JP5577401B2 - Method for producing flame retardant fiber material - Google Patents

Description

  The present invention relates to a method for producing a flame-retardant fiber material used for interior materials of automobiles and buildings.

Conventionally, ammonium polyphosphate has been used for this kind of flame-retardant fiber material, but since the ammonium polyphosphate is easily soluble in water, the product made of the flame-retardant fiber material has poor water resistance, and the product Is affected by moisture and the like, there is a problem that the ammonium polyphosphate is eluted into the water, and the flame retardant effect is lost.
Therefore, a melamine resin-coated ammonium polyphosphate in which the surface of the ammonium polyphosphate is coated with a melamine resin or the like is provided.

JP 2001-294212 A

  Although the melamine resin-coated ammonium polyphosphate prevents the ammonium polyphosphate from coming into direct contact with water by the melamine resin coating, it is difficult to completely cover the ammonium polyphosphate surface with the melamine resin. When fiber materials containing ammonium polyphosphate are heat-press molded, there is a risk that the melamine coating may be broken by the molding pressure. Thus, if melamine resin-coated ammonium polyphosphate with a defective portion in the melamine coating is used, product storage There is a problem in that ammonium polyphosphate that has come out from the defective portion of the melamine coating is deposited on the surface of the product and whitens, thereby deteriorating the appearance.

As a means for the present invention is to solve the conventional problems, and step 1 of impregnating the phenolic resin to the fiber material, phenolic resin precondensate to the fiber material a surface impregnated with the phenolic resin is added A method for producing a flame-retardant fiber material comprising the steps 2 and 2 of applying and drying an aqueous dispersion of melamine polyphosphate powder is applied. Since the above melamine polyphosphate is almost insoluble in water, it is not necessary to apply a resin coating. Conventionally, it has been disclosed to use mainly as a flame retardant for molding resins, but examples added to fiber materials are disclosed. It has not been.

For the above fiber material which imparts formability, but phenol resin is impregnated, using the up notated phenol resins, good flame retardancy in cooperation with the melamine polyphosphate it is exhibited. The phenolic resin is preferably sulfomethylated and / or sulfimethylated.

When the melamine polyphosphate powder is simply mixed with an untreated fiber material and then impregnated with a phenolic resin, it is extremely difficult to uniformly mix the melamine polyphosphate powder into the fiber material, and flame retardancy is difficult. The melamine polyphosphate powder then flows out from the fiber material and is separated when it is impregnated with a phenolic resin.
The phenolic resin solution to impregnate the fiber material untreated, to impregnate the phenolic resin solution after allowed to disperse the polyphosphoric acid melamine powder, when impregnating the phenolic resin solution to the fiber material In addition, the melamine polyphosphate powder may be separated from the phenolic resin liquid, or the melamine polyphosphate powder may be discharged to the back side of the fiber material together with the phenolic resin liquid. It is easy to become.

The aqueous dispersion of the melamine polyphosphate powder is added with a phenol-based resin initial condensate to slightly increase the viscosity so as to uniformly disperse the melamine polyphosphate powder. The melamine polyphosphate in the aqueous dispersion It is desirable to ensure that the powder does not escape to the back side of the fiber material.
The desirable ratio of the phenol resin initial condensate and the polyphosphate melamine powder in the aqueous dispersion of the melamine polyphosphate powder is: phenol resin initial condensate: melamine polyphosphate powder = 5: 95 to 50:50 mass ratio (solid The desirable viscosity of the aqueous dispersion of melamine polyphosphate powder is in the range of 50 to 1000 cps at 23 ° C. The phenolic resin initial condensate is preferably an initial condensate of a phenolic resin that is sulfomethylated and / or sulfimethylated.

  The flame-retardant fiber material of the present invention exhibits high flame resistance with water resistance and durability, and is particularly useful as an automotive material or a building material.

Explanatory drawing which shows the manufacturing method of a flame-retardant fiber material Explanatory drawing which shows the manufacturing method of a flame-retardant fiber material

An embodiment of the present invention will be described in detail below.
[Fiber material]
The fiber material used in the present invention is provided mainly in the form of a sheet.
Examples of fibers used in the fiber material include polyester fibers, polyamide fibers, acrylic fibers, urethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers, polyethylene fibers, polypropylene fibers, and other polyolefin fibers, aramid fibers, etc. Synthetic fibers, wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, silk thread, cotton, gama fiber, pulp, cotton, palm fiber, hemp fiber, bamboo fiber, kenaf fiber, etc., starch fiber, Biodegradable fiber such as polylactic acid fiber, chitin chitosan fiber, cellulosic artificial fiber such as rayon (human silk, sufu), polynosic, cupra, acetate, triacetate, glass fiber, carbon fiber, ceramic fiber, asbestos fiber, etc. Of inorganic fibers and fiber products using these fibers It is obtained reproduction fibers by fibrillating crap. These fibers are used alone or in combination of two or more. The fineness of the synthetic fiber and inorganic fiber is usually 0.01 to 30 dtex, and the average fiber diameter of the natural plant fiber is usually 0.01 to 1.0 mm.
Further desirable fibers include hollow fibers.

