Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
  • D06M13/453—Phosphates or phosphites containing nitrogen atoms

Definitions

• the present invention relates to a flame retardant processing chemical, a method for producing a flame retardant fiber, and a flame retardant fiber.
• a flame-retardant processing agent in which a bromine-based or phosphorus-based flame retardant is dispersed or emulsified in water at the time of dyeing is placed in a bath, and heat treatment is performed while the fiber material is immersed.
• a method of attaching a flame retardant is used (for example, Patent Documents 1 and 2).
• Patent Documents 1 and 2 a method of attaching a flame retardant.
• this method since the adhesion efficiency of the flame retardant to the fiber material is low, it is necessary to treat in large quantities, and the flame retardant that does not adhere to the fiber material has a problem of being discharged into the environment.
• this method is problematic in that the flame retardant inhibits dyeing, so that the color changes or stains (spec stains) or kettle stains (can body contamination) occur on the fiber material.
• a flame retardant processing agent in which a phosphoric flame retardant such as guanidine phosphate or carbamate phosphate is dispersed, emulsified or dissolved in water is applied to the fiber material. Then, a heat treatment method is taken (for example, Patent Documents 3 and 4).
• a heat treatment method is taken (for example, Patent Documents 3 and 4).
• the flame retardant property is higher than that in the dyeing method, and the phosphorus-based flame retardant is not easily discharged into the environment.
• the flame retardant since the flame retardant is not exhausted inside the fiber material, if water adheres to the fiber material, the fire retardant (ring-like spots) due to the flame retardant is generated after drying.
• a phosphorus flame retardant when a phosphorus flame retardant is used in an automobile interior material, if a snow melting agent (calcium chloride) adheres to the interior material, the phosphorus flame retardant reacts with the snow melting agent (calcium chloride) and becomes a white calcium insoluble material. The problem of whitening of the fiber material occurs.
• An object of the present invention is to impart good flame retardancy to a fiber material, and to suppress the occurrence of wrinkles (ring-shaped spots) when water adheres to the fiber material and dries, and a snow melting agent is added to the fiber material.
• a flame retardant processing agent capable of suppressing the occurrence of whitening when (calcium chloride) adheres
• a method for producing a flame retardant fiber using the flame retardant processing agent, and a flame retardant fiber obtained by the production method It is.
• the present inventors have found that the above-mentioned problems can be solved if the flame retardant processing agent essentially contains a specific acidic phosphate ester or a salt thereof.
• this invention is a flame retardant processing chemical
• medical agent which essentially contains acidic phosphate ester or its salt, Comprising:
• the said acidic phosphate ester or its salt is a compound represented by following General formula (1).
• R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
• An aryl group, and R 1 and R 2 may be connected to each other through an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring
• M 1 is a hydrogen atom, an alkaline group
• M 2 is A hydrogen atom or an alkaline group
• m and n are each independently an integer of 1 to 3.
• R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. It is an aryl group, and R 1 and R 2 may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring, and m is an integer of 1 to 3.
• R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• M 1 is a hydrogen atom, an alkaline group, a functional group represented by the general formula (2) or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Is preferred.
• the present inventors have found that the above-mentioned problems can be solved if they are flame retardant processing agents that essentially contain the following specific acidic phosphate ester or salt thereof.
• the headline the present invention has been reached. That is, the present invention is a flame retardant processing agent that essentially contains an acidic phosphate ester or a salt thereof, wherein the acidic phosphate ester contains a hydroxyl group-containing compound containing a compound represented by the following general formula (3): It is formed by phosphoric esterification.
• R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 6 to 12 carbon atoms.
• An aryl group, and R 3 and R 4 may be linked to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring, where l is an integer of 1 to 3.
• R 3 and R 4 are preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• the hydroxyl group-containing compound further includes a compound represented by the following general formula (4).
• R 5 is an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• R 5 is preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• the flame retardant processing agent of the present invention preferably further contains an alkyl acidic phosphate ester or a salt thereof.
• the flame retardant processing chemical of the present invention is preferably used for vehicle interior materials.
