 grams of acetone was added slowly, with vigorous stirring, to a further 2500 grams of distilled water preheated to 40 ° C. The resulting dispersion was allowed to cool and then mixed with the silane solution. Finally, the pH was adjusted to 5.0 with dilute acetic acid to form a final lubrication bath.

B. Preparation of Lubricated Glass Fiber

The glass fiber was made of E-glass (which is a commonly used symbol for glass suitable for electrical purposes due to its low electrical conductivity and suitable use as a dielectric), having the following composition (in% by weight):

SiO ₂

Na ₂ K ₂ O

A1 ₂ O ₃

Fe ₂ O ₃

MgO

54.4

0.5

0.2

14.1

0.2

0.4

-12GB 286935 B6

CaO22.4

B ₂ O ₃ 8.0

F ₂ 0.4.

Glass fibers having a nominal titre of 68 Tex (corresponding to a fiber diameter of 13 microns) were drawn from this glass using a 204-hole ball oven at a plate temperature of 1200 ° C, a drawing speed of 1200 meters per minute and a drawing time of 4. minutes to give a glass yield of 80 grams per minute and a molding cake of 330 grams. The lubrication bath prepared according to paragraph A was applied to the fibers immediately after formation by means of a cylindrical applicator operating at 8 meters per minute. In this way 40 cakes were prepared, which were dried in an oven at 140 ° C for 10 hours and then at 120 ° C for 2 hours.

The oven was then cooled to 40 ° C and the molding cakes were removed. Of the 36 cakes, strands of a nominal titer of about 2400 Tex were prepared at a winding speed of 30 meters per minute. The winding speed was limited by the bonding of the fibers, the formation of loops and deposits on the brake pads, although the strands had the correct shape with a slight yellowing on their surfaces. The fiber properties were as follows:

LOI glass fibers 0.46% migration index 1.9 fiber titer 62.0 Tex tensile strength 53 cN / tex (using 500 mm samples at a drawing speed of 200 millimeters per minute).

C. Mixing and injection molding of the composite

The strands prepared in paragraph B were then blended with a polypropylene homopolymer (Moplen C 30 G having an MFI melt index at 230 ° C and a load of 2.16 kilograms, 6 dg / min) in a Comec Plast EB-386 extruder, with a length of 38 millimeters with twin-screw worms with a length to diameter ratio of 25: 1. This extruder was operated at 100 rpm at a melt temperature of 225 ° C and a melt pressure of 49 bar. The temperature profile in the extruder was as follows:

temperature (° C)

polymer dosing 230 zone 2 240 zone 3 235 fiber dosing 230 zone 5 230 nozzle 220 slot 220

The covalent fiber binder used in this process contained a mixture of 4 parts of a mixture of substantially equal amounts of trimethylolpropanetriacrylate and gamma-methacryloxypropyltrimethoxysilane in a 1: 1 ratio with one part by weight of an 8% solution of dicumylperoxide in vinyltriethoxysilane. For ease of handling, this liquid mixture was mixed with an equal amount of inert carrier (sold by Degussa under the trade name Sipemat 22) to give a 50% dry powder concentrate.

The proportions used in the extruder were 67.6% polypropylene, 30% glass fiber strands and 2.4% dry powder concentrate containing a covalent fiber binder.

-13GB 286935 B6

Polypropylene was mixed with a covalent fiber binder in the form of a concentrate, and the resulting mixture was dosed as pellets with a metered dispenser and metered into a mixing line. The covalent fiber binder may be mixed with other components of the composite material by other methods. For example, the covalent fibrous binder may be added to the glass fibers whether the glass fibers are fed separately to the extruder or added in chopped form to the same hopper as the polyolefin. The lubricated glass fibers were fed at the end of the melting zone as a 4 x 2400 tex strand. The extrudate was cooled in a water bath and chopped into pellets.

The composite pellets thus obtained were injection molded in a 75 ton Arburg Allrounder press using an Arbid screw and a 30 millimeter diameter cylinder and a 20 length / diameter polymer at a screw speed of 30 rpm, a cycle time of 55 seconds and a subsequent temperature profile. .

dosage 220 DEG zone 2 218 ° C zone 3 220 DEG nozzle 220 DEG form 60 ° C D. Properties of composite The molded composite material had the following properties: LOI composite 70% yield strength 99 MPa tensile extension 1,8% yield strength 112 MPa bending module 4190 MPa non-notched Charpy impact strength 36 J / m ² Thermal deformation temperature of HDT 161 ° C MFI (230 ° C, 21.6 N) 5.2 g / 10 minutes

Comparative example

This example shows that the use of a silane containing one amino-functional group and not an unsaturated functional group does not exhibit the properties of the composite as good as those obtained in Example 1 above.