The hollow fiber is made of polyester such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyamide such as nylon 6, nylon 66, nylon 46 or nylon 10, polyethylene, polypropylene or the like. It consists of thermoplastic resins such as polyolefin, acrylic, urethane, polyvinyl chloride, polyvinylidene chloride, and acetate. These hollow fibers are used alone or in combination of two or more.
The hollow fiber is produced by a known method such as a melt spinning method or preferentially eluting and removing one component of a fiber obtained by composite spinning of two kinds of polymers.
The hollow fiber has one or two or more hollow tube portions having a circular cross section, an elliptical shape, etc., and the hollow ratio is 5% to 70%, preferably 10% to 50%. The hollow ratio is the ratio of the cross-sectional area of the hollow tube portion to the cross-sectional area of the fiber.
The fineness of the hollow fiber is in the range of 1 dtex to 50 dtex, and desirably in the range of 2 dtex to 20 dtex.
When the hollow fiber is used by mixing with other fibers, the hollow fiber is desirably mixed by 10% by mass or more.
When the hollow fiber is used, the rigidity of the fiber sheet is improved by the tube effect.

Further, in the present invention, a low melting point fiber having a melting point of 180 ° C. or less may be used. Examples of the low melting point fiber include polyolefin fibers such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl chloride fiber, polyurethane fiber, polyester fiber, and polyester copolymer fiber. , A polyamide fiber, a polyamide copolymer fiber, or a core-sheath type composite fiber having a normal fiber having a melting point of 180 ° C. or more as a core and the low-melting fiber as a sheath. These low melting point fibers are used alone or in combination of two or more.
The fineness of the low-melting fiber is in the range of 0.1 dtex to 60 dtex.
The low-melting fiber is usually mixed with 1 to 50% by mass in the fiber.

  The fiber material is usually provided as a nonwoven fabric or a knitted fabric as a sheet. As the nonwoven fabric, a needle punched nonwoven fabric, a resin nonwoven fabric using a synthetic resin binder described later, the above-mentioned low melting point fiber alone or a mixed fiber web in which the above low melting point fiber is mixed with a normal fiber, or a needle punched nonwoven fabric are heat-treated to form a fiber. There are fused non-woven fabrics and the like.

[Melamine polyphosphate]
Among the melamine derivatives, melamine polyphosphate powder is a useful melamine derivative that imparts high flame retardancy to the above fiber material and is easily available, and is commercially available.

[ Phenolic resin]
The fiber material of the present invention is impregnated with a phenolic resin, if desired, in order to impart moldability and rigidity .

Upper Symbol phenolic resin has affinity with the melamine polyphosphate, excellent flame retardancy in coordination applied to the fiber material.

[Phenolic resin]
The phenolic resin is obtained by condensing a phenolic compound and an aldehyde and / or an aldehyde donor. The phenolic resin is desirably sulfomethylated and / or sulfimethylated to impart water solubility.
The phenolic resin is impregnated into the fiber material as an aqueous solution of an initial condensate (initial condensate liquid). The initial condensate liquid is optionally methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, methyl amyl alcohol. Alcohols such as 2-ethylbutanol, n-heptanol, n-octanol, trimethylnonyl alcohol, cyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, abiethyl alcohol, diacetone alcohol, acetone, methylacetone, Methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, diethyl ketone, di-n-propyl ketone, diisobutyl keto , Ketones such as acetonylacetone, methyl oxide, cyclohexanone, methylcyclohexanone, acetophenone, camphor, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, ethylene Glycol ethers such as glycol monoethyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether; esters of the above glycols such as ethylene glycol diacetate and diethylene glycol monoethyl ether acetate; -Ethers such as dioxane, diethyl ether Lube, diethyl carbitol, ethyl lactate, isopropyl lactate, diglycol diacetate, a water-soluble organic solvent such as dimethylformamide may be used.

(Phenolic compounds)
The phenolic compound used in the phenolic resin may be a monohydric phenol, a polyhydric phenol, or a mixture of a monohydric phenol and a polyhydric phenol. When only monohydric phenol is used, formaldehyde is easily released during and after curing. Therefore, polyhydric phenol or a mixture of monohydric phenol and polyhydric phenol is preferably used.

(Monohydric phenol)
Examples of the monohydric phenol include phenol, alkylphenols such as o-cresol, m-cresol, p-cresol, ethylphenol, isopropylphenol, xylenol, 3,5-xylenol, butylphenol, t-butylphenol, and nonylphenol, and o-fluoro. Phenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodo Phenol, p-iodophenol, o-aminophenol, m-aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitro Examples include monohydric phenol substitutes such as enol and 2,4,6-trinitrophenol, and polycyclic monohydric phenols such as naphthol. These monohydric phenols may be used alone or in combination of two or more. I can do it.

(Polyhydric phenol)
Examples of the polyhydric phenol include resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol, dihydroxynaphthalene, and the like. These polyhydric phenols are used alone or in combination of two or more. can do. Among the polyhydric phenols, preferred is resorcin or alkylresorcin, and particularly preferred is alkylresorcin, which has a higher reaction rate with aldehyde than resorcin.