• the manufacturing method of the flame-retardant fiber of this invention includes the process of processing said flame-retardant processing chemical
• the flame-retardant fiber of the present invention is a fiber material in which the above-mentioned flame-retardant processing chemical is adhered.
• the flame retardant processing agent of the present invention can impart good flame retardancy to the fiber material by containing a specific acidic phosphate ester or a salt thereof as an essential component. Moreover, generation
• the flame retardant fiber obtained by the method for producing a flame retardant fiber of the present invention or the flame retardant fiber of the present invention is treated with the above flame retardant processing agent, and thus has good flame retardancy.
• a snow melting agent calcium chloride
• the flame retardant processing chemical of the present invention essentially contains a specific acidic phosphate ester or salt thereof, and the acidic phosphate ester or salt thereof is a compound represented by the above general formula (1).
• 1 type may be sufficient as the compound represented by the said General formula (1), and it may contain 2 or more types.
• acidic phosphate ester means the phosphate ester or condensed phosphate ester which has at least 1 acidic hydroxyl group in a molecule
• R 1 and R 2 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number. 6 to 12 aryl groups, and R 1 and R 2 may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring.
• R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent from the viewpoint that excellent flame retardancy can be imparted to the fiber material.
• a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
• M 1 is a hydrogen atom, an alkaline group, a functional group represented by the general formula (2), an alkyl group having 1 to 6 carbon atoms which may have a substituent, or 2 carbon atoms.
• M 1 is a carbon atom which may have a hydrogen atom, an alkaline group, a functional group represented by the above general formula (2), or a substituent from the viewpoint that excellent flame retardancy can be imparted to the fiber material.
• a C 1-6 alkyl group is preferable, a hydrogen atom or an alkaline group is more preferable, and a hydrogen atom or a guanidine salt is further preferable.
• M 2 is a hydrogen atom or an alkaline group.
• M 2 is preferably a hydrogen atom, an ammonium salt, an organic amine salt, a quaternary ammonium salt, a melamine salt, or a guanidine salt from the viewpoint that excellent flame retardancy can be imparted to the fiber material. More preferably, it is a guanidine salt.
• m and n are each independently an integer of 1 to 3.
• M is preferably 2 from the viewpoint that excellent flame retardancy can be imparted to the fiber material, and the volatility is small, and in the use of vehicle interior materials, the glass is clouded by volatilization of the flame retardant. From the viewpoint of excellent hydrolysis resistance, n is preferably 1.
• R 1 and R 2 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number. 6 to 12 aryl groups, and R 1 and R 2 may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring.
• m is an integer of 1 to 3. The preferred ranges of R 1 , R 2 and m are the same as those for R 1 and R 2 in the general formula (1).
• alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and the like.
• alkenyl group having 2 to 6 carbon atoms examples include a propenyl group.
• a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferable, a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable, and a methyl group, an ethyl group, Groups are more preferred.
• Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, and an alkylaryl group (tolyl group, xylyl group, cumyl group, methylnaphthyl group, etc.).
• a phenyl group and an alkylaryl group are preferable, a phenyl group and a tolyl group are more preferable, and a phenyl group is more preferable.
• the above substituents include a hydroxyl group, an amino group, and the like.
• Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a hydroxymethyl group, a 2-hydroxyethyl group, and a 2-hydroxypropyl group. Of these, a 2-hydroxyethyl group is preferable.
• R 1 and R 2 are connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring (hereinafter sometimes simply referred to as a cyclic group)
• examples of the cyclic group include a piperidino group Pyridine group, morpholino group, imidazole group and the like. Among these, a morpholino group is preferable.
• alkaline group examples include alkali metal salts, alkaline earth metal salts, metal salts, ammonium salts, organic amine salts, quaternary ammonium salts, melamine salts, guanylurea salts, guanidine salts and the like.
• alkali metal examples include sodium, potassium, lithium and the like.
• alkaline earth metal examples include magnesium, calcium, and barium.
• the metal examples include zinc, aluminum, and zirconium.
• Organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, monoethylamine, diethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, Monomethylethanolamine, dimethylethanolamine, monoethylethanolamine, diethylethanolamine, tris (hydroxymethyl) aminomethane, etc.), polyamine (ethylenediamine, diethylenetriamine, polyethyleneimine, dicyandiamide condensate, dicyandiamide and polyalkylenepolyamine condensate, Condensation of dicyandiamide, polyalkylenepolyamine and urea Condensates of dicyandiamide with formaldehyde and the like) and the like.
• alkylamines trimethylamine, triethylamine, monomethylamine, dimethylamine,
• quaternary ammonium examples include tetramethylammonium, tetraethylammonium, tetramethanolammonium, and tetraethanolammonium.
• the alkaline group is preferably an ammonium salt, an organic amine salt, a quaternary ammonium salt, a melamine salt, a guanylurea salt, or a guanidine salt, more preferably an ammonium salt, an organic amine salt, or a guanidine salt, and further a guanidine salt. preferable.
• the flame retardant processing agent of the present invention essentially contains an acidic phosphate ester or a salt thereof, and the acidic phosphate ester contains a hydroxyl group-containing compound containing a compound represented by the above general formula (3). It is formed by acid esterification.
• the hydroxyl group-containing compound refers to a component having a hydroxyl group in the molecule and capable of constituting phosphoric acid and an ester.
• the compound represented by the general formula (1) is formed by phosphorylating a hydroxyl group-containing compound including the compound represented by the general formula (3) (or neutralizing the acidic phosphate ester). ).
• the hydroxyl group-containing compound essentially contains the compound represented by the general formula (3).
• R 3 and R 4 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number. 6 to 12 aryl groups, and R 3 and R 4 may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring.
• Examples and preferred ranges of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the cyclic group which may have a substituent include those represented by the general formula (1).
• R ⁇ 1 >, R ⁇ 2 > can be mentioned.
• R 3 and R 4 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent from the viewpoint that excellent flame retardancy can be imparted to the fiber material.
• a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.
• l is an integer of 1 to 3, and l is preferably 2 from the viewpoint that excellent flame retardancy can be imparted to the fiber material, and because it has low volatility and is excellent in the problem of fogging in vehicle interior materials.
• Examples of the compound represented by the general formula (3) include monoethanolamine, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, butylaminoethanol, dibutylaminoethanol, diethylaminoethanol, monoisopropanolamine, dimethylaminopropanol, diethylaminopropanol , Diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine and the like.
• monoethanolamine methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, monoisopropanolamine, diethanolamine, and triethanolamine are preferable, and monoethanolamine, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, and diethanolamine are preferable. More preferred is monoethanolamine.
• the proportion of the compound represented by the general formula (3) in the entire hydroxyl group-containing compound is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and further preferably 65 to 100 mol%.
• the hydroxyl group-containing compound is represented by the above general formula (4) because the pH of the flame retardant processing agent can be adjusted and the occurrence of whitening when the snow melting agent (calcium chloride) adheres to the fiber material can be suppressed. It is preferable that a compound is further included.
• R 5 is an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• Examples and preferred ranges of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, and the aryl group having 6 to 12 carbon atoms which may have a substituent include R 1 in the general formula (1), it can be exemplified similar to that described in R 2.
• R 5 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of imparting excellent flame retardancy to the fiber material and excellent resistance to wrinkles.
• a methyl group is more preferable.
• Examples of the compound represented by the general formula (4) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1- Examples include hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol propanol, ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol and the like.
• methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, ethylene glycol, and propylene glycol are preferable, and methanol, ethanol, and ethylene glycol , Propylene glycol is more preferable, and methanol and ethanol are more preferable.
• the proportion of the compound represented by the general formula (3) in the entire hydroxyl group-containing compound is preferably 30 to 99 mol%. 50 to 99 mol% is more preferable, and 65 to 95 mol% is more preferable.
• the proportion of the compound represented by the general formula (4) in the total hydroxyl group-containing compound is preferably 1 to 70 mol%, more preferably 1 to 50 mol%, and further preferably 5 to 35 mol%.
