KR20030026238A - Thermosetting resin-fiber composite and method and apparatus for the manufacture thereof - Google Patents

Abstract

The present invention relates to a structure of a composite material comprising a thermosetting resin and a fiber reinforcement or fiber filler; And to a method for producing the same. The thermosetting resin composition contains a particulate thermosetting phenol-aldehyde resin and the particulate curing agent for the thermosetting resin. The curing agent is encapsulated in a water-insoluble thermoplastic resin having a softening point higher than (1) the melting point of the thermosetting resin and (2) the temperature at which the thermosetting resin flows on the solid substrate. In addition, the encapsulating thermoplastic resin can be dissolved in the thermosetting resin capable of curing the thermosetting resin by melting the encapsulating thermoplastic resin and heating the curing agent when it is released. Phenol-aldehyde resins are novolacs formed by condensation of phenolic components, wherein the phenolic component is one represented by the formula R-CHO, wherein R represents a hydrogen atom, a methyl group or a halogenated methyl group. It contains one or more difunctional phenols having at least aldehyde components.

Description

Thermosetting resin-fiber composite and its manufacturing method and apparatus TECHNICAL FIELD

Panels, rolls, typically encased in a matrix of dendritic products used in building trades, especially thermosetting resins, including glass fiber wool, rock wool and other inorganic fibers The production of products in the form of the back is well known.

Conventionally, the product is obtained by spraying an aqueous phenol-formaldehyde resin solution containing urea optionally added on glass fibers, wool, and the like, and then crosslinking onto the fibers by a heat treatment process to obtain a compact barrier structure (compact A product having an insulating structure was obtained.

The conventional method described above has a disadvantage in that it is difficult to control the resin distribution on the surface of a single glass fiber. Thus, the resin tends to disperse in an irregular or unpredictable direction along the entire length of the fiber, which contributes to curing the fiber upon crosslinking to a rigid structure. The fibers tend to be easily cut during the operation of the final product. In addition, the cleavage of the fiber adversely affects the surrounding environment, since the finely divided fragments produce objectionable emission upon release into the surrounding environment. Given the fact that the hardening of the fibers required to mechanically join the individual fibers together produces glass fibers coated with multiple layers of cured material that make the product more brittle and difficult to manipulate. The above phenomenon is particularly serious. Moreover, this conventional method has the additional drawback of requiring excess resin, which leads to higher production costs of the product and disposal of waste contaminated by other chemicals, such as the decomposition and mixing of polymers. do.

The present invention is directed to a construction of a composite material comprising a thermosetting resin and a fibrous reinforcing agent or fibrous filling agent; And to a method for producing the same.

1 is an overall schematic diagram of the main steps of the method according to the invention.

2 shows a detailed schematic of a system for bonding a resin onto glass fibers.

3 shows an example of a product according to the invention.

4 to 6 show the steps of the process described in FIG.

Summary of the Invention

The present invention relates generally to novel methods and apparatus for producing thermal and acoustic barrier products, for example in the building industry. The process of the present invention enables the production of novel thermoset phenol-aldehyde (eg, novolac) resin / fiber composites, wherein the thermoset phenol-formaldehyde resin / fiber composite has a weaker stiffness of fibers in the composite ( thermoset phenol-formaldehyde in the prior art in that it exhibits less rigidity and thus less breakability in the final product and requires less resin to form the matrix of the composite. Better than resin / fiber composites.

The present invention further relates to (1) a system or apparatus for carrying out the above invention, (2) a composition for the production of said product, and (3) a product obtained by said method.

Detailed description of the invention

The foregoing and other objects are achieved by the methods, devices, compositions and articles described below.

The present invention results in improved mechanical strength in the composite due to the inhibition of structural stiffness in the fiber. In addition, the present invention allows the use of smaller amounts of binder resin, thereby reducing not only the cost of manufacturing the product but also the cost of waste disposal.

These and other objects, features and advantages will be more apparent from the following description of the preferred embodiments of the invention and the drawings shown.

