TW200829616A - Fire-retardant processing liquid, fire-retardant fiber material and interior material obtained by using the fiber material - Google Patents

Abstract

The object of the present invention is to impart fire-retardance with water resistance and durability to interior materials of automobiles and the like. To attain said object, a fire-retardant processing liquid in which polyammonium phosphate particles having solubility to water of 5 % by mass or less are dispersed in an aqueous solution of a primary condensate of a phenolic resin is provided. In the processing liquid, a phenolic resin coat is formed on the surface of the polyammonium phosphate particles and thereby imparting water resistance.

Description

200829616 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a flame retardant treatment liquid used in a fiber material. [Prior Art] In the past, ammonium polyphosphate having low toxicity has been used as a flame retardant. However, ammonium polyphosphate has a water-soluble property, such as being mixed or impregnated into a fibrous material, and may be eluted from the fibrous material in contact with moisture or moisture to lower the flame retardancy. Therefore, there is provided a resin-coated ammonium phosphate particle coated with melamine, urea, or the like on the surface of ammonium polyphosphate particles, which is made to be contacted with fumarin and resinized in the above-mentioned resin-coated polyacrylic acid-recorded particles. The surface of the ammonium polysilicate is coated with resinized melamine, urea, etc., and the inhibitor 1 is dissolved in water. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 7-277713 (Draft of the Invention) [Technical Problem to be Solved by the Invention] The above conventional resin-coated ammonium polyphosphate particles have a high production cost and a high price. The coated ammonium polyphosphate particles are usually adhered to the fibers by being dispersed in a resin liquid for coating or impregnation into the fiber sheet, and the dispersibility of the above-mentioned sapphire-coated polysulfate particles in the resin liquid is poor and is easily separated. And if the amount of the resin is dispersed in a large amount, the viscosity of the resin liquid is increased by two. Further, the adhesion between the above-mentioned resin-coated ammonium amide particles and the fibers is not good, for example, the fiber sheet containing the resin-coated ammonium polyphosphate particles is 319583 5 200829616 When it is alone or combined with other sheets, the moisture contained in the fiber sheet is volatile, such as moisture, and it is steamed and steamed from the heat of the U7. Particle shift J St: At the same time, the resin is coated with a dish of acid saddle ancestors on the surface of the moon and the surface of the moon is smashed. I pass out... the surface of the moon has a heterochromatic spot. The purpose of the present invention is to solve the above problem. The price is as good as the water-based scalar acid, so that the present invention is effective in the aqueous solution of the tree = condensate, and the solubility in the water is 5 mass 2 = the flame retardant treatment liquid of the ammonium polyphosphate particles is the key. (4) The initial condensate of the resin is a multi-(four) initial condensate or an initial condensate containing a multi-cut is a good person## m Θ 糸 糸 糸 月 “ 勿 勿 勿 勿 勿 勿 勿 勿 勿 勿It is preferable to use a water-soluble resin as a dispersing agent in the aqueous solution of the initial condensate of the variegated resin. Further, the present invention provides Mix or (4) the above-mentioned 卩 卩 的 叙 叙 叙 叙 叙 , , : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : (Effect) The invention of claim 1 identifies that the initial condensate of the phenolic resin has an acoustic affinity to the surface of the ammonium polyphosphate particle, and the polyphosphorus filament is dispersed in the aqueous solution of the initial shrinkage. The initial condensate is firmly attached to the polyphosphoric acid = 319583 6 200829616 (4) Site dispersion When the compound becomes a lactic acid-containing particle having a protective colloid of 5% by mass, the solubility in water is over*, and the particle is dissolved in water and reported in difficulty: 2 = the invention of the second application of the aqueous solution application scope D-shaped sorrow. The initial condensate of the phenolic resin causes the cheese to be opened, and is the initial condensate of the kimono age or the initial condensate of the age of the package, especially the initial wall containing the alkyl benzene bismuth... The age of the compound is accelerated, so the hardening yield η ΐ ... and the reaction speed of the vine (4) basin J Shilian 'for example, the treatment liquid is impregnated with the fiber _ _ phase condensate rapidly hardened resinized and coated The particles are blocked to prevent the water from being dissolved on the fiber sheet. The 'particles are firmly adhered to the invention of claim 3 of the patent application _ the initial condensate of the resin such as sulfonic acid methylation and/or Aarene The methyl group-based treatment is stable because the aqueous solution of the initial condensate is stable in a wide range of pH. Therefore, a wide range of pH hardeners can be used regardless of the acidic hardener or the test hardener. In the aqueous solution of the bismuth resin initial condensate, if a water-soluble resin as a dispersing agent is added, the dispersion stability of the ammonium polyphosphate particles is improved. " Invention No. 5 of claim 5, if the flame retardant treatment liquid is mixed or coated on a fiber sheet or a mat, the ammonium polyphosphate particles in the treatment agent are firmly adhered to the initial condensate by 339583 7 200829616 On the fiber sheet, a flame retardant fiber material having water resistance durability can be obtained. According to the invention of claim 6, if the flame-retardant fiber material is adhered to the surface of the substrate as a surface material and formed into a predetermined shape, the initial condensate coated on the surface of the ammonium polyphosphate particle attached to the fiber material is coated. The water resistance is formed by hardening and resinizing, but as described above, the ammonium acrylate-based particles are firmly adhered to the fiber sheet by the phenol-based resin of the resin of the initial condensate, so that even if hot pressing is applied The molding does not cause the water or other volatile components contained in the surface material or the substrate to be evaporated, so that the ammonium polyphosphate is not exposed to the surface of the sheet. [Effects of the Invention] Accordingly, the present invention provides a flame retardant treatment liquid which imparts flame retardancy with water resistance durability and which is inexpensive. [Embodiment] The present invention will be described below in detail. [Amount of ammonium polyphosphate) The ammonium polyphosphate salt used in the present invention is in the form of particles having a solubility in water of 5% by mass or less. These ammonium polyphosphates have an ammonium polyphosphate having a degree of polymerization of 10 to 40. The ammonium polyphosphate having the above polymerization degree is poorly soluble or insoluble in water, and is decomposed at a high temperature to generate a flame retardant gas, but the flame retardant gas is low in toxicity to humans and animals. Here, the degree of polymerization n of ammonium polyphosphate is calculated from the following calculation formula. 319583 8 200829616 [Calculation 1]