The procedure of Example 1 was repeated except that the lubricating bath had the following composition:

gamma-aminopropyltriethoxysilane

Epikote 255 water

0.6%

3.0%

96.4%

The molded composite material produced had the following properties:

LOI composite tensile strength at yield strength tensile elongation at yield strength

69.0%

MPa

2.2%

110 MPa

-14GB 286935 B6 bending modulus 4470 MPa non-notched Charpy impact strength 25 J / m ²

HDT thermal deformation temperature 161 ° C

MFI (230 ° C, 21.6 N) 5.6 g / 10 min

When comparing these values to those in Example 1, it is apparent that although many of the properties of the two mixtures were similar, a control mixture in which the silane did not contain unsaturated functional groups had a Charpy impact strength equivalent to about 70% of the toughness achieved in Example 1.

Example 2

This example illustrates the process of the present invention, wherein the silane mixture contained one silane having both amine groups and vinyl functional groups, but the film forming material used in the lubricating bath was different from the material used in Example 1.

Example 1 was repeated except that Epikote 225 was replaced by Hordamer PE-03, an oxidized polyethylene emulsion from Hoechst Corporation.

The composition of the lubricating bath was as follows (% by weight):

Silane 1,0%

Film-forming material, Hordamer PE-03 3.0%

Water 96.0%

The use of an oxidized polyethylene emulsion as a film-forming material had the advantage that no processing problems were found in the production of strands, so that the strands could be wound at a speed of 300 meters / minute and were of good quality.

The properties of the resulting composite were as follows:

LOI composite 71% yield strength 97 MPa tensile extension 1,8% yield strength 112 MPa bending module 4500 MPa non-notched Charpy impact strength 25 J / m ² HDT 160 ° C MFI (230 ° C, 21.6 N) 4.7 g / 10 minutes

Comparative example

This example demonstrates that the use of a silane containing only amine functionalities and not unsaturated functionalities does not exhibit composite properties as good as those obtained in Example 2 above.

The procedure of Example 2 was repeated except that the silane was replaced with the silane used in Comparative Example A, the lubricating bath having the following composition (% by weight):

-15GB 286935 B6

gamma-aminopropyltriethoxysilane 0.6% Hordamer PE-03 3.0% water 94.6%

The shaped composite material that was produced had the following characteristics:

LOI composite 68% yield strength 90 MPa tensile extension 1,7% yield strength 107 MPa bending module 4970 MPa non-notched Charpy impact strength 20 J / m ² HDT 160 ° C MFI (230 ° C, 21.6 N) 4.4 g / 10 minutes

When comparing these values to those obtained in Example 2, it is apparent that although many of the properties of the two mixtures were similar, the control direction in which the silane did not contain unsaturated functionalities, Charpy impact strength was only 80% of the impact strength achieved in Example 2.

Comparative Example

This example demonstrates that the use of commercial fiberglass strands (which were probably modified to be used in combination with acid-modified polyolefins) does not result in composite properties as good as those obtained in Example 1.

The procedure of Example 1 was repeated except that the strands were replaced with Vetrotex P 365, a commercially available 20 glass fiber roving. The shaped composite material had the following properties:

LOI composite 69% yield strength 88 MPa tensile elongation 2.0% yield strength 100 MPa bending modulus 4170 MPa non-notched Charpy impact strength 22 J / m ²

160 ° C

MFI (230 ° C, 21.6 N) 4.4 g / 10 min

When comparing these values to those obtained in Example 1, it is apparent that although many of the properties of the two mixtures were similar, in the case of the control mixture, the Charpy impact strength was only about 60% of that obtained in Example 1.

Examples 3 and 4

Comparative Examples D and C

These examples illustrate processes of the invention in which the silane mixture comprises a first silane having amine functional groups and a second silane having vinyl functional groups. For comparison, they were

Comparative examples were performed in which each of the two silanes was used alone in a similar lubricating bath.