Examples of the alkyl resorcin include, for example, 5-methyl resorcin, 5-ethyl resorcin, 5-propyl resorcin, 5-n-butyl resorcin, 4,5-dimethyl resorcin, 2,5-dimethyl resorcin, 4,5-diethyl resorcin, 2 , 5-diethyl resorcin, 4,5-dipropyl resorcin, 2,5-dipropyl resorcin, 4-methyl-5-ethyl resorcin, 2-methyl-5-ethyl resorcin, 2-methyl-5-propyl resorcin, 2 , 4,5-trimethylresorcin, 2,4,5-triethylresorcin and the like.
A polyhydric phenol mixture obtained by dry distillation of an Estonia oil shale is inexpensive and contains a large amount of highly reactive various alkylresorcins in addition to 5-methylresorcin. Therefore, it is a particularly preferable polyhydric phenol raw material in the present invention.

  In this embodiment, the phenolic compound is condensed with an aldehyde and / or an aldehyde donor (aldehydes), and the aldehyde donor means a compound or a mixture thereof that generates and provides an aldehyde when decomposed. Examples of such aldehyde include formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. Examples of aldehyde donors include paraformaldehyde, trioxane, hexamethylenetetramine, tetraoxymethylene and the like.

  As described above, in order to improve the stability of the water-soluble phenolic resin, it is desirable to sulfomethylate and / or sulfmethylate the phenolic resin.

(Sulfomethylating agent)
Examples of sulfomethylating agents that can be used to improve the stability of water-soluble phenolic resins include sulfite, bisulfite or metabisulfite, and alkali metals or quaternary amines or quaternary compounds such as trimethylamine or benzyltrimethylammonium. Examples thereof include water-soluble sulfites obtained by reacting with secondary ammonium and aldehyde adducts obtained by reacting these water-soluble sulfites with aldehydes.
Examples of the aldehyde adduct include formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. An aldehyde adduct composed of formaldehyde and sulfite is, for example, hydroxymethanesulfonate.

(Sulfimethylating agent)
Sulfimethylating agents that can be used to improve the stability of water-soluble phenolic resins include aliphatic and aromatic aldehyde alkali metal sulfoxylates such as formaldehyde sodium sulfoxylate (Longalite) and benzaldehyde sodium sulfoxylate. Examples thereof include alkali metals such as sodium hydrosulfite and magnesium hydrosulfite, hydrosulfites (dithionates) of alkaline earth metals, and hydroxyalkanesulfinates such as hydroxymethanesulfinate.

  When producing the phenolic resin, for example, hydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid, oxalic acid, formic acid, acetic acid, butyric acid, benzenesulfonic acid, phenolsulfonic acid, paratoluenesulfonic acid, naphthalene-α- Inorganic or organic acids such as sulfonic acid, naphthalene-β-sulfonic acid, esters of organic acids such as dimethyl oxalate, acid anhydrides such as maleic anhydride, phthalic anhydride, ammonium chloride, ammonium sulfate, ammonium nitrate, oxalic acid Ammonium salts such as ammonium, ammonium acetate, ammonium phosphate, ammonium thiocyanate, ammonium imide sulfonate, monochloroacetic acid or its sodium salt, organic halides such as α, α'-dichlorohydrin, triethanolamine hydrochloride, aniline hydrochloride Hydrochloride of amines such as Urea adducts such as urea salicylate adduct, urea stearate adduct, urea heptanoate adduct, acidic substances such as N-trimethyltaurine, zinc chloride, ferric chloride, ammonia, amines, sodium hydroxide, potassium hydroxide, water Alkali metals such as barium oxide and calcium hydroxide, hydroxides of alkaline earth metals, oxides of alkaline earth metals such as lime, weak acid salts of alkali metals such as sodium carbonate, sodium sulfite, sodium acetate, sodium phosphate, etc. These alkaline substances may be mixed as a catalyst or a pH adjuster.

[Production of phenolic resins]
The phenolic resin (initial condensate) can be produced by a conventional method. Specifically, (a) a method of condensing monohydric phenol and / or polyhydric phenol and aldehydes, (b) monohydric A method of condensing an initial condensate obtained by condensing a phenol and an aldehyde and / or an initial condensate obtained by condensing a polyhydric phenol and an aldehyde with a monohydric phenol and / or a polyhydric phenol; A method of condensing a monohydric phenol and / or a polyhydric phenol with an initial condensate obtained by condensing a monohydric phenol, a polyhydric phenol and an aldehyde, and (d) an initial condensation of condensing a monohydric phenol and an aldehyde. A product and an initial condensate obtained by condensing a polyhydric phenol and an aldehyde, (e) an initial condensate obtained by condensing a monohydric phenol and an aldehyde And a spare / or precondensate obtained by condensation of polyhydric phenols with aldehydes, monohydric phenol and polyhydric phenol with aldehydes and can be produced by a method in which condensation of the initial condensation product by condensation of.