Here, 'P m. 1 means the number of moles of phosphorus contained in ammonium polyphosphate, and Nm()1 means the number of moles of nitrogen, and Pm〇i and Nm〇i are calculated by the following calculation formula. [Calculation 2] d - p content (% by mass) / 1 〇〇 P atomic weight (30.97) [Formula 3] f, N = N content (% by mass) / 1 〇〇 " m〇1 (14.01 )

The analysis of the P content, for example, by ICP emission spectrometry, analysis of the N content, for example, by the CHN method. If the degree of polymerization is 10 or more, ammonium polyphosphate is hardly soluble in water. However, if the degree of polymerization exceeds 40, the ammonium polyphosphate is dispersed in water or an aqueous dispersion solvent. When the viscosity of the dispersion is abnormally increased, it is difficult to uniformly coat or impregnate the coating or impregnation of the fiber sheet or the like, and the coating amount or The amount of impregnation is not uniform, and its fruit is not sufficiently flame retardant. /, " [expanded graphite]

3υυ to 30 mesh. [Heat-expandable granules] The fuels are used together. The above / in the concentrated sulfuric acid, linic acid, citric acid and other non-perchlorate, permanganate, heavy road, the expansion start temperature is about 30 to 300ml / g, the particle size is about 319583 9 200829616 will be the present invention When the flame retardant treatment agent is applied or impregnated into the fiber sheet or the mat, the heat-expandable granules may be added. The heat-expandable granules are composed, for example, of a thermoplastic resin having a low softening point and a solvent having a low boiling point. The thermoplastic resin having a low softening point may, for example, be decyl acrylate, ethyl acrylate, human propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid 1 B. Hexyl hexyl ester, cyclohexyl acrylate, tetrahydrofurfuryl acrylate (furan), methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, decyl propyl (enoic acid) n-Butyl ester, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, stearyl methacrylate, lauryl methacrylate, etc. Group or cyclic acrylate and / or methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, different Vinyl (ether) ether such as butyl vinyl ether, styrene such as styrene or fluorene methyl styrene, nitrile monomer such as acrylonitrile or methacrylonitrile, vinyl acetate or propionic acid Fatty esters such as vinyl esters (groups of ethylene, vinyl chloride, vinylidene chloride, a halogen-containing monomer such as vinyl fluoride or vinylidene fluoride, an olefin such as acetam or propylene, a diene such as isoprene, chloropredylene or butadiene, acrylic acid, methacrylic acid or itaconic acid. , horse end 酉夂, crotonic acid, atr〇pic acid, citraconic acid, etc. α, uncoated and carboxylic acid, 2-hydrocarbyl methacrylate, acrylic acid 2 - a hydrocarbon-containing monomer such as a hydrocarbon ethyl ester, a methacrylic acid propyl ester, a 2-hydroxypropyl acrylate or an allyl alcohol; a decylamine such as acrylamide, methacrylamide or diacetone acrylamide; Amino group-containing monomer such as dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate, 319583 10 200829616 monomethylaminopropyl propylate, propylene An epoxy group-containing monomer such as acid glycidyl ester, glycidyl methacrylate or glycidyl allyl ether, and other ethylene. Compared with each other, vinylpyrrolidone, ethylene, vinylpyridiene, ethylene Water-soluble monomer such as vinylcarbazole, and ethyl bromide and dipropylene A cross-linking agent such as diethylene glycol or a polyacrylic acid ester or methacrylate, diallyl phthalate (DAp, diallylphthalate) or acrylyl glycidyl ether (r) will be as 7- (methacryloxy)oxypropyltrimethoxy oxime, (vinyltriethoxydecane, p-trimethoxysulfonyl styrene, p-triethoxydecane styrene, p-three曱 矽 矽 曱 曱 、 、, p-diethoxydecane methyl styrene, (propylene methoxy) propyl trimethoxy decane, vinyl trimethoxy decane, stone (沁 vinyl benzyl) One or more polymers such as an amino group containing a hydrolyzable alkylene group such as an aminoethyl-γ-aminopropyl)trimethoxy decane hydrochloride; or a polymer having a % by weight of the above polymer, Low-softening point polyamine, low-softening point polyester, etc. (having a thermoplastic resin preferably having a softening point of 180 C or less, as a low-boiling solvent, for example, n-hexane, cyclohexane, n-pentane, isopentane, positive Butane, isobutane, n-gum octyl sulphate 'isolated, gasoline, di-butyl scale, propionate, benzene and other boiling point 150. (The following organic solvent. The heat-expandable particle system is composed of the above-mentioned thermoplastic resin particles, the foamable particles impregnated with the above-mentioned low-boiling solvent, and the microcapsules filled with the low-point solvent in the low-softening point thermoplastic resin. The diameter of the granules is usually 〇·5 to 1 〇〇〇#m. As the heat-expandable granules used in the present invention, there are also heat-expandable inorganic granules such as vermiculite, bun iron, and silica gel. 319583 11 200829616 [Convergent resin] The resin is expected to have flame retardancy and also has affinity for the surface of the ammonium polyphosphate particles and firmly adheres to the surface of the particles. The above-mentioned ageing resin is obtained by using a compound and an acid and/or The acid donor is obtained by condensation. [Different compound] The phenolic compound used in the above phenolic resin may be a single test of a single spoon, or a mixture of a single test and a plurality of ages, but only When monohydric phenol is used, it is preferred to use a single-multiple or one-dimensional mixture and multiple test mixture when curing and after curing, because it is easy to release formic