The procedures were the same as in Example 1 except that the following silane was used in each example (the proportions indicate the percentage of each silane in the lubricating bath).

Example 3

A mixture of 0.35% vinyl-tris (2-methoxyethoxy) silane and 0.30% gamma-aminopropyltriethoxysilane;

Example 4

A mixture of 0.30% methacryloxypropyltrimethoxysilane and 0.30% gamma-aminopropyltriethoxysilane;

Comparative Example D

0.7% vinyl-tris (2-methoxyethoxy) silane and Comparative Example E

0.6% methacryloxypropyltrimethoxysilane.

The properties of the composites produced are shown in the following table. For clarity, this table also repeats the results of Comparative Example A in which 0.6% gamma-aminopropyltriethoxysilane was used as the silane.

Example 3 Example 4 Cf. ex. D Cf. ex. E Cf. ex. AND

LOI (%) 31 30 31 32 31 Tensile strength (MPa) 102 100 ALIGN! 96 95 98 Tensile Elongation (%) 2.6 2.4 1.4 0.5 2.2 Flexural strength (MPa) 112 110 110 106 110 Modulus of bending (MPa) 4230 3940 4560 4310 4470 Charpy's toughness (J / m ² ) 35 33 23 23 25 HDT (150 ° C) 161 161 162 161 161 Melt flow index MFI (g / 10 minutes) - - 8.2 5.3 5.6 From the above data in the table it is obvious, that blends aminosilanes and vinylsilanes used

in Examples 3 and 4, they exhibited substantially higher Charpy impact strength than any of the base silanes used alone.

Claims (32)

CLAIMS 1. A glass fiber reinforced composite material comprising a polyolefin matrix and glass fibers dispersed in a polyolefin matrix, the glass fibers being bound to the polyolefin matrix by the reaction product of a silane composition comprising silane molecules having amine functional groups and silane molecules having ethylenically unsaturated functional groups, with a fibrous binder comprising (a) from 0.05% to 15% by weight of the composition; and (b) from 0.05% to 5% by weight of a polymerizable unsaturated organic compound having at least 2 polymerizable unsaturated groups. % of an unsaturated hydrolyzable silane with vinyl groups capable of polymerization, and optionally further comprising (c) from 0.0025% to 2.5% by weight of a polymer; free radicals providing a weight percent of components (a) to (c) based on the total weight of the treated glass fibers. Fiber-reinforced composite material according to claim 1, characterized in that the reaction product is derived from a silane composition comprising at least one silane having an amine function and an ethylenically unsaturated function in the same molecule. Fiber-reinforced composite material according to claim 2, characterized in that the silane composition comprises any fatty ethylenic acylaminoorganosilane compound of the general formula Y [N (Y) _c R ₂ J _x [N (W) R 1] _y [N (Y) _b R ² ₂ _ _b ] _z (HX) _w in which: R ¹ and R ¹ are individually selected from the group consisting of divalent alkylene groups having from 2 to 6 carbon atoms inclusive, divalent arylene groups having from 6 to 12 carbon atoms inclusive, divalent substituted arylene groups having from 7 to 20 carbon atoms inclusive, and divalent groups of the formula -C (= O) R ³ -, wherein R ³ is a divalent alkylene group containing 2-6 carbon atoms inclusive, R ² is a monovalent alkyl or aryl group containing 1 to 10 carbon atoms or hydrogen, W is either hydrogen or -C (= O) R ⁴ -, wherein R ⁴ is a monovalent hydrocarbon group containing 8 to 24 carbon atoms and containing at least one double bond, Y is selected from the group consisting of hydrogen, -C (= O) R ⁴ -, wherein R ⁴ is as defined above, R ² and -R ⁵ Si (OR ⁶ ) _{3 - and} (R ⁷ ) a, Wherein R ² is as defined above and R ⁵ is a divalent alkylene group containing 2 to 6 carbon atoms inclusive, R ⁶ and R ⁷ are individually alkyl or aryl groups having 1 to 6 carbon atoms inclusive, and R ⁶ may also be a silicon-containing moiety where the oxygen atom is directly bonded to the silicon atom R ⁶ in the silicon-containing moiety and is 0,1 or 2, b is 0,1 or 2, c is 0 or 1, x and y have values such that x + y = 1 to 30, provided that x is at least 1, z is 0 or 1 X is a halogen atom or an esterhydroxyl or anhydride group, w having a value of 0 to the sum of x + y + z provided that w does not exceed the total number of nitrogen atoms in the free amine form, provided that at least one Y is -R'Si (OR ⁶ ) ³ -a (R ⁷ ) and at least one other Y is -C (= O) R ⁴ -, and if x = 1, y = 0 and z = 0, then c = 1. The fiber-reinforced composite material of claim 3, wherein the silane composition comprises [CH ₃ (CH ₂ CH = CH) ₃ (CH ₂ ) ₇ CO] [NCH ₂ CH ₂ NH] [CH ₂ CH ₂ CH ₂ Si (OMe) _{3] 2,} where Me is methyl. The fiber-reinforced composite material of claim 1, wherein the reaction product is derived from a silane composition comprising a first silane having an amine functional group and a second silane having an ethylenically unsaturated functional group. The fiber-reinforced composite material of claim 5, wherein the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, 1,2-bis- (trimethoxysilylpropyl) ethanediamine, and their isomers, and trimethoxysilylpropylsubstituted diethylenetriamine. -19GB 286935 B6 The fiber-reinforced composite material of claim 6, wherein the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane. 8. The fiber-reinforced composite material of claim 5, wherein the second silane is vinyl silane. A method for producing a glass fiber reinforced composite material according to claims 1 to 8, characterized in that the glass fibers are treated with a silane composition comprising silane molecules having amine functional groups and silane molecules having ethylenically unsaturated functional groups, such treated glass fibers. the fibers are mixed with a polyolefin resin and a fiber binder comprising (a) from 0.05% to 15% by weight of the composition. % of polymerizable unsaturated organic compounds having at least 2 polymerizable unsaturated groups; % of unsaturated hydrolyzable silane with vinyl groups capable of polymerization; components (a) and (b) are based on the total weight of the treated glass fibers, free radicals are formed in the resulting mixture or the free radicals are added to the mixture in an amount sufficient to form the treated glass fibers with polyolefin resin, and the resulting glass mixture The polyolefin resin fibers and fibrous binder are exposed to a temperature and pressure sufficient to induce the formation of a fiber-reinforced composite material. The method of claim 9, wherein the added free radical providing substance is admixed as part of the fibrous binder in an amount of from 0.0025 wt%. % to 2.5 wt.% based on the total weight of the treated glass fibers. 