In this embodiment, a desirable phenol-based resin is a phenol-alkylresorcin cocondensate. The phenol-alkylresorcin cocondensate is stable in an aqueous solution of the cocondensate (initial cocondensate) and is stored for a long time at room temperature as compared to a condensate (initial condensate) composed only of phenol. There is an advantage that you can. The resin-impregnated fiber material obtained by impregnating the fiber material with the aqueous solution and pre-curing has good stability, and the moldability is not lost even if the fiber material is stored for a long period of time. Furthermore, since alkylresorcin is highly reactive with aldehydes and captures and reacts with free aldehydes, it also has the advantage of reducing the amount of free aldehydes in the resin.
A desirable method for producing the above-mentioned phenol-alkyl resorcin cocondensate is to first react phenol with an aldehyde to produce a phenol-based resin initial condensate, and then add alkyl resorcin to the phenol-based resin initial condensate. In other words, it is a method of reacting by adding an aldehyde.

  For example, in the above-mentioned condensation of (a) monohydric phenol and / or polyhydric phenol and aldehydes, usually 0.2 to 3 mol of aldehydes per mol of monohydric phenol and aldehydes per mol of polyhydric phenol 0.1 to 0.8 mol of the compound and, if necessary, a solvent and a third component are added, and the mixture is heated and reacted at a liquid temperature of 55 to 100 ° C. for 8 to 20 hours. At this time, the whole amount of aldehydes may be added at the start of the reaction, or may be added in portions or continuously.

When the above-mentioned phenolic resin initial condensate is sulfomethylated and / or sulfimethylated, a sulfomethylating agent and / or a sulfimethylating agent may be added to the initial condensate at an optional stage to obtain a phenolic compound and / or initial condensate. Is sulfomethylated and / or sulfimethylated.
The addition of the sulfomethylating agent and / or the sulfymethylating agent may be performed at any stage before, during or after the condensation reaction.

  The total amount of the sulfomethylating agent and / or sulfmethylating agent is usually 0.001 to 1.5 mol with respect to 1 mol of the phenol compound. When it is 0.001 mol or less, the hydrophilicity of the phenolic resin is not sufficient, and when it is 1.5 mol or more, the water resistance of the phenolic resin is deteriorated. In order to satisfactorily maintain performance such as curability of the initial condensate to be produced and physical properties of the resin after curing, the content is preferably about 0.01 to 0.8 mol.

  The sulfomethylating agent and / or sulfimethylating agent added to sulfomethylate and / or sulfmethylate the initial condensate reacts with the methylol group of the initial condensate and / or the aromatic ring of the initial condensate, A sulfomethyl group and / or a sulfimethyl group is introduced into the initial condensate.

  The aqueous solution of the precondensate of the phenolic resin thus sulfomethylated and / or sulfimethylated is stable in a wide range from acidic (pH 1.0) to alkaline, and in any of acidic, neutral and alkaline regions. Can be cured. In particular, when cured on the acidic side, the remaining methylol groups are reduced and the cured product is not decomposed to generate formaldehyde. In addition, when a phenol-based resin that is sulfomethylated and / or sulfimethylated is used, a fiber material having higher flame retardancy than that when a phenol-based resin that is not sulfomethylated and / or sulfmethylated is used.

  Furthermore, as the phenolic resin, if desired, urea, thiourea, melamine, thiomelamine, dicyandiamine, guanidine, guanamine, acetoguanamine, benzoguanamine, 2,6 diamino-1,3-diamine amino resin monomer Alternatively, an initial condensate composed of the amino resin monomer may be added to cause co-condensation with the phenolic compound and / or the initial condensate.

In addition, a curing agent such as an aldehyde and / or an aldehyde donor or an alkylolated triazone derivative may be added to and mixed with the initial condensate of the phenolic resin (including the initial cocondensate).
As the aldehyde and / or aldehyde donor, the same aldehyde and / or aldehyde donor used for the production of the initial condensate (initial cocondensate) of the phenolic resin is used, and the alkylolated triazone derivative is used. Is obtained by the reaction of a urea compound, an amine, and an aldehyde and / or aldehyde donor. Examples of the urea compounds used in the production of alkylolated triazone derivatives include alkylureas such as urea, thiourea and methylurea, alkylthioureas such as methylthiourea, phenylurea, naphthylurea, halogenated phenylurea and nitrated alkyl. Examples thereof include urea alone or a mixture of two or more. A particularly desirable urea compound is urea or thiourea. In addition, amines such as aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and amylamine, amines such as benzylamine, furfurylamine, ethanolamine, ethylenediamine, hexamethylenediamine and hexamethylenetetramine, as well as ammonia. These are used alone or as a mixture of two or more. The aldehyde and / or aldehyde donor used in the production of the alkylolated triazone derivative is the same as the aldehyde and / or aldehyde donor used in the production of the initial condensate of the phenolic resin.

  For synthesizing the alkylolated triazone derivative, usually 0.1 to 1.2 mol of amines and / or ammonia and 1.5 to 4 of aldehyde and / or aldehyde donor are used with respect to 1 mol of urea compound. The reaction is carried out at a rate of 0.0 mol. In the above reaction, the order of addition is arbitrary, but as a preferred reaction method, the required amount of aldehyde and / or aldehyde donor is first charged into the reactor, and the amines are usually kept at a temperature of 60 ° C. or lower. In addition, there is a method in which a required amount of ammonia is gradually added, a required amount of a urea compound is further added, and the reaction is performed by stirring and heating at 80 to 90 ° C. for 2 to 3 hours. As the aldehyde and / or aldehyde donor, 37% formalin is usually used, but a part thereof may be replaced with paraformaldehyde in order to increase the concentration of the reaction product. When hexamethylenetetramine is used, a reaction product having a higher solid content can be obtained. The reaction of a urea compound, an amine and / or ammonia, and an aldehyde and / or aldehyde donor is usually carried out in an aqueous solution, but methanol, ethanol, isopropanol, n-butanol, Alcohols such as ethylene glycol and diethylene glycol may be used alone or as a mixture of two or more kinds, and water-soluble organic solvents such as ketones such as acetone and methyl ethyl ketone may be used alone or in combination of two or more kinds. . The addition amount of the curing agent is 10 to 100 parts by mass with respect to 100 parts by mass of the phenolic resin initial condensate (initial cocondensate) in the case of aldehydes and aldehyde donors, and in the case of alkylolated triazone derivatives. It is 10-500 mass parts with respect to 100 mass parts of initial stage condensates (initial cocondensate) of a phenol resin.

[Third component]
In the present embodiment, flame retardants other than the above-mentioned melamine polyphosphate, such as phosphorus compounds, nitrogen compounds, sulfur compounds, aluminum hydroxide, boron compounds, bromine compounds, guanidine compounds, phosphate compounds, phosphoric acid Flame retardants such as ester compounds, amino resins, and cyclic phosphonates may be used in combination.
In addition, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium oxide, titanium oxide, iron oxide, zinc oxide, alumina, silica, diatomaceous earth, Inorganic fillers such as dolomite, gypsum, talc, clay, asbestos, mica, calcium silicate, bentonite, white carbon, carbon black, iron powder, aluminum powder, glass powder, stone powder, blast furnace slag, fly ash, cement, zirconia powder Natural rubber or derivatives thereof; synthetic rubber such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, isoprene-isobutylene rubber; polyvinyl alcohol Water, sodium alginate, starch, starch derivatives, glue, gelatin, blood powder, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyacrylate, polyacrylamide and other water-soluble polymers and natural gums; calcium carbonate, talc, gypsum, carbon Fillers such as black, wood flour, walnut flour, coconut powder, wheat flour, rice flour; surfactants; higher fatty acids such as stearic acid and palmitic acid; higher alcohols such as palmityl alcohol and stearyl alcohol; butyryl stearate, glycerin Esters of fatty acids such as monostearate; fatty acid amides; natural waxes such as carnauba wax, synthetic waxes; paraffins, paraffin oil, silicone oil, silicone resin, fluororesin, polyvinyl alcohol, grease, etc. Mold release agents; organic foaming agents such as azodicarbonamide, dinitrosopentamethylenetetramine, p, p'-oxybis (benzenesulfonylhydrazide), azobis-2,2 '-(2-methylgropionitrile); bicarbonate Inorganic foaming agents such as sodium, potassium bicarbonate and ammonium bicarbonate; hollow particles such as shirasu balloon, perlite, glass balloon, foamed glass and hollow ceramics; plastic foams and foamed particles such as foamed polyethylene, foamed polystyrene and foamed polypropylene Pigments, dyes, antioxidants, antistatic agents, crystallization accelerators, expanded graphite, flameproofing agents, water repellents, oil repellents, insecticides, preservatives, waxes, lubricants, antiaging agents, UV absorbers Phthalate ester plasticizers such as DBP, DOP, dicyclohexyl phthalate and other tricresyls Adding a plasticizer such as Sufeto may be mixed.

[Manufacture of flame retardant fiber material]
In order to produce the flame retardant fiber material, first, when the fiber material is impregnated with the phenol resin, the fiber material is usually immersed in the phenol resin solution or a synthetic resin solution is added to the fiber. The material is sprayed or applied by a knife coater, roll coater, flow coater or the like.
To adjust the phenolic resin impregnation amount of the fiber material after phenolic resin-impregnated, narrow using a roll or press platen stop the fiber material.
The phenolic resin-impregnated fiber material after squeezing reduces the thickness, but when the phenolic resin-impregnated fiber material contains hollow fibers, the rigidity is high, and after squeezing, the thickness is elastically restored. And a certain thickness is ensured. In particular, when the fiber material contains low-melting fibers, it is desirable to heat the fiber material in advance to melt the low-melting fibers and bind the fibers with the melt. If it does so, intensity | strength and rigidity will improve further, this fiber material will improve the workability | operativity at the time of a phenol-type resin impregnation, and the restoration | restoration of the thickness after drawing will also become remarkable.
If it contains hollow fibers to the fiber of the present embodiment as described above, a sheet when a sheet of goes high rigidity, the content of phenolic resin in the phenolic resin impregnated fibrous material, not including the hollow fibers phenol can be reduced than the content of phenolic resin systems resin impregnated fibrous material.