acid. [One yuan] The above one The age can be exemplified by ethyl phenol, isopropyl phenol, xylenol, 3,5-diphenol, butyl phenol, dibutyl phenol, nonylphenol and other alkylphenol 'o-fluorophenol, Fluorophenol, p-fluorophenol, hearing, inter-chlorine, chlorine, neighboring, secret, _, adjacent = 1 (10) '(10)' o-amino group, inter-amino acid, amino-based Age, (4) basic test, inter-nitrogen wire, nitroxide, 2, heart dinitro-test, Μ 6-three renewed base - (4) substitute; naphthalene material polycyclic - meta-time, and such mono-phenol It can be used alone or in combination of two or more. [Multiple] The above polyhydric phenol can be exemplified by: inter-cage one. . . v 1 phenol, alkyl resorcinol, pyrogallol, catechol, alkyl Catechol, hydrogen cone ^ L also burns hydroquinone, phloroglucinol, bisphenol, trihydroxynaphthalene, etc. These polyphenolic compounds j are mixed as early or as a mixture of two or more 319583 12 200829616 or burnt base Benzene is the second one, and the second test is used for rapid cooking. The preferred system of polyphenols is isophthalic acid. The reaction rate with aldehyde is more complicated than that of styrene. Benzene-=5 propylbenzene The second can be exemplified by: 4 base resorcinol, 5- Base, soil, phenol, 5_n-butyl resorcinol, 4,5-dimethyl A, phenol, 2,5-dimercapto-p-phenylene terephthalate, 45... ::-Ethyl-based, 2,5-phenol, 4-methyl, <, _-propyl intermediate diphenol, 2,5-dipropyl isophthalate...ethylm-phenylene U-A _5_Ethyl phenylethylmethyl sulfonyl benzene new phenyl benzoate, 2, 4, 5 2 - phenylene bismuth, etc. by the dry house Estonia (EstQnia) made in China It is cheap, and in addition to 5-methyl-m-phenylene-diene, it is a particularly good raw material for the present invention because of the various benzene-based tests of ruthenium. [Aldehyde donor] '0, the above The phenolic compound is condensed with an aldehyde and/or an aldehyde donor (aldehyde), and the above-mentioned I-administration system means that a compound or other mixture which supplies an aldehyde can be produced upon decomposition. Such an aldehyde donor can be exemplified by a secondary aldehyde aldehyde, a dialdehyde, a hexamethylenetetramine, a tetrafurfural or the like. In the present invention, an aldehyde and an aldehyde donor are combined, hereinafter referred to as an aldehyde. Mouth [Production of phenolic resin] ―Only = phenolic resin has two types, and the phenolic compound is obtained by reacting a base catalyst (catalyst) with a phenolic compound. And excess phenol with respect to aldehydes and reacted by acid catalyst (catalyst) 319583 13 200829616 = type resin, A (4) resin is formed from a mixture of alcohols, usually provided by an aqueous solution of an initial condensate (4) The lipid system is formed by the condensation of the two kinds of derivatives of the two kinds of derivatives; the powder of the initial condensate is usually condensed to mono-phenol by the powder of the initial condensate: As early as the (four) condensate, and can also condense - the multi-materials and the genus of the condensate into a multi-component condensate of the initial condensate, one or two = one condensate of one dollar and a plurality of condensates can be reserved in advance. As a kind of initial priming, the 树脂 树脂 树脂 _ _ _ _ _ 苯 纷 二 二 二 二 么 炫 炫 炫 炫 炫 炫 , , : : : : : : : : : : : : : : : : : : : : : : : : : : : Compared with the first condensate formed by the age, it can be long-term under normal temperature conditions; (4) the aqueous solution is impregnated or coated on the sheet substrate, and the fiber is pre-supplied; the culture is good, and even if it is preserved for a long time. The fiber sheet does not lose the type ^. Moreover, the reactivity between the benzene and the acid in the base is high, and the reaction is free. The reaction is so that the amount of free aldehyde in the resin is gradually reduced, etc. The best manufacturing method of the alkyl resorcinol cocondensate, the eucalyptus reaction to produce the initial condensate of the variegated resin' followed by the enthalpy: adding or subtracting the benzoic acid to the compound, if necessary The method of reaction. The buccal sputum = such as 'the above (4) - secret and / or more S is expected to be condensed with the acid, :: add 0 2 to 3 moles of aldehydes to i mole monophenol, for !, more (four) Add 0.1 to 0.8 moles of acid and add 319583 14 200829616 to the third ingredient, if necessary Heat the anti-w to 2 〇小日守 under the condition of liquid temperature Λ Q ^ r ^ Wang. At this time, the genus can be used later # yV , Ding Xin Ha Da Bei 7 is added at the beginning of the reaction, or can be added in stages or Further, in the present invention, the above I (four) fat, if necessary, may also be added with urea, thiourea, melamine, thiomelamine, dichloramine, vein, adenine (mercaptoamine), Methyl decylamine, benzoguanamine, 2,6-diaminol- 13 y =, the initial shrinkage of resin monomers and urethane resin monomers: body sub- and (d) compounds and / or initial condensates Co-condensation. When the above phenolic resin is produced, if necessary, it may be mixed with a catalyst or a pH adjuster before, during or after the reaction, for example, sulphuric acid, orthophosphoric acid, orthoic acid, oxalic acid, Formic acid, acetic acid, butyric acid, ^ sulfonic acid, successive acid, p-methylbenzene acid, Cai_α_continued acid, naphthalene I continued acid and other inorganic or organic acids, dimethyl oxalate and other organic acid esters , cis-butenedic anhydride, sputum and other anhydrides, ammonium chloride, sulphuric acid, m oxalic acid, ammonium acetate, acid, thiocyanate, imine Acid recordings such as salt, chloroacetic acid or its sodium salt 'α,α, _ dichloropropanol and other organic dentate, triethanolamine