The process shown in FIG. 1 begins with the provision of a mass of molten material (from which fibers are made), in which the mass of molten glass 1 is introduced into a melting furnace 2. Housing and passing through a die 3 yields a flow 4 of molten glass. This fluid is then dropped into the collecting tank 5 of the high speed rotary fiberizing device or spinneret 6. The device has a hole or opening 7 on its outer surface, the corresponding fiber 8 exiting from the hole or opening due to the centrifugal force. The fiber is then deflected towards an underlying conveyor belt 9 via a flame deflector 10. On the conveyor belt 9, a mass or mattress 16 made of glass fiber wool is formed, the thickness of which is controlled by the length of operating time of the fiberizing device 6.

Phenol-formaldehyde resin binder in the form of a dry powder or a dispersion of resin powder in a water slurry, supplied by a sprayer 11, before falling onto the conveyor belt 9, Spray glass fiber 8. Particle materials formed by powders or slurries of phenol-formaldehyde resins and crosslinkers in powder form are sprayed onto the resulting glass fibers 8 and placed in a final structure forming the mattress 16 and sealed (see FIG. 3). . The binder is delivered through a pipe 15 having a double pipe structure, one of which is present inside the other to ensure proper temperature control of the binder. The flow rate of water and binder is controlled by flow controllers and pressures derived from separate reservoirs. The particle diameter of the catalyst resin powder is in the range of 0.5 to 2.5 m.

Subsequently, through a furnace 12 having two heating sectors 13 and 14 with different temperatures, more precisely the phenol-formaldehyde resin can be converted to its melting point (up to 105). Heating) passes the treated mattress 16 through the sector 13. The resin is melted in a mass that concentrates at most on a joint knot while in contact with the encapsulated catalyst particles (see FIGS. 4-6). More specifically, the molten resin tends to concentrate as it moves by surface tension at the location of the joint knot or fiber-fiber junction of the fiber mass. Preferably, the resin is directed towards the seam knot of the structure by adding a small amount (1.5% to 5%) of an aqueous emulsion to the slurry based on the weight of the phenol-formaldehyde resin that changes the surface tension of the resin on the fiber. Enhances sliding. The presence of the surfactant ensures the formation of a thin layer of phenol-formaldehyde resin on the glass fibers, thereby reducing the brittleness of the glass fibers. In addition, if necessary, the flow characteristics of the novolak can be improved. For example, we alkoxylated some (about 5%) phenolic OH (with ethylene or propylene carbonate, or ethylene or propylene oxide), so that novolac tends to flow more easily along the glass fiber. I found this to be.

Furthermore, in contrast to the prior art methods using liquid resoles, it is desirable to apply the hardener and solid novolac in the form of a water slurry (not costly) sprayed into the glass at high speed. In doing this, the glass acts to some extent as a filter, and by itself, the particles tend to trap preferentially at the point of intersection only by physical means.

In sector 14, by bringing the temperature of the mattress to the melting temperature of the catalyst encapsulant (temperature> 105 ° C), a crosslinking reaction of the resin occurs, and the fibers are interconnected at the fiber-fiber junction, i. A layer of cured material to connect is formed to provide a compact structure 16 (see FIG. 6). Thus, at the intersections or joint knots between the fibers 8, ie where molten phenol-formaldehyde resin accumulates due to a decrease in its surface tension, the structure is only locally cured.

In this way, heat and acoustic barrier products (16), which are more resistant, easier to operate and do not cause harmful scattering of the cured resin fragments into the surrounding environment as compared to conventionally known products. ) Is possible (see FIG. 3).

In phenol-formaldehyde resins, the encapsulating agent disperses a suitable crosslinker or curing agent in the form of an encapsulated powder having the property of melting or degrading at temperatures higher than the melting temperature of the phenol-formaldehyde resin. The average particle diameter of the encapsulated curing agent is between 30 μm and 50 μm.

The high molecular weight novolak-type substituted phenolic resin incorporated into the setting-type resin composition of the present invention contains a bifunctional phenol mainly used in coating and construction techniques. It can be any one of the conventional substantially linear high molecular weight novolak-type substituted phenolic resin containing the phenol component which is a component. The high molecular weight novolak-type substituted phenolic resin (hereinafter referred to as "high molecular weight novolak-type resin") used in the present invention may be composed of a novolak-type recurring unit, The repeating units may all be linear or contain intervening or bridging groups composed of divalent hydrocarbon groups that appear alternately within a block of repeating units of novolac type. As used herein, “substantially straight” means that the molecular structure of the polymer is a straight structure, including straight or branched chains, but is substantially free of crosslinks (gelled moieties). The novolac type resins are described in US Pat. No. 4,342,852 and the like.

Typical high molecular weight novolak type substituted phenolic resins that can be used in the practice of the present invention are 70 to 100 mol%, preferably 80 to 100 mol% of at least one difunctional phenol represented by the following formula [I]: %, Particularly preferably a substantially straight novolak type repeating unit formed by condensation of the phenol component containing 90 to 100 mol%:

(R ¹ ) ₃ -Z (OH)-(R) ₂

[Wherein Z (OH) is phenol; Two of the three R ¹ are hydrogen atoms, the remaining R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom or a hydroxyl atom, preferably Is a substituent selected from alkyl groups having 1 to 8 carbon atoms, particularly preferably methyl, ethyl, isopropyl, sec-butyl, tert-butyl and octyl; Two R, which may be the same or different, represent a member selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a halogen atom and a hydroxyl group. Preferably, one of the two R's is a hydrogen atom, and the remaining R's are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. Trifunctional phenol of up to 30 mol%, preferably up to 20 mol%, particularly preferably up to 10 mol%, in which both R have a hydrogen atom and at least one aldehyde component represented by the formula [II] Phosphorus phenol is particularly preferred:

R ² -CHO

[Wherein, R ² is a hydrogen atom or a substituent selected from the group consisting of a methyl group and a halogenated methyl group, preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom].

The novolak-type repeating units constituting the high molecular weight novolak-type resin form a substantially straight chain structure in which the aforementioned hydroxyarylene units and alkylidene units are alternately arranged and interconnected. More specifically, the structure of the novolak type repeating unit constituting the high molecular weight novolak type resin is that the resin is linear when the phenol consists only of the bifunctional phenol represented by the above formula [I], Increasing the content of trifunctional phenols is such a structure that the resin sometimes has a branched structure. The ratio of the aldehyde component to the total phenol component in the novolak type repeating unit is usually in the range of 0.90 to 1 mole, preferably 0.93 to 1.0 mole per mole of the total phenol component. Typically, novolac type repeating units are free of methylol groups, but may contain very small amounts, such as 0.01 mole of methylol groups per mole of total phenol component.

In the phenol component in the novolak-type repeating unit constituting the high molecular weight novolak-type resin (B), the bifunctional phenol has the above chemical formula having two hydrogen atoms on the benzene nucleus active for substitution reaction. It is a phenol represented by [I]. More specifically, the difunctional phenol is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, in the ortho- or para-position to the hydroxyl group, Phenol of formula [I] having a halogen atom or a hydroxyl group. Examples include ortho- or para-isomers of alkylphenols (e.g. cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, sec-amylphenol, tert-amylphenol, hexylphenol, heptylphenol and octylphenol), halogenated phenols (eg fluorophenols, chlorophenols and bromophenols), and arylphenols (eg phenylphenols and tolylphenols). In addition, examples of the bifunctional phenol represented by the above formula [I] include 2,3-xylenol, 3,4-xylenol, 2,5-xylenol, 2,3-diethylphenol, 3,4-diethylphenol, 2,5-diethylphenol, 2,3-diisopropylphenol, 3,4-diisopropylphenol, 2,5-diisopropylphenol, 2,3-dichlorophenol, 3,4-dichlorophenol, 2,5-dichlorophenol, 2-methyl-3-phenylphenol, 3-methyl-4-phenylphenol and 2-methyl-5-phenylphenol are mentioned. The bifunctional phenol component in the novolak type repeating unit constituting the high molecular weight novolak type resin (B) is at least one component selected from the above-described phenols, and may be a mixture of two or more of the above phenols.

The trifunctional phenol which may be contained in the novolak type repeating unit constituting the high molecular weight novolak type resin (B) is a phenol having three hydrogen atoms active on the benzene nucleus on the substitution reaction, Examples of such trifunctional phenols include meta-substituted phenols and 3,5-substituted phenols. Examples of the substituent which the trifunctional phenol has in the meta-position or the 3,5-position include an alkyl group, a halogen atom and a hydroxyl group. Among the trifunctional phenols, trifunctional phenols represented by the following general formula [III] are preferable:

[R] ₂

[Wherein R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom or a hydroxyl group, and two Rs may be the same or different].

Specific examples include phenol, meta-substituted phenol (e.g. m-cresol, m-ethylphenol, mn-propylphenol, m-isopropylphenol, mn-butylphenol, m-sec-butylphenol, m-tert- Butylphenol, mn-amylphenol, m-sec-amylphenol, m-tert-amylphenol, m-hexylphenol, m-heptylphenol, m-octylphenol, m-fluorophenol, m-chlorophenol, m- Bromophenol and resorcinol), and 3,5-di-substituted phenols such as 3,5-xylenol, 3,5-diethylphenol, 3,5-di Isopropylphenol, 3,5-di-sec-butylphenol, 3,5-di-tert-butylphenol, 3,5-di-sec-amylphenol, 3,5-di-tert-amylphenol, 3, 5-dihexylphenol, 3,5-diheptylphenol, 3,5-dioctylphenol, 3,5-dichlorophenol, 3,5-difluorophenol, 3,5-dibromophenol and 3,5 Diiodophenol). In the trifunctional phenol, one of two R groups is a hydrogen atom, the other R group is a functional group selected from the group consisting of a hydrogen atom, an alkyl group having one or eight carbon atoms, and a chlorine atom Particularly preferred are trifunctional phenols represented by the formula [III]; Particular preference is given to phenols in which one of the two R groups is a hydrogen atom and the other R group is a hydrogen atom, a methyl group, isopropyl group, sec-butyl group, tert-butyl group or octyl group.

The aldehyde component in the novolak-type repeating unit constituting the high molecular weight novolak-type resin (B) is an aldehyde represented by the formula [II]. Examples of the aldehydes include formaldehyde, acetaldehyde, monochloroacetaldehyde, dichloroacetaldehyde and trichloroacetaldehyde. Of the above aldehydes, formaldehyde and acetaldehyde are preferable, and formaldehyde is particularly preferable. The aldehyde component is present in the high molecular weight novolak type substituted phenolic resin in the form of an alkylidene group represented by the formula [V].

In the present invention, as pointed out earlier in the present specification, a novolak type repeating unit (a) composed of the above-described phenol and aldehyde components is an intervening or crosslinking group consisting of a divalent hydrocarbon group (hereinafter referred to as an "extender component unit"). "), Which alternately appear in a block of repeating units of the novolak type. This type of resin is characterized by a somewhat lower molecular weight, novolak type repeating unit blocks (a) having chain extender constituent units (b) alternately aligned and connected to each other and increasing the molecular weight of the resin, The novolak type repeating unit block (a) is characterized by being bonded to the terminal of the resin molecule. The simplest structure of this type of resin comprises a two-molecule novolak-type repeating unit block (a) connected to each other via one molecule of chain extender component units (b), followed by the simplest structure described above. A trimolecular novolac type repeating unit block (a) and a two-molecule chain extender component unit (b), which are alternately arranged and connected to each other. Furthermore, mention may be made of structures comprising similarly arranged four-molecule novolak-type repeating unit blocks (a) and three-molecule chain extender component units (b) that are alternately aligned and interconnected, alternately arranged and mutually Mention may be made of structures comprising repeating unit blocks (a) of the novolak type of linked n molecules and chain extender component units (b) of (n-1) molecules.

If the molecular weight of these chain extender component units (b) is too large, the melting point of the high molecular weight novolak-type substituted phenolic resin formed is reduced but the flexibility is increased. Therefore, even when such a resin is incorporated into a setting type resin, it is hard to obtain a curable resin composition having excellent heat resistance and mechanical properties. Accordingly, the molecular weight of the chain extender component unit (b) is preferably from 14 to 200, particularly preferably from 14 to 170.

The high molecular weight novolac resin used in the present invention is prepared by a process comprising the following steps:

(i) a phenol composed mainly of at least one difunctional phenol represented by the formula [I], or (ii) a phenol composed mainly of the bifunctional phenol and an aldehyde represented by the following formula [II]. Substituted phenolic resin of the rock type type is reacted under acidic catalyst until the number average molecular weight of the final phenolic substituted phenolic resin reaches a desired level, and at least 70 mol% in the final novolak type substituted phenolic resin. Allowing a phenolic component to be occupied by the bifunctional phenol.

According to a preferred embodiment of the invention, the crosslinking agent comprises a formaldehyde derivative, preferably hexamethylene tetramine (hexamine), the grains of which have a higher melting point or decomposition temperature than the phenol-formaldehyde resin and It is encapsulated in the coating material. Instead of hexamine, the following crosslinking agents or curing agents may also be used, all of which are material paraformaldehyde, hexamethoxymelamine, trimellitic anhydride, epoxy resin, phenolic resolic resin, melamine resin, pre-reacted epoxy It is coated by high fusion encapsulation such as polyester resin.

The encapsulant is preferably a copolymer of propylene-ethylene-butadiene type.

The encapsulated curing agent is preferably contained in an amount of about 3 to 12% by weight relative to the phenol-formaldehyde resin, and usually has a boiling point of 102 ° C or higher.

In addition, the use of encapsulated hexamethylenetetramine or any other aforementioned encapsulant can be extended to so-called "pultrusions" (ie, drawing products) of phenol-formaldehyde resins. Examples include grate and draw pieces used in "off-shore" platforms. It is evident that the invention can be refined as discussed and illustrated above to form variations of the invention while remaining within the scope of the following claims. Thus, for example, glass fibers may be replaced with any other inorganic fibers of the type corresponding to the purpose of the present invention.

For maximum efficiency and effectiveness, the form of particulates, such as novolacs in powder form (the term “novolac” is understood to refer to any thermoset resin included in the present invention) and encapsulated curing agents are uniformly The novolacs must be adequately and fully catalyzed when heated together and melted in the intended use of the present invention to be mixed together. If desired, small amounts of flow modifiers such as fumed silica, alumina or calcium stearate can be added to ensure proper dispersion or prevent premature agglomeration, sintering or fractionation of the particles.

In applications such as cast powders, uniform and intimate contact between the novolak powder and the hardener is easily achieved if the components are thoroughly mixed in advance. However, in applications such as fiberglass bonding, the dilute phase dispersion of the two powders allows the novolac and encapsulated curing agent to be significantly physically separated from each other and not in close enough contact to promote efficient curing. In such cases, there are several ways to improve the compound or application technique to significantly increase and preserve the contact between the novolac and the curing agent. This adhesion strength need not necessarily be strong, but still the adhesion must be strong enough to preserve and maintain contact after any mechanical process involving the dispersion of the particles.

In addition, due consideration should be given to the relative particle size of the novolac and encapsulated curing agent, whereby the number of curing agent particles and the total mass of each adhering to the individual novolak particles, on average, are preferably in the required weight ratios indicated in the overall formulation. Try to respond closely. Since the weight ratio of novolak to hardener is usually about 9: 1, this can be most practically done by making harder particles on average much smaller than novolak particles.

In one embodiment, contact may be by direct attachment between the novolac and the encapsulating polymer. For example, the polyamides used to encapsulate the curing agent can be made by known methods that utilize the reaction of diamines or triamines (eg ethylenediamine or diethylenetriamine) with dibasic acids, fatty acids or dimer acids. These types of polyamides are commonly used in a wide variety of adhesive applications. By selection of appropriate acids and amines, polyamides can vary from very high tack at a certain high temperature, while still being a tacky and rather high melting point at room temperature. In addition, the degree of adhesion may depend on the dry composition of the temperature polyamide, and in particular may reflect the glass transition properties of the polyamide. The glass transition point represents the point at which the polymer changes from a hard glass state to a rubbery or tacky state.

If the polyamide has a slight tack, the novolak is made whenever the hardener particles are in uniform contact with the encapsulated novolac in a suitable device, such as a fluid bed or flat belt, which can be mixed or sprayed onto the dispersed novolac particles. Can be combined with the particles. This contact is carried out at a temperature where the encapsulant surface can be somewhat tacky but still below the novolak's melting point or glass transition point.