After the phenolic resin was applied or impregnated into the fibrous material, the phenolic resin impregnated fibrous material is caused to ambient or heat drying. During pressurization heat drying, idea Suffice phenolic resin in the B state, moldability is maintained over a long period of time, and allows for low-temperature short-time molding.

The phenolic resin-impregnated fiber material is given rigidity, moldability, and the like by the phenolic resin. For the above purpose, the phenolic resin is preferably 5 to 200% by mass with respect to the fiber material, preferably It is desirable to impregnate at a rate of 10 to 100% by mass, more preferably 20 to 70% by mass. When the phenolic resin impregnation amount is less than 5% by mass, the rigidity and moldability of the phenolic resin impregnated fiber material are not improved, and when it exceeds 200% by mass, the rigidity is too high and the moldability is deteriorated.

[Aqueous dispersion of melamine polyphosphate powder added with phenol resin initial condensate]
Phenol resin initial with the deposit of the melamine polyphosphate powder in the fiber material or a phenolic resin impregnated fibrous material, the melamine polyphosphate powder dispersed in water on the surface of the fiber material or phenolic resin impregnated fibrous material A method of applying the aqueous dispersion added with the condensate by spraying or the like is applied.
The phenolic resin initial condensate exhibits good miscibility with the melamine polyphosphate powder, and the viscosity of the aqueous dispersion is increased moderately, whereby the aqueous dispersion is converted into the fiber material or the phenolic resin-impregnated fiber. When applied to the surface of the material, the melamine polyphosphate powder in the aqueous dispersion is prevented from oozing out to the back surface of the fiber material or phenolic resin-impregnated fiber material.
When melamine polyphosphate powder in aqueous dispersion seep to the back surface of the fibrous material or phenolic resin impregnated fibrous material, spots due to melamine polyphosphate powder on the back surface of the fibrous material or phenolic resin impregnated fibrous material Occurs and the appearance deteriorates.
As the above-mentioned thickening phenolic resin initial condensate, the same phenolic resin initial condensate impregnated into the above-mentioned fiber material is used. In order to obtain a stable homogeneous aqueous solution, sulfomethylation and / or Alternatively, it is desirable to use a sulfimethylated phenolic resin precondensate.

The ratio of the phenol-based resin initial condensate and the melamine polyphosphate powder in the aqueous dispersion is phenol resin initial condensate: melamine polyphosphate powder = 5: 95 to 50:50 mass ratio (solid content), and the water The viscosity of the dispersion is desirably in the range of 50 to 1000 cps at 23 ° C.
When the ratio of the phenolic resin initial condensate: melamine polyphosphate powder is smaller than 5:95 mass ratio (solid content) (when the phenolic resin initial condensate is less than 5 mass ratio), the water dispersion the viscosity of the liquid becomes less than 50cps at 23 ° C., the fiber material or phenolic resin impregnated fibrous material the aqueous dispersion liquid applied to the surface, easily exudes to the fiber material or phenolic resin impregnated fibrous material back surface, also When the ratio of the phenolic resin initial condensate: melamine polyphosphate powder exceeds 50:50 mass ratio (solid content) (when the phenolic resin initial condensate is more than 50 mass ratio), the viscosity increases. It becomes larger 1000cps above, the aqueous dispersion be uniformly coated impregnated into the fiber material or a phenolic resin impregnated fibrous material surface frame To become.
The melamine polyphosphate powder is usually adhered to 5 to 80% by mass with respect to the fiber material or the phenol resin-impregnated fiber material.

For example, as shown in FIG. 1, the flame retardant fiber material is produced by first pulling out a sheet-like fiber material 2 from a raw roll 7 of the production apparatus 1, passing through a guide roller 8, and impregnating roller 9 to produce the fiber material 2. after impregnating the phenolic resin 5 to the diaphragm to adjust the impregnated amount of the phenolic resin 5 in the fiber material 2 by a roller 10, brought heated drying the phenolic resin by subsequent heater 11, a phenolic resin impregnated fibrous material 3 is produced. Further, a melamine polyphosphate powder aqueous dispersion 6 containing a phenolic resin initial condensate prepared in an aqueous dispersion mixing tank 13 is applied to the phenolic resin-impregnated fiber material 3 from the spout 12 and dried by a heater 14. By doing so, the flame-retardant fiber material 4 is manufactured.
Alternatively, as shown in FIG. 2, the step of the heater 11 may be omitted, and after impregnating the synthetic resin 5, the process may proceed to the step of applying the phenol resin initial condensate-containing melamine polyphosphate powder aqueous dispersion 6.
The flame retardant fiber material 4 is then cut into a predetermined length or formed into a predetermined shape to obtain a product.

[Example 1]
(Phenolic resin)
The following three types of initial condensates were used as phenolic resins.
Normal alkaline resol type phenol resin initial condensate aqueous solution using sodium hydroxide as condensation reaction catalyst (1)
Sulfomethylated phenol-alkylresorcin cocondensation resin initial condensate aqueous solution (2)
Sulfimethylated phenol-alkylresorcin cocondensation resin initial condensate aqueous solution (3)
The three types of properties are shown in Table 1. The measuring method is as follows.
Nonvolatile content: Conforms to JIS K 6802 5.2.
pH: Conforms to 5.6 of JIS K 6802.
Viscosity: Conforms to 5.7 of JIS K 6802.
Water miscibility: Conforms to JIS K 6802 5.4.