hydrochloride '(tetra) aniline and other amines hydrochloride 'salicylic acid urea addition Urea adducts such as stearic acid urea adducts, heptanoic acid urea adducts, N-tdmethylt bribes, zinc chloride, ferric chloride and other acidic substances, ammonia, Amines such as sodium hydroxide, potassium hydroxide, chlorine oxide locks, chlorine oxide dance and other alkaline metals or soil-measuring metal hydroxides, lime and other soil-measuring metal oxides, sodium carbonate, sodium sulfite, sodium acetate, An experimental substance such as a weak acid salt of an alkali metal such as sodium phosphate. In the initial condensate of the age-containing resin of the present invention (including initial co-condensation 319583 15 200829616 '), a hardening agent such as the above-mentioned rattan may be further added. . - 兀 二 二 二 衍生物 衍生物 derivative The above alkanoylated trimorphone derivative and _ reaction obtained. Used in the manufacture of soaking alcohol=== with amine-based silk urea, methylthiourea and other thiourea-urea benzene on the second one: medium base:::: chemical base urea, etc. alone or two , amines can be exemplified;, =, special aliphatic amine 'nodal amine' 糠 (yl) amine, ethanol butyl:: diamine, hexamethylenetetramine and other amines, other Ammonia, such a: ": can be used alone or in combination of two or more. Used in; =,: aldehydes of erythritol triacetone derivatives 槲:. The class of the compound is the same. ^ The initial shrinkage of eucalyptus gambling: In the synthesis of the above-mentioned alcoholic tri-derivatives, it is usually used for "5 urea compounds, amines and/or ammonia." ....2 Moer, the discs reacted at a ratio of .4.0 moles. In the above reaction, although the order of addition is arbitrary, the optimum reaction method is first maintained at 6 〇 in the (four)' of the ruthenium demand. . The following temperature; H is added with the desired amount of amines and / or ammonia, and then added to the desired 'then' and then heated under stirring at 80 to 9 (TC conditions for 2 to 3 hours, the reaction method. Aldehydes usually The use of 37% furfural water, but: the concentration of the soil, a part of the middle can be replaced by polymethyl ketone.:,: ', methylenetetramine can get a higher solids reaction product. Urea 319583 16 200829616 Compounds and amines and / or ammonia and aldehydes in a row 'but can also use methanol, ethanol, Xian Tian 2, usually in aqueous solution into the diethylene glycol and other alcohols alone or more than two positive - Butanol, ethylene glycol, all neighbors $7fc.廿Β, /t0 compound, to replace part or °, and, can also be added with acetone, first-class water-soluble organic solvent alone or - " soil- The amount of the ketone ketone compound added is _3; == compound. The initial condensate of the above hard phenolic resin (the first berry of the invention, the octagonal, 'complex) is 10 to 1 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 ' [Sulphonylation of sulfonic acid groups and/or methylation of sulfonic acid groups] In order to improve the stability of water-soluble phenolic resins: xanthate methylation and / or sulfhydryl methyl It is preferred that the tree (the succinic acid methylating agent) can be used to improve the stability of the water-soluble variegated resin, and the rhein acid methylation can be exemplified by sulfuric acid, sulfurous acid or The sulfite obtained by the reaction of the sulfite with the quaternary amine or the quaternary amine or the quaternary sulfite obtained by the fourth-order reaction, or the aldehyde obtained by the reaction of the water-soluble sulfite Addition. " The aldehyde adduct is formaldehyde, acetaldehyde, propionaldehyde, chloral, furfural, ethanedi-n-butyraldehyde 'hexanal, acrolein, benzaldehyde, crotonaldehyde, acrolein, = base B A product obtained by an addition reaction of an aldehyde, an o-tolualdehyde, a salicylaldehyde or the like with an aqueous sulfite, such as an aldehyde adduct of formaldehyde and a sulfite. 319583 17 200829616 [ A sulfinic acid thiolating agent] may be used to improve the stability of a water-soluble I-based resin, and may be exemplified by formic acid. Sulfuric acid steel (carved white powder, R〇ng_, benzoic acid, sodium sulfite, etc., aliphatic, aromatic, noble, rank, alkali metal sulfite, sodium hydrogen sulfite, hydrogen sulfite cake, winter wish A temple 1 bi-metal, alkaline earth metal bisulfite (dithionite)-based transalkylene sulfinates such as meso methane sulfinates, etc. & When the methylation and/or sulfinate group is methylated, a stone '"mercaptomethylating agent and a sulfinyl methylating agent" may be added to the initial condensate at any stage, and then a phenolic compound and/or an initial condensation (tetra) acid group methylation and/or a methylene group methylation. The addition of a rhesin acid methylating agent and/or a sulphate methylating agent can be The S-reaction is carried out in any stage after the reaction. The total addition of ^', 酉文基 methylating agent and/or sulfinic acid methylating agent is usually 0.001 to 1.5 moles per 1 mole of the phenolic compound. When the temperature is 0+001 or less, the hydrophilicity of the phenol resin is insufficient, and when it is more than or equal to the molar content, the water resistance of the phenol resin is deteriorated. In order to satisfactorily maintain the properties such as the curability of the initial/monthly shrinkage produced and the physical properties of the resin after curing, it is preferably about 〇·8·mole. In order to make the rhodamine group methylation and/or the sulfinic acid methyl group added to the rhodamine condensate, and/or the sulfinic acid methylating agent, The hydroxymethyl group of the initial condensate and/or the aromatic reaction of the initial condensate introduces a sulfonic acid methyl group and/or a sulfinic acid group 18 319583 200829616 base in the initial condensate of δ. An aqueous solution of a phenolic compound such as sulfonate methylation and/or sulfinic acid methylation, which is static, and has a wide range of hardness from acidic to alkaline: even if it is acidic, neutral and In the range of the testability, it is also possible to make the resin '%'-acidic' hardened, and the residual methyl group is reduced, and the decomposition of the compound does not cause formaldehyde. Further, an aqueous solution of the initial condensate of the above lanthanide resin may be added as needed: methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol 'second-butanol, Tri-butanol, n-pentanol, isoamyl alcohol, n-hexyl, methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, trimelliticol, cyclohexanol, sterols, sterols, Tetrahydrofurfuryl alcohol, pine alcohol, bis(tetra) alcoholic cut; acetone, methyl acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl, diethyl ketone , di-n-propyl ketone, di-n-butyl ketone, acetone acetone, methyl ether, cyclohexanone, methyl cyclohexanone, benzene acetate: ethylene glycol such as camphor, diethylene glycol, triethylene glycol, propylene glycol 'Dimethyl glycol' polyethylene glycol and other glycols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether 'ethylene glycol isopropyl ether, = ethylene glycol single, triethylene glycol monomethyl scales, etc. Glycol ether; ethylene glycol diacetate ' ' 二 二 二 单 单 二 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 ; ; ; ; ; ; ; ; , triethyl card Shaw, vinegar, ethyl lactate, isopropyl lactate vinegar, - (iv) ethylene glycol diacetate 'dimethylformamide and other water-soluble organic solvent. The aqueous solution of the initial condensate of the present invention thus produced usually contains the condensate at a concentration of from 5 to 80% by mass. [Preparation of Flame Retardant Treatment Solution] 319583 19 200829616 The above ammonium polyphosphate particles are dispersed in the above phenolic aqueous solution. In this case, the ammonium polyphosphate is dissolved in water, and the amount of the ammonium polyphosphate particles added to the initial condensate is usually 5 to 200 f%, and the liquid mixture may be in the treatment liquid: =0Λ]5. quality%. Expanded granules 4 Expanded stone s stalk expanded graphite or hot-coated graphite slings are added in an amount of 2 to 30% by mass in the range of j to 5 分散, and/or granules are usually 0.1 to 20 f% by weight, good A 'The above thermal expansion is in the above treatment liquid. "^41 to 1 (% by mass) is dispersed in the above-mentioned treatment liquid, and the above-mentioned initial adhesion to the surface of the poly-alkali soda: exerts the action of (4) the body and stably disperses the poly-acid acid in the solution, However, the dispersion stability can be improved by adding a water-soluble resin. The water-soluble resin can be exemplified by, for example, sodium poly(tetra)ate, arsenic polyacrylate, polyglycol, carboxymethyl Cellulose (cmc), methyl cellulose, ethyl cellulose, carboxyethyl cellulose, etc., in addition to the use of propyl acrylate and / or methyl acrylate vinegar and propyl benzoic acid and or An alkali-soluble resin such as a copolymer of acrylic acid or a micro-crosslinked product of the copolymer. The above-mentioned copolymer or micro-crosslinked copolymer is usually provided in an emulsion form as in the above-mentioned flame-retardant treatment liquid, and dissolved in the above water-soluble solution. In the case of a resin, the polyphosphorus ruthenium particles or the expanded graphite dispersed in the aqueous solution are not easily precipitated by the core-adhesive effect or the dispersion effect, thereby obtaining a uniform impregnation liquid. 319583 20 200829616 Furthermore, the water-soluble resin It can enhance the polyphosphorus to go to the particles or the graphite of the graphite, Adhesion sheet or mat, and the right to teach secret ,, "effectively prevented the money polyphosphate particles or expanded graphite sheet or the fibers detached from the mat. [Use of Flame Retardant Treatment Liquid] The flame-retardant treatment liquid of the present invention is mainly used for fibers such as Guwei tablets or crepe (four), but other materials such as polystyrene, polypropylene, polyurethane, polyvinyl chloride, and amine resin. A foam sheet of a synthetic resin such as a fat or a urea resin, or a fiber used in the above fiber sheet or mat, for example, a polyester fiber, a polyamide fiber, an acrylic fiber, Synthetic fibers such as polyamine vinegar fiber, polyvinyl chloride fiber 2, polyvinylidene chloride, acetic acid g fiber, wool, horse hair, cashmere, riding hair, sheep, insulting it, llama, Angola Wool, silk, cotton, yarrow fiber, pulp, kapok, coconut fiber, hemp fiber, bamboo fiber, kenaf fiber and other natural fibers, temple powder, polylactic acid and other biodegradable fibers, rayon (rayon, artificial Cotton), high-moisture modulus (polynosic fiber), cuprammonium (cupra), acetic acid vinegar, barium triacetate, cellulose-based rayon, glass fiber, carbon fiber, ceramic fiber, asbestos fiber, etc. Inorganic fibers, and waste of such fibers Recycled fiber obtained by spreading the fiber, etc. These regenerated fibers may be used singly or in combination of two or more kinds. Further, in the present invention, a low melting point fiber having a melting point of 180 ° C or lower may be used as the low melting point fiber. For example, polyethylene, polypropylene, ethylene: vinyl acetate g copolymer "ethylene _ acrylate § | copolymer and other poly-hydrocarbon fiber, polyvinyl chloride fiber, polyurethane (urethane) fiber, polyester fiber 319583 21 200829616