11. The process of claim 10 wherein the silane mixture comprises at least one silane having amine functionalities and ethylenically unsaturated functional groups in the same molecule. A process according to any one of claims 9 to 11, wherein the silane mixture comprises any one fatty ethylenic acylaminoorganosilane compound of the general formula YtNÍYjcR. ^ JxtNÍWjR ^ tNÍYjbRVblÁHXk in which: -20GB 286935 B6 R ¹ and R ¹ are individually selected from the group consisting of divalent alkylene groups containing from 2 to 6 carbon atoms inclusive, divalent arylene groups containing from 6 to 12 carbon atoms inclusive, divalent substituted arylene groups containing from 7 to 20 carbon atoms inclusive, and divalent radicals of formula -C (= O) R ³ -, wherein R ³ is a divalent alkylene group containing 2-6 carbon atoms inclusive, R ² is a monovalent alkyl or aryl group containing 1 to 10 carbon atoms or hydrogen, W is either hydrogen or -C (= O) R ⁴ -, wherein R ⁴ is a monovalent hydrocarbon group containing 8 to 24 carbon atoms and containing at least one double bond, Y is selected from the group consisting of hydrogen, -C (= O) R ⁴ -, wherein R ⁴ is as defined above, R ² and -R ⁵ Si (OR ⁶ ) 3 .a (R ⁷ ) a, wherein R ² is as defined above and R ⁵ is a divalent alkylene group having 2 to 6 carbon atoms inclusive, R ⁶ and R ⁷ are individually alkyl or aryl groups having 1 to 6 carbon atoms inclusive, and R ⁶ may also be a moiety containing silicon, where the oxygen atom is directly bonded to a silicon atom of R ⁶ in the silicon-containing and has a value of 0, 1 or 2, b is 0, 1 or 2, c has a value of 0 or 1, x and y have values such that x + y = 1 to 30, provided that x is at least 1, z is 0 or 1 X is a halogen atom or an esterhydroxyl or anhydride group, w having a value of 0 to the sum of x + y + z provided that w does not exceed the total number of nitrogen atoms in the free amine form, provided that at least one Y is -R ⁵ Si (OR ⁶ ) 3 -a (R ⁷ ) and and at least one other Y is -C (= O) R ⁴ -, and if x = 1, y = 0 and z = 0, then c = 1. The method of claim 12, wherein the silane composition comprises [CH ₃ (CH ₂ CH = CH) ₃ (CH ₂ ) ₇ CO] [NCH ₂ CH ₂ NH] [CH ₂ CH ₂ CH ₂ Si ( OMe) ₃ ] ₂ , Wherein Me represents a methyl group. The method of claim 10, wherein the silane composition comprises a first silane having an amine functional group and a second silane having an ethylenically unsaturated functional group. The method of claim 14, wherein the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, 1,2-bis- (trimethoxysilylpropyl) ethanediamine, and isomers thereof, and trimethoxysilylpropylsubstituted diethylenetriamine. The method of claim 15, wherein the first silane is at least one silane selected from the group consisting of gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane. 17. The process of claim 14 wherein the second silane is vinyl silane. The method of claim 17, wherein the second silane is at least one silane selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane and gamma-methacryloxypropyltrimethoxysilane. 19. The method of claim 10, wherein the fiber binder further comprises a maximum of about 2.5% by weight of the surfactant based on the weight of the glass fiber comprising (i) a siloxane containing at least one silicon bonded alkyl group of at least 12 atoms or (ii) a polyoxyalkylene compound having one or more polyoxyalkylene blocks, each bound to one end of the siloxane block, an alkyl group having at least 12 carbon atoms or an alkenyl group, and bound to the other end to an alkoxy, siloxane block, or hydroxy group. The method of claim 10, wherein the fiber binding composition further comprises at most about 15 wt. % of inert carrier, based on the weight of the glass fiber. -22EN 286935 B6 21. The method of claim 20, wherein the inert carrier comprises at least one of porous silica, silicates, alumina, aluminosilicate, and polymeric material. The method according to claim 10, wherein the glass fibers are treated with an amount of silane of 0.01 to 1% by weight. glass fiber. The method according to claim 10, wherein the glass fibers are treated with a lubricating bath containing from 0.1 to 2 wt. silane. The method of claim 22, wherein the lubricating bath further comprises a film-forming material. 25. The method of claim 24, wherein the film-forming material comprises at least one of polyvinyl acetate, acrylate, polyolefin, polyester, phenol-formaldehyde resin, urea, polyurethane, epoxy resin, and phenoxy resin. 26. The method of claim 25, wherein the film-forming material comprises at least one epoxy resin. 27. The method of claim 25, wherein the film-forming material comprises 1-20 wt. lubrication bath. 28. The method of claim 9, wherein the polyolefin resin is polypropylene. 29. The method of claim 10, wherein in the fiber binder, the polymerizable unsaturated organic compound having at least two polymerizable unsaturated groups is selected from the group consisting of polyvinyl alcohol tri-, tetra-, and pentaacrylates, pentaerythritol, methylolpropane and dipentaerythritol, and pentaerythritol tri-, tetra- and pentamethacrylates, methylolpropane and dipentaerythritol. 30. The method of claim 10 wherein in the fibrous binder, the unsaturated hydrolyzable silane with vinyl polymerization groups is selected from the group consisting of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltrichlorosilapropyl, vinyltrichloroshoxysilane, vinyltrichloroshoxysilane, vinyltrichloroshoxysilane , ethinylriethoxysilane and 2-propynyltrichlorosilane. 31. The method of claim 10, wherein in the fiber binder, the free radical providing agent is selected from the group consisting of dicumyl peroxide, lauryl peroxide, azobisisobutyronitrile, benzoyl peroxide, tertiary butyl perbenzoate, di (tertiary butyl) peroxide, cumene hydroperoxide, 2,5-dimethyl- 2,5-di (tert-butylperoxy) hexane, tertiary butyl hydroperoxide and isopropyl percarbonate. 32. The method of claim 10 wherein the fibrous binder is added in powder form formed by absorbing the liquid constituents of the fibrous binder onto a porous inert support.