After contacting and attaching, it is important that there is no overall agglomeration or fusion which then decreases the tack and subsequently hardens the mixture into agglomerates. This can most easily be achieved by simply chilling the mixture in a fluidized or separated state at temperatures below the glass transition point of the polyamide. For example, if the melting point or glass transition point of novolac is 75 ° C., the polyamide may be selected to exhibit a glass transition property of approximately 60 ° C. When contacted in the 60-75 ° C. range, the particles will adhere due to the tacky or rubbery state of the polyamide, but if cooled well below 60 ° C., the stickiness is avoided, but still the glass transition point of the polyamide It is high enough to prevent clumping during normal storage of the mixture prior to use. Any residual tack in the final product can be further minimized by inserting inert inorganic fillers such as talc, fumed silica, and the like into the final product.

In addition, the solvent used to encapsulate the curing agent is completely removed from the polyamide, so that when the polyamide is characterized by some tack and subsequently contacted with novolac, bonding will occur. The remaining solvent can then be removed in a separate step using vacuum conditions to avoid temperatures at which novolaks can melt. Fumed silica or other suitable additives may be further blended into the final step to effectively adhere to the residual tacky surface to avoid agglomeration or agglomeration of the particles during product storage or to enhance free flow of the particles.

In another embodiment, the third binding component can be added to the novolak and encapsulated curing agent mixture by a uniform dispersion method such that weak but still sufficient bonding occurs between the particles. The level of such binder is usually 5% or less of the total formulation. Examples of such third binder components are polyvinyl acetate emulsions, lignin, polyesters and the like.

The present invention has been described in terms of specific embodiments thereof, and numerous alternatives, improvements, and variations will be apparent to those skilled in the art. Accordingly, the preferred embodiments described herein above are exemplary and not intended to be limiting. Various changes may be made without departing from the true spirit and overall scope of the invention as set forth above and defined in the claims.

Claims (36)

A water-insoluble thermoplastic having a fine particle thermosetting phenol-aldehyde resin and a fine particle curing agent for the thermosetting resin, wherein the curing agent has a softening point higher than (1) the melting point of the thermosetting resin and (2) the temperature at which the thermosetting resin flows on the solid substrate. Encapsulated in a resin, the encapsulating thermoplastic resin can also be dissolved in the thermosetting resin by heating, and the curing agent is capable of curing the thermosetting resin when the encapsulating thermoplastic resin is melted and released. Thermosetting resin composition. The thermosetting resin composition of claim 1, wherein the encapsulated curing agent comprises particles dispersed almost uniformly throughout the thermosetting resin. The thermosetting resin composition according to claim 1, wherein the encapsulated curing agent is an emulsion-type microcapsule curing agent formed from an emulsion containing the water-insoluble thermoplastic resin and the curing agent as a particulate material. The thermosetting resin composition according to claim 1, wherein an average particle diameter of the encapsulated curing agent is in a range of 30 μm to 50 μm. The thermosetting resin composition according to claim 1, wherein the average particle diameter of the particulate thermosetting resin is in the range of 30 µm to 50 µm. The thermosetting resin composition of claim 1, wherein the thermoplastic encapsulating agent is a propylene / ethylene / butadiene block copolymer, polyamide, melamine, epoxy, polystyrene styrene acrylic, glycid and acrylic copolymer. The method of claim 1, wherein the curing agent is hexamethylenetetramine, paraformaldehyde, hexamethoxymelamine, trimellitic anhydride, epoxy resin, phenolic resolic resin, melamine resin, pre-reacted epoxy- It is a polyester resin, meta-triphenyl phosphine (mela-tripphenyl phosphine) and a quaternary ammonium salt (ammoniumsall) thermosetting resin composition. The thermosetting resin composition according to claim 1, comprising a prepreg containing the thermosetting resin and the encapsulated curing agent. The thermosetting resin composition according to claim 1, wherein the phenol-aldehyde resin is novolac. The thermosetting resin composition of claim 1, wherein the phenol-aldehyde resin is a novolac having a molecular weight of about 300-2000. The phenol-aldehyde resin according to claim 1, wherein the phenol-aldehyde resin is a novolac formed by condensation of a phenolic component, wherein the phenolic component is a formula R-CHO wherein R represents a hydrogen atom, a methyl group or a halogenated methyl group. A thermosetting resin composition comprising at least one bifunctional phenol having at least one aldehyde component. The thermosetting resin composition according to claim 11, wherein the phenol-aldehyde resin is a phenol-formaldehyde resin. The thermosetting resin composition of claim 1, wherein at least one particle of the particulate encapsulated curing agent is attached to at least one particle of the thermosetting resin. A curing agent for a thermosetting phenol-aldehyde resin, wherein the curing agent is encapsulated in a water-insoluble thermoplastic resin having a softening point higher than (1) the melting point of the thermosetting resin and (2) the temperature at which the thermosetting resin flows on a solid substrate, and the encapsulated thermoplastic A resin can also be dissolved in the thermosetting resin by heating, and the curing agent can cure the thermosetting resin when the encapsulating thermoplastic resin melts and is released. 15. The curing agent of claim 14 in the form of particulates. The curing agent of claim 15, wherein the curing agent comprises particles having an average particle diameter in the range of 30 μm to 50 μm. The curing agent according to claim 14, wherein the encapsulating curing agent is an emulsion-type microcapsule curing agent formed from an emulsion containing the water-insoluble thermoplastic resin and the curing agent as a particulate material. A method of curing a thermosetting phenol-aldehyde resin, the method comprising contacting the resin with the curing agent of claim 14 and heating the formed formulation to a temperature above the melting point of the encapsulating thermoplastic resin. The method of claim 18, wherein the thermosetting resin is in particulate form. 19. The method of claim 18, wherein the curing agent comprises particles dispersed substantially uniformly throughout the thermosetting resin. The method of claim 18, wherein the curing agent comprises particles having an average particle diameter in the range of 30 μm to 50 μm. The method of claim 18, wherein the average particle diameter of the particulate thermosetting resin is in the range of 30 μm to 200 μm. The method of claim 19, wherein at least one particle of the particulate encapsulated curing agent is attached to at least one particle of the thermosetting resin. 19. The method of claim 18, wherein said blend is cured in the presence of a substrate that is substantially chemically inert to said thermosetting resin and said hardener. The method of claim 24, wherein the result is a composite material comprising the cured thermosetting resin and the substrate. The method of claim 25, wherein the composite comprises the substrate substantially surrounded by a matrix comprising the thermoset resin. The method of claim 25, wherein the substrate is fiberglass. A process for producing a material consisting of interconnected inorganic fiber masses, the method comprising: connecting fibers at a localized fiber-fiber junction or knot by distributing particles of crosslinker and binder material in the fiber mass; And activating the binder material and the crosslinker by heating the binder material and the crosslinker to their respective melting points, wherein the melting point of the crosslinker is higher than the binder material. 29. The process of claim 28 wherein said binding material and said crosslinker are in the form of a powder. 29. The process of claim 28, wherein said binding material is in the form of an aqueous dispersion (slurry) of phenolic resin. 29. The process of claim 28, wherein said binding material is comprised of a phenolic resin and said crosslinker is comprised of a derivative of formaldehyde coated with a film of a material having a higher melting point than the phenolic resin. 32. The method according to claim 31, wherein the formaldehyde derivative is composed of hexamethylenetetramine powder encapsulated with a coating of a material having a higher melting point than the phenolic resin, and the coating comprises a block copolymer of propylene-ethylene-butylene type. Process. 33. The process of claim 32, wherein said binding material is comprised of a phenolic resin and said crosslinker is selected from one or more of the following compounds: paraformaldehyde, hexamethoxymelamine, trimellitic anhydride, epoxy resin, resol- Type phenolic resin, melamine resin, pre-reacted epoxy-polyester resin A first furnace for melting a glass inorganic material, a die connected to the furnace to obtain a flow of molten glass, a plurality of glass fibers delivered through the opening in the spinner when receiving and rotating the flow A rotatable spinner disposed to direct heat, a flame deflector disposed in the fiber path to direct heat to the fiber delivered onto the conveyor belt disposed below the fiber, and before the fiber is transferred onto the conveyor belt. And means for adjoining the fibers to disperse the binding material and the powdered crosslinker simultaneously in the mass formed by the fibers. 35. The apparatus of claim 34, further comprising a second furnace for receiving the fibers on a conveyor belt and for heating the fibers to below the melting point temperature of each of the bonding material and the crosslinker. 36. The system of claim 35, wherein the second furnace comprises two compartments through which the fiber passes, each compartment being adjusted to operate at a different temperature, and the second compartment having an operating temperature higher than the operating temperature of the first compartment. Device.