The P-polyester copolymer fiber, the polyamide fiber, and the low-melting point fiber may be used alone or in combination of two or more types, and the fiber may be read. The low melting point fiber has a denier of 6 〇 diex. Hehe. The above-mentioned low-spot fiber is usually mixed with the above-mentioned fiber in a mass ratio of u5 〇::: a sheet or a lanthanum is a method of abutting the above-mentioned fiber web or ruthenium by needle punching, or a fiber mesh or a mat is low. When the low-melting point fiber is used for the low-melting point fiber, the mesh of the mixed fiber is directly used, or the thorn==sheet: heating to soften the low-melting point fiber to bond the fibers to each other (four) to the fiber web or A method for impregnating or mixing a synthetic resin in a crucible or a fiber, a solution, an emulsion, a latex, or a mixture of the above-mentioned fiber web or a mat after mixing or impregnating a synthetic tree Made by the same. Mixing: Liquid, usually before the above fibers are formed into sheets or mats: treatment liquid. Upper: 1 = immersion in the wafer or pad, or coating the above-mentioned imaginary I ammonium and the mixing between the fibers. This ratio can be used: the rentong system adds the polydark acid to the fiber, and uses the expansion. Graphite 瞎, 天, 里/0 ... Μ 50% by mass, using this thermal expansion plus the granules 0.u 50% by mass. The expanded graphite or the granules may be immersed in the treatment liquid without being added to the treatment liquid and additionally mixed in the fiber sheet or the mat or the synthetic resin foam sheet or the syrup. Sheet ~, or hunting by spraying, scraping 'painting, flow coating, etc. on the above sheet or mat 319583 22 200829616 coating the above treatment liquid. The second sheet of the above-mentioned sheet or pad coated with the above-mentioned treatment liquid is subjected to impregnation or mixing of the above treatment liquid, and the sheet or the mat is twisted using a wringer or a platen. m = the sheet mat is impregnated or coated with the above flame retardant treatment liquid, and dried, in the step, if the phenolphthalein resin in the flame retardant treatment liquid is a B-shaped bear, the sheet or the mat is It can be stored for a long time and can be molded at a low temperature for a short time. When the sheet or the mat is used as a surface material, the thickness is set to "face" to 5 mm, and when used as a substrate, the thickness is generally set to _ to 60 mm. [Manufacture of interior materials] The interior material of the present invention is produced. At 7 o'clock, as shown in FIG. 1 , in the (four) molding apparatus 1 composed of the upper mold 2 and the lower mold 3, the silk material 4 is usually the upper side, and the base material 5 is the lower side and is superposed and hot pressed. . (The % resin in the flame-retardant treatment liquid applied or impregnated in the surface material 4 and/or the substrate 5 penetrates the joint surface between the surface material 4 and the substrate 5 to function as an adhesive. However, in addition to this, an adhesive may be applied to the joint surface of the skin seal 4 and the octa base material 5. When the hot melt adhesive powder is used, it may be spread on the joint surface of the surface material 4 and/or the substrate 5. The powder may be coated with the flame-retardant treatment liquid T on the joint surface of the surface material 4 and/or the substrate 5, and the heat-fusible adhesive powder may be dispersed in the flame-retardant treatment. For example, polyethylene, polypropylene, ethylene-acetate acetonitrile copolymer, ethylene-vinyl acrylate copolymer, and other dense hydrocarbons 319583 23 200829616 resin (including modified polyolefin resin), polyurethane (a urethane), a low melting point resin such as a polyester, a polyester copolymer, a polyamide or a polyamine copolymer, or a mixture of two or more kinds thereof. Further, in the present invention, the above-mentioned skin material 4 A thermal melt adhesive film can also be used for bonding to the substrate 5. The film is usually pre-formed. The surface of the surface material 4 or the substrate 5 is adhered to the joint surface. The interior material 7 is formed into a flat shape or as shown in the drawing, and the predetermined shape 1 is usually formed by hot press molding. When the swelled graphite is adhered to the surface material 4 and/or the substrate 5, the pressurization temperature is determined to be lower than the expansion start temperature of the expanded graphite, and the fiber (or) is thermally mixed. The thermal expansion of the thermal expansion (four) granules is limited to the fiber sheet or the whole thickness of the product when the galvanic molding is formed. When the expansion temperature of the body is above, the heat-expandable particles are (4). The fiber sheet or the crucible restricts the expansion of the granular body as described above to compress the density of the surrounding fibers and the fiber portion: However, the void ratio of the entire fiber sheet or mat is not affected by the weight. The above-mentioned hot pressurization, the surface material 4 and the initial condensate of the phenolic resin in the substrate burning treatment liquid are passed through the resin 3 ' And the shape of the shape is fixed, and the shape is maintained and maintained. Period: the compound 'is the variegated resin coating film, thereby blocking == the particles are dissolved in the water' while the poly-disc acid recording particles are firmly:: 2, on the leather material and/or the substrate. The table 319583 24 200829616 is evaporated from the side of the skin material 4 on the upper side by the moisture, the solvent, or the volatile component generated by the synthetic resin contained in the surface material 4 or the substrate 5 by the above-described hot pressing. However, since the ammonium permeate particles are firmly fixed to the surface material 4 and/or the substrate 5, the ammonium polyphosphate does not migrate to the surface of the surface material 4 as the volatile component evaporates. The interior material of the invention can also be used as, for example, a roof material for a car, a trimming of a door, an instrument panel, an acoustic material for an instrument panel, a sound insulation material for a car, a sound insulation material for a hood, a sound insulation material for an engine bottom, a sound insulation material for a cylinder front cover, Internal and external materials for sound insulation materials, bedding, instrument panels, etc. of the instrument panel, or sound absorbing materials, heat insulation materials, building materials, etc. Hereinafter, the present invention will be described in detail by way of a yoke example. However, the invention is not limited to the embodiments shown below. [Example 1] A fiber sheet made of polyester fiber and made into a non-woven fabric having a basis weight of 4 〇g/m by a spunbonding method to achieve the mass% of the fiber sheet; ^"Including and applying 40 mass parts of the initial condensate of the novolac type phenolic resin (solid content: 45 mass% aqueous solution), 2 parts by mass of carbon black (solid two-knife · 30 bergere / water dispersion solution), 3 mass Part of the fluorine-based water-repellent oil-removing agent (solid content: 25 mass% aqueous solution)" mass part of the butterfly internal mold release agent (solid knife, 4 〇 two-massed water dispersion solution), 54 parts by mass of water , on the back side of the Qianwei tablet, by spraying the applicator to achieve the quality of the fiber sheet / 6 coating 'coated by 4 〇 mass parts of the resol phenolic initial condensate ^ mouth ^ knife · 45 Berry% Aqueous solution), 30 parts by mass of ammonium polyphosphate powder (particle size: 30 to 4 〇 / / m, solubility in water: 1 mass% or less), 30 parts by mass 319583 25 200829616 flame retardant treatment of mixed dispersion composed of water After the liquid, the pre-baking was dried at a temperature of 13 ° C for 3 minutes to obtain a flame-retardant fiber sheet. The flame-retardant fiber sheet is used as a skin material, and a glass raw cotton (weight per unit area: 1000 g/m 2 ) which has been coated with 15% by mass of an unhardened resol-type phenol resin is used as a substrate, and the flame-retardant fiber is used. The back of the sheet is laminated with the glass raw cotton, and then at 18 inches. The molded product having a thickness of 10 mm was molded by hot pressing at 200 ° C and 220 ° C for 60 seconds. [Comparative Example 1] The same procedure as in Example 丨 except that the initial condensate of the resol type phenol resin used in the flame retardant treatment liquid of Example 1 was changed to an acrylic copolymer emulsion (solid content: 45 mass% aqueous solution) A molded article 0 having a thickness of 10 mm was obtained [Example 2] except that the initial condensate of the resol type phenolic resin in Example 1 was changed to the acid-based methylated phthalocyanine benzene U-life condensate.