• the total proportion of the compound represented by the general formula (3) and the compound represented by the general formula (4) in the hydroxyl group-containing compound is preferably 35 to 100 mol%, more preferably 50 to 100 mol%, More preferred is ⁇ 100 mol%.
• the hydroxyl group-containing compound is a trihydric or higher polyhydric alcohol (except for the compound represented by the general formula (3) and the compound represented by the general formula (4)) as long as the effects of the present invention are not impaired. It may contain.
• the trihydric or higher polyhydric alcohol include sorbitol, sorbitol, sorbide, sorbitan, pentaerythritol, trimethylolpropane, glycerin, xylitol, erythritol, saccharides and the like.
• the proportion of the polyhydric alcohol in the total hydroxyl group-containing compound is preferably 0.1 to 20 mol%, more preferably 0.1 to 10 mol%, and further preferably 0.1 to 5 mol%.
• An acidic phosphate ester obtained by converting a hydroxyl group-containing compound into a phosphate ester reacts with a hydroxyl group-containing compound and phosphoric anhydride, phosphoric acid, condensed phosphoric acid (eg, pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid)), etc. It means an acidic phosphate ester obtained.
• phosphoric acid esterification A well-known method is employable.
• the reaction composition may vary depending on the reaction conditions such as the charging method, charging order, reaction temperature, reaction time, reaction pressure, etc. of each component, but the reaction conditions are not limited, and multiple reactants can be mixed. Also good.
• the reaction temperature is usually 0 to 200 ° C., and the reaction time is usually 0.1 to 20 hours.
• the reaction product is a mixed ester mainly composed of the monoester, diester, and condensed phosphate ester represented by the general formula (1).
• phosphoric acid, condensed phosphoric acid pyrophosphoric acid, polyphosphoric acid ( Metaphosphoric acid) etc.
• phosphoric acid, condensed phosphoric acid may remain as unreacted substances or may be by-produced. These ratios are various and are not particularly limited.
• By-product phosphoric acid and condensed phosphoric acid are by-produced because a calcium insoluble matter may be generated by reaction with a snow melting agent (calcium chloride). Less phosphoric acid and condensed phosphoric acid are preferred.
• the ratio of phosphoric acid and condensed phosphoric acid to the compound represented by the general formula (1) is preferably 0 to 30% by weight, and more preferably 0 to 10% by weight.
• the reaction molar ratio of the hydroxyl group-containing compound and the phosphorus element is not particularly limited, but is usually 1.5 / 1 to 1/1. If it is larger than 1.5 / 1, the hydroxyl group-containing compound is likely to remain unreacted, which may adversely affect fogging and bleeding properties. On the other hand, if the ratio is less than 1/1, the amount of condensed phosphate increases, but phosphoric acid, condensed phosphoric acid (such as pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid), etc.) remain as unreacted substances, or are by-produced. It becomes easy.
• the reaction molar ratio of the hydroxyl group-containing compound and phosphorus element is usually 1.5 / 1, and the molar ratio of the monoester to diester to be formed is about 1/1. It is.
• the phosphorous element source includes phosphoric acid, condensed phosphoric acid (eg, pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid))
• the reaction molar ratio between the hydroxyl group-containing compound and the phosphorous element is usually smaller than 1.5 / 1, Usually 1.5 / 1 to 1/1.
• the molar ratio of the monoester and diester produced at this time is usually 1/1 to 1/0.
• the obtained acidic phosphate ester can be neutralized by adding an alkali or the like as necessary to obtain a salt of the acidic phosphate ester.
• alkali include sodium hydroxide, potassium hydroxide, sodium phosphate, sodium tripolyphosphate, sodium carbonate, ammonia, alkylamine (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamine (monoethanolamine, diethanolamine, triethanolamine).
• Ethanolamine monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethylethanolamine, tris (hydroxymethyl) aminomethane, etc.
• polyamine ethylenediamine, diethylenetriamine, polyethyleneimine, dicyandiamide condensate, dicyandiamide and poly Condensates of alkylene polyamines, dicyandiamide and polyalkylene polyamines And condensates of urea, dicyandiamide condensation products of formaldehyde and the like), guanyl urea, guanidine, guanidine carbonate, melamine, and the like.