[Mixture of phenolic resin initial condensate and melamine polyphosphate powder]
Melamine polyphosphate having an average particle size of 4.0 ± 2.0 μm as a melamine polyphosphate powder (MPP-A, trade name, manufactured by Sanwa Chemical Co., Ltd.) as a melamine polyphosphate powder in the aqueous phenol resin condensate solutions (1) to (3). Was prepared by mixing so that the ratio of the initial condensate: MPP-A was 5:95 mass ratio and 50:50 mass ratio, respectively. 1-No. The viscosity of 6 is shown in Table 2.

[Comparative Example 1]
In Example 1, a processing liquid in which the blending ratio of the phenolic resin initial condensate and the melamine polyphosphate powder was changed, and a processing liquid in which only the melamine polyphosphate powder was mixed and dispersed in water without adding the phenolic resin initial condensate. Further, Table 3 shows the viscosities of the working fluid in which the melamine polyphosphate powder was replaced with melamine resin-coated ammonium polyphosphate (melamine-coated APP) as a flame retardant.

Three types of mixed liquids comprising 30 parts by mass of the phenol-based resin initial condensates (1) to (3) used in Example 1, 1 part by mass of carbon black (40% by mass aqueous dispersion), and 69 parts by mass of water. A nonwoven fabric by a spunbond method having a mass per unit area (weight per unit area) of 50 g / m ^{2 made} of polyester fiber was impregnated with a roll so as to be a coating amount of 30% by mass of the nonwoven fabric. Next, with respect to the resin-impregnated nonwoven fabric, the processing liquid No. 1 described in Table 2 was used. 1-No. If 6 is stirred, spray coating is applied at a coating amount of 80 g / m ² (solid content of 32 g / m ² ) on one side by a spray method, and heated at 140 ° C. for 2 minutes in a dryer while sucking, and then phenolic. Using the processing liquid of each formulation shown in Table 4 by setting the resin initial condensate to the B state and fixing the flame retardant (MPP-A) to the nonwoven fabric with the phenolic resin initial condensate contained in the processing liquid as a binder at the same time Various flame retardant fiber sheets were prepared.
Next, the obtained flame-retardant fiber sheet was used as a skin material, and polymerized into a glass wool raw cotton having a basis weight of 800 g / m ² and a thickness of 30 mm mixed with 10% by mass of an uncured phenol resin. A molded sheet No. shown in Table 4 was press-molded for 2 seconds and the thickness of the middle part of the product was 10 mm and the peripheral thickness was 2 mm. 1-No. 6 was produced. Table 4 shows the whitening test on the surface of the skin material, which is the flame-retardant fiber sheet of the obtained molded sheet, and the test results of the spray workability of each processing liquid when creating the flame-retardant fiber sheet.

[Comparative Example 2]
In Example 2, the working fluid No. 7-No. In the same manner except that 16 was used, the molded sheet No. 1 shown in Table 4 was used. 7-No. 16 was produced. Table 4 shows the test results of each molded sheet.

〔Test method〕
Sprayability Processing fluid Nos. Of each formulation according to Table 2 and Table 3. 1-No. About No. 16, the state at the time of spray-coating to the nonwoven fabric by which the phenol-type resin initial condensate was impregnated was investigated. The processing liquid was spray-coated on the nonwoven fabric surface by an air spray (spray gun caliber: 2.4 mm) method, and the state in that case was examined.
A: There is no abnormality during spraying, the spraying work is good, and the resin does not ooze out to the back of the nonwoven fabric.
(Triangle | delta): A viscosity is high and uniform application | coating cannot be performed. There is no seepage of resin on the back of the nonwoven fabric.
X: The viscosity is low and the spraying work is good, but the resin oozes out to the back of the nonwoven fabric.
Whitening test Each flame-retardant fiber sheet and laminated wool sheet No. 1-No. The No. 16 was subjected to a moisture resistance test for 48 hours in a state of 40 ° C. × 95% RH and then allowed to stand at room temperature for 30 days, and the state of the skin material surface of the molded sheet was observed.
◯: No whitening phenomenon is observed on the surface (surface portion of 10 mm) surface and the surrounding surface (portion of 2 mm thickness) on the surface of the skin material.
Δ: Whitening phenomenon due to the flame retardant is not observed on the surface of the surface of the skin material (10 mm thick part) and the surrounding (2 mm thick part) surface, but color unevenness is observed as a whole.
X: Although the whitening phenomenon is not seen in the center part (10-mm-thickness) surface of a skin material surface, whitening is seen in several places on the surrounding (2-mm-thickness) surface part.
XX: No whitening phenomenon is observed on the surface of the skin material surface (portion having a thickness of 10 mm), but whitening is observed on the entire surface (portion having a thickness of 2 mm).

From the results of Table 4, the working fluid No. in the range of the ratio of the phenol-based resin initial condensate / melamine polyphosphate powder = 5: 95 to 50:50 mass ratio. 1-No. The viscosity at the time of processing of No. 6 is 50 to 1000 cps / 23 ° C., and it can be seen that the sprayability is good. In addition, a molded sheet No. 1-No. No whitening phenomenon is seen in 6.
Working fluid No. 5 containing 5% by mass or less of phenol-based resin initial condensate. 7-No. No. 9 and a processing fluid No. 1 in which melamine polyphosphate powder is dispersed only in water not containing the phenol-based resin initial condensate. No. 13 does not thicken to an appropriate viscosity, and the melamine polyphosphate powder in the processing liquid oozes out to the back surface of the nonwoven fabric during spraying, resulting in poor appearance.
On the other hand, the processing liquid No. in which the phenol-based resin initial condensate exceeds 50% by mass. 10-No. No. 12 is so thick that the viscosity exceeds 1000 cps / 23 ° C., and the melamine polyphosphate powder does not ooze out to the back of the nonwoven fabric, but causes poor appearance such as uneven coating.
Further, a processing fluid No. 1 using ammonium polyphosphate coated with melamine as a flame retardant. 14-No. No. 16 has good workability at the time of spraying. 9, no. 13, no. In No. 16, the melamine coating is destroyed at a high-density portion (thickness 2 mm) by heating and pressurization at the time of molding, and whitening due to the ammonium polyphosphate that has gone out occurs.
Molded sheet No. 7, no. 8, no. 10, no. 11, no. 12, no. 14, no. In No. 15, the viscosity of the processing liquid is less than 50 cps / 23 ° C. or more than 1000 cps / 23 ° C., and no whitening is observed, but the appearance is poor due to uneven coating on the surface or the back surface of the melamine polyphosphate powder in the sprayed resin. It can be seen.

Example 3
A non-woven fabric having a basis weight of 80 g / m ² by a needle punching method made of polyester fiber was used as a fiber sheet.
Next, as a synthetic resin, 30 parts by mass of phenol-formaldehyde initial condensate (50% by mass nonvolatile solution), 2 parts by mass of a fluorine-based water / oil repellent (20% by mass aqueous solution), carbon black (30% by mass aqueous dispersion) 2 A mixture composed of part by mass and 66 parts by mass of water was impregnated with a roll so that the coating amount was 50% by mass of the fiber sheet.
Furthermore, a viscosity of 380 cps / 23 comprising 30 parts by mass of melamine polyphosphate (MPP-B, trade name, manufactured by Sanwa Chemical Co., Ltd., particle size: 12 ± 2 μm), 20 parts by mass of the phenol-formaldehyde initial condensate and 50 parts by mass of water. A flame retardant mixed solution at a temperature of 60 ° C. is applied to one side of the synthetic resin impregnated fiber sheet by a spray method at a coating amount of 60 g / m ² and dried at 140 ° C. to make the phenolic resin initial condensate into a B state. A fiber sheet was prepared.
Glass wool raw cotton coated with an uncured phenolic resin with a basis weight of 800 g / m ² is polymerized as a base material on the flame retardant application surface side of the flame retardant fiber sheet, and hot-pressed at 200 ° C. for 70 seconds. A molded product having a predetermined shape was produced.
The resulting molded product is flame retardant UL-94 standard V-0, and there is no abnormality such as whitening in appearance even after long-term storage, automotive hood silencer, engine under cover silencer, cylinder head cover silencer, This molding is useful for dash silencers.

(Delete)

  The flame-retardant fiber material of the present invention exhibits water resistance and high durability flame retardancy, is excellent in appearance, and is useful as an automotive material or a building material, and thus can be used industrially.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 2 Fiber material 3 Phenolic resin impregnation fiber material 4 Flame retardant fiber material 5 Phenolic resin 6 Melamine polyphosphate powder aqueous dispersion 7 Raw material roll 8 Induction roller 9 Impregnation roller 10 Squeezing roller 11 Heater 12 Sprinkle opening 13 Water dispersion tank 14 heater

Claims (4)

Step 1 of impregnating the fiber material with phenolic resin,
Step 2 of drying was coated an aqueous dispersion of melamine polyphosphate powder phenolic resin precondensate to the fiber material a surface impregnated with the phenolic resin is added,
The manufacturing method of the flame-retardant fiber material characterized by consisting of the above processes 1 and 2. The method for producing a flame-retardant fiber material according to claim 1 , wherein the phenolic resin is sulfomethylated and / or sulfimethylated. The ratio of the phenol resin initial condensate to the polyphosphate melamine powder in the aqueous dispersion of the melamine polyphosphate powder to which the phenol resin initial condensate was added was phenol resin initial condensate: melamine polyphosphate powder = 5: 95. The method for producing a flame-retardant fiber material according to claim 1 or 2, wherein the viscosity of the water dispersion is in the range of 50 to 1000 cps at 23 ° C. The flame retardant fiber material according to any one of claims 1 to 3 , wherein the phenol-based resin initial condensate is a sulfo-methylated and / or sulfimethylated phenol-based resin initial condensate. Method.

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