A molded product having a thickness of 10 mm was produced in the same manner as in Example 1 except that. [Example 3] A fiber sheet of a woven fabric having a basis weight of 4 deniers was formed by a needle-punching method to achieve the quality of the fiber sheet 40. "" Immersion coating consists of 4 parts by mass of sulfinic acid methylated phenol-dishyl bisphenol _ furfural initial liquid "mass parts carbon black (solid form::; quality = upper 4,

Fluorine-based water-repellent oil-removing agent (solid content: 25 quality ° two administration / liquid), = quality I internal mold release agent (solid content · 'mass% water dispersion solution:), 5: two t 319583 26 i 200829616 A mixture of water consisting of 30 parts by mass of the sulfinic acid methylated phenol-coated on the back side of the fiber sheet by a sprayer to a coating amount of 3% by mass of the fiber sheet. Alkyl resorcinol-formaldehyde initial condensate (solid content: 45 mass% aqueous solution), 30 parts by mass of ammonium polyphosphate powder (particle size: 3〇 to 4〇# melon, solubility in water: 2% by mass or less ), after 1 part by mass of the polyacid amine powder (particle size: 20 to 30 #m, softening temperature · 13 (rc), 4 parts by mass of water, the mixed dispersion of the flame retardant treatment liquid, 13 〇 χ: The temperature is dried and pre-baked for 3 minutes to obtain a flame-retardant fiber sheet. The flame-retardant fiber sheet is used as a skin material, and the melamine resin foam (thickness: 2 mm, density: 85 kg/m 2 ) It is used as a flame-retardant substrate, and the back surface of the flame-retardant fiber sheet and the melamine resin foam are laminated, and then formed at a temperature of 200 t: for 6 sec to form a film having a thickness of 10 mm. [Comparative Example 2] Except that the sulphite-based sub-base used as the flame-retardant treatment liquid in Example 3 = the initial condensate of the benzene-based benzene n-jun is changed to the polyester copolymer, the amount of the aqueous solution is And Example 3 A molded article having a thickness of 10 mm. Ding [Example 4] For the fiber made of poly-I fiber and made into a single 8 〇g/m non-woven fabric by needle punching, the amount of lining coating is from cold to the outer surface of the fiber sheet 45. Hunting by the coating roller impregnation coating by Dan * Meimen +, Lizhi Shi page 酉夂 methyl methylation - Institute: between the early winter stagnation condensate (solid part of the amount of carbon black (five): 30% by mass Water-dispersed solution, ^2 water-repellent oil-removing agent (solids: 2, squid, squid, water, liquid), 1 part by mass, wax, internal 319583 27 200829616 denucleating agent (solid content: 40% by mass water dispersion) a mixture of 1 part by mass of an anionic surfactant and 53.9 parts by mass of water, and the fiber: 2 pieces of f-face by a sprayer to achieve a coating amount of the fiber 4 3 " 30 parts by mass of the sulfonic acid methylated phenol-alkyl resorcinol-furfural initial condensate (solid content: 45 mass% aqueous solution), and 3 parts by mass ammonium polyphosphate (particle size to 40) #m, solubility in water 〇 5% by mass or less), 10-mass hydrazine copolymerized polyamide powder (particle size: 2 〇 to softening temperature: mt;), 40 parts by mass of water After the flame-retardant treatment liquid of the mixed dispersion liquid of the composition is dried, pre-baking at a temperature of 130 ° for 3 minutes to obtain a flame-retardant fiber sheet. The flame-retardant fiber sheet is used as a skin material, and an expansion stone is added. The polyurethane foam (thickness: 30 mm, density: 15 kg/m2) is used as a flame-retardant ruthenium substrate, and the back surface of the flame-retardant fiber sheet and the aggregated vinegar foam to which the expanded graphite is added are laminated. Further, a molded product having a thickness of 1 mm was formed by hot pressing at a temperature of 18 (TC for 4 sec.) [Comparative Example 3] V In addition to the sulfonic acid thiolated phenol used in the flame retardant treatment liquid of Example 4. A molded product having a thickness of 1 mm was produced in the same manner as in Example 4 except that the alkyl sulphate-formaldehyde initial condensate was changed to ethylene-vinyl acetate oligopolymer emulsion (solid content: 45 mass% aqueous solution). [Comparative Example 4] A molded product having a thickness of 1 mm was produced in the same manner as in Example 1 except that the solubility of the ammonium polyphosphate powder in Example 1 was changed to water. [Forming test] Examples 1 and 2 were prepared. 3, 4 and the molded articles prepared in Comparative Examples i, 2, 3, and 4, 319583 28 200829616, were placed at room temperature, and observed. Skin whitening strip surface state after each of the time over which the results shown in Table 1. [Table 1] a molding temperature (° c)

Good

State I, white I, face j, material I, skin, one table, I, time, I

Day I

XXX days 〇o©x>Ax>©@©©x©xxxxxxxx

XXX

〇 Δ X A little whitening The surface area of the skin material is about 0.5 to 1% whitening. The surface area of the skin material is about 2 to 5%, and the total whitening XX: the surface area of the skin material is about 8 to 10%. Whitening is shown in Table 1. The use of the ammonium polyphosphate particles in the phenolic resin 7j solution is blocked by the present invention. The surface of the molded product of the flammable treatment liquid did not have a whitening phenomenon of 4 319 583 29 200829616. It was found from the first embodiment and the second embodiment that the phenolic resin and the benzoic acid co-condensation were lower than the phenol resin alone, and the effect was also good. [Example 5] 70% by mass of kenaf fiber, 1% by mass of polylactic acid fiber, and a low-melting polyester fiber having a core-sheath structure (softening point: 130. 〇20% by mass is made into a thickness by an opener) After 4 mm of a mesh sheet having a basis weight of 6 〇〇g/m2, the mesh sheet was blown with hot air of 1% of it for 20 seconds while being evacuated in a hot air furnace to melt the low melting point. The polyester fiber is used to bond the fibers to each other to obtain a fiber sheet having a thickness of 35 mm and an apparent density of 2 〇kg/m 3 . Secondly, the fiber sheet is impregnated by a coating roller to achieve a coating amount of 35 mass % of the fiber sheet. From 40 parts by mass of the acid group methyl (tetra)-pyristylbenzene (4) disk: condensate (solid content: 4G mass% aqueous solution), 25 mass parts of polywei powder particle size: 3〇 to 40#m, The solubility in water: 1% by mass or less), the flame retardant treatment liquid of the mixed dispersion composed of 35 parts of water, and dried at a temperature of 11 〇 for 1 minute to obtain a thickness of 2 〇. a pre-baked flame-retardant fiber substrate of 111111. The flame-retardant fiber sheet obtained in Example 4 is used as a skin material, and the flame-retardant fiber is used. The back surface of the sheet is laminated with the curable fibrous base material, and then molded at a temperature of 9 Gsec to obtain a molded product having a predetermined shape. The flame retardancy of the molded product is UL94-compliant, sound absorbing property and water resistance. The weather resistance is excellent, and the surface of the surface material does not appear white; the 匕 phenomenon can be used as an inner and outer member of an automobile. [Example 6] A unit made of poly ray fiber and made by needle punching has a weight per unit area of 319583 30 200829616 After calendering treatment of the back surface of the 9W non-woven fabric, the calendered surface was coated with an acrylic acid copolymer emulsion at a coating amount of 50 g/m 2 and dried to form a uniform coating film. Secondly, the surface of the film formed thereon was formed. By spraying with a sprayer to achieve a coating amount of 40% by mass of the fiber sheet, it is coated with 30 parts by mass of sulphuric acid base. The condensate base benzoic acid powder_formic acid initial condensate (solid knife. 45 ber. % aqueous solution) ), 3 parts by mass of ammonium polyphosphate powder (particle size: 3 〇 to 4 〇 / zm, solubility in water · 2 mass % or less), 1 part by mass of copolymerized guanamine powder (particle size: 20 to 30 (four) , softening temperature: 13 〇. 混合, 4 〇 mass parts of water mixed dispersion The flame retardant treatment liquid of the liquid is pre-baked for 13 minutes with a temperature of 13 而 to obtain a flame-retardant fibrous sheet surface material, and the substrate Z ^ is 7% by mass of the kenaf fiber by the opening machine. Polyurethane fiber enamel!%, and core-sheath type low melting point polyester fiber (softening point: 13 〇. 〇2 〇 quality!% opening to make thickness 40mm, unit area weight 5〇〇g/m2 After the mesh sheet is blown, the hot air of the mesh material is blown with a hot air of 135 ° C for 20 seconds in a hot air oven to melt the low melting point fibers, and the fibers are bonded to each other to obtain a thickness of 35 mm and an apparent density. It is a "/" fiber sheet. Secondly, the fiber sheet is impregnated and coated with 40 parts by mass of sulfonic acid methylated phenol_alkyl resorcinol by a coating amount of 35 mass% of the fiber sheet. Formaldehyde initial condensate (solid content: 40% by mass aqueous solution), 25 parts by mass of ammonium: end (particle size: 30 to 40 / ζ π, solubility in water: 1% by mass or less), % 夤 1 part of water The flame retardant treatment liquid of the dispersion liquid is mixed, and dried at a temperature of 10 minutes while being evacuated to obtain a pre-flooded flame-retardant fiber sheet substrate.Further, the obtained flame-retardant fiber substrate and the flame-retardant fiber sheet skin material were laminated and set at 200. The temperature of the crucible is hot pressed for 9 seconds to form a molded product. 319583 31 200829616 A molded product having a predetermined shape is obtained. This molding (4) Μ (10) is like 4 m V 〇 ‘ 曰 曰 ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异(Industrial Applicability) The flame-retardant treatment liquid of the present invention can be provided at low cost, and is particularly useful for interior and exterior of automobiles because it imparts flame retardancy to the surface material or substrate treated by the treatment liquid. Loading materials. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a hot pressing step. [Main component symbol description] 1 Press molding device 2 Upper die 3 Lower die 4 Skin material 5 Substrate

319583 32

Claims (1)

200829616 X. Patent application scope: 1. A kind of flame retardant treatment liquid, characterized in that: (4) in the aqueous solution of the tree wax, the dispersion is dissolved in water;; ammonium phosphate particles. Baili from the next poly 2 · For example, the patented Fan Yi 1 W brother 1 flame retardant treatment liquid, in which the initial condensate of the resin is transmitted more than the initial condensate of the phenol. On the same day, 3·= the flame-retardant treatment liquid of the first or second patent application scope, (4) the initial condensate is methylated by lysyl sulfinate. The long-term/sub-Asian (=, the flame-retardant treatment of the patent range "to the third item" - the water-soluble resin as a dispersing agent is added to the aqueous solution of the initial condensate of the variegated resin. 5. A flammable fibrous material characterized by being formed by mixing or coating a fiber sheet or mat of a flame-retardant treatment liquid of any one of items 1 to 4 of the application range. The inner material is characterized in that the flame-retardant fiber material of the patent application scope item (#) is adhered to the surface of the substrate as a surface material, and is formed into a predetermined shape. 7·If the material is in the sixth item of the patent application scope Wherein the skin material and the substrate are bonded by a hot melt adhesive film or a hot melt adhesive powder. 319583 33