• ammonia, alkylamine, alkanolamine, guanidine, guanidine carbonate, and melamine are preferable, ammonia, alkylamine, alkanolamine, guanidine, and guanidine carbonate are more preferable, and guanidine and guanidine carbonate are more preferable.
• the neutralization is preferably performed so that the pH of the flame retardant processing chemical is 3-7.
• a diluent, a solvent, or the like can be used.
• the diluent and solvent include water, hydrocarbon (hexane, cyclohexane, etc.), ketone (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon (toluene, xylene, etc.), acid (phosphoric acid, sulfuric acid, etc.), ether ( Diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, etc.), esters (ethyl acetate, dimethyl sulfate, trimethyl phosphate, diethyl phosphate, etc.) and the like.
• hydroxyl group-containing compound when converted to a phosphoric ester, other components other than those described above can be used.
• a catalyst, an antioxidant, a light stabilizer, a coloring inhibitor, an antifoaming agent, a flame retardant and the like can be mentioned.
• the flame retardant processing chemical of the present invention is not particularly limited as long as it contains the above acidic phosphate ester or a salt thereof.
• the proportion of acidic phosphate ester or salt thereof in the total flame retardant processing chemical is preferably 0.01 to 100% by weight, more preferably 0.1 to 70% by weight.
• the flame retardant processing agent of the present invention preferably contains water in order to impart flame retardancy to the fiber material.
• the water may be pure water, distilled water, purified water, soft water, ion exchange water, industrial water, well water, tap water, or the like.
• the ratio of water in the total flame retardant processing chemical is preferably 0.01 to 99.9% by weight, and more preferably 30 to 99.9% by weight.
• a component comprising an acidic phosphate ester or a salt thereof other than the above acidic phosphate ester or a salt thereof (hereinafter sometimes referred to as the component (A)), because of its excellent resistance to kicking. It is preferable that (B) is included.
• the component (A) is an acidic phosphate ester formed by phosphorylating a hydroxyl group-containing compound including the compound represented by the general formula (1) and the compound represented by the general formula (3). It means at least one selected from the salts.
• an acidic phosphate ester obtained by converting the compound represented by the general formula (4) into a phosphoric ester or a salt thereof can be exemplified, and is represented by the general formula (4). It can be obtained by reacting a compound with phosphoric anhydride, phosphoric acid, condensed phosphoric acid (such as pyrophosphoric acid or polyphosphoric acid (metaphosphoric acid)) and the like.
• phosphoric acid esterification A well-known method is employable similarly to the above-mentioned.
• Examples of the acidic phosphate ester of component (B) include alkyl acidic phosphate esters (methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, etc. ), Acidic phosphate esters such as 2-hydroxyethyl phosphate, and salts thereof.
• alkyl acidic phosphate esters methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, etc.
• Acidic phosphate esters such as 2-hydroxyethyl phosphate, and salts thereof.
• the salt may be an alkali metal salt, alkaline earth metal salt, ammonium salt, organic amine salt, quaternary ammonium salt, metal salt, melamine salt, guanidine salt, or the like.
• alkali metal include sodium, potassium, lithium and the like.
• alkaline earth metal include magnesium, calcium, and barium.
• Organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethyl) Ethanolamine, etc.), polyamines (ethylenediamine, diethylenetriamine, polyethyleneimine, dicyandiamide condensate, dicyandiamide and polyalkylenepolyamine condensate, dicyandiamide, polyalkylenepolyamine and urea condensate, dicyandiamide and formaldehyde condensate, etc.) It is done.
• Examples of quaternary ammonium include tetramethylammonium, tetraethylammonium, tetramethanolammonium, and tetraethanolammonium.
• Examples of the acidic phosphate ester salt of component (B) include methyl guanidine phosphate, dimethyl guanidine phosphate, and methyl monoethanolamine phosphate.
• alkyl acid phosphates or salts thereof are preferred from the viewpoint of excellent flame retardancy and excellent resistance to wrinkles.
• Methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, phosphorus Isopropyl acid, diisopropyl phosphate or a salt thereof is more preferable, and methyl phosphate, dimethyl phosphate or a salt thereof is more preferable.
• the weight ratio of component (A) to component (B) (component (A) / component (B)) is preferably 99/1 to 1/99, more preferably 99/1 to 40/60, and 95/5. More preferred is 60/40.
• the weight ratio of the component (A) in the nonvolatile content of the flame retardant processing chemical of the present invention is preferably 1 to 100% by weight, more preferably 30 to 100% by weight, and further preferably 60 to 95% by weight.
• the non-volatile content is measured when a certain amount of sample is spread flat on an aluminum sheet and dried at 110 ° C. under irradiation with an infrared lamp, and the fluctuation range of volatile content for 150 seconds becomes 0.15% by weight. It is the remainder when it is set as the end point of.
• the flame retardant processing agent of the present invention is phosphoric acid, condensed phosphoric acid (pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid)) in order to further suppress the occurrence of whitening when a snow melting agent (calcium chloride) adheres to the fiber material.
• Etc.) and at least one component (C) selected from these salts is preferably substantially not contained.
• the weight ratio of the component (C) in the nonvolatile content of the flame retardant processing chemical is preferably 30% by weight or less, more preferably 10% by weight or less, and further preferably 1% by weight or less.
• the component (C) include phosphate carbamate, polyphosphate carbamate, ammonium polyphosphate salt, guanidine phosphate salt, and guanylurea phosphate salt.
• the flame retardant processing chemical of the present invention may contain components other than those described above as long as the effects of the present invention are not impaired.
• Other components include, for example, solvents (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pen Tanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2 -Methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether,
• the ratio of the solvent in the whole flame retardant processing chemical is preferably 20% by weight or less. There is no limitation in particular about the content rate of said other component other than that.
• the pH of the flame retardant processing chemical of the present invention is not particularly limited, but is preferably 1 to 9, more preferably 3 to 7, from the viewpoint of the stability of the flame retardant processing chemical.
• the flame retardant processing chemical of the present invention is preferably composed of water and components that dissolve in water. If an insoluble component is contained in water, problems such as poor product stability and uneven adhesion during processing may occur. In addition, if a surfactant or the like is used to dissolve, emulsify, or disperse components insoluble in water, the bleed property may be poor.
• the method for producing the flame retardant processing chemical of the present invention is not particularly limited, and a known method can be adopted.
• it can be produced by adding water to the above acidic phosphate ester or a salt thereof and dissolving it, and adding other components as necessary.
• the flame retardant processing agent of the present invention is not limited to a target material as long as the effects of the present invention can be exhibited, but it is preferably used for imparting flame retardancy to a fiber material. That is, the flame retardant processing agent of the present invention is preferably for fibers. Although there is no limitation in particular about the usage form of the flame retardant processing chemical
• the manufacturing method of the flame-retardant fiber of this invention includes the process (processing process) which processes the said flame-retardant processing chemical
• Textile materials include natural fibers such as cotton, hemp, wool, silk, polyester, nylon, polyamide, polyacryl, polyvinyl chloride, polyvinyl alcohol, polyurethane, polyimide, rayon, diacetate, triacetate, polyarylate, polylactic acid, Examples thereof include synthetic fibers such as polyethylene and polypropylene.
• it is a fiber material containing synthetic fibers such as polyester, nylon, polyamide, polyacryl, polyvinyl chloride, polyvinyl alcohol, polyurethane, polyimide, rayon, diacetate, triacetate, polyarylate, polylactic acid, polyethylene, polypropylene, More preferably, it is a fiber material containing polyester.
• polyester examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sodiosulfoisophthalate polyethylene / polyoxybenzoyl terephthalate, polybutylene.
• polyester examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sodiosulfoisophthalate polyethylene / polyoxybenzoyl terephthalate, polybutylene.
• examples include terephthalate / isophthalate.
• the fiber material may be composed of only one kind or plural kinds. It may be either blended or woven.
• the form of the fiber material is not limited, and examples thereof include yarn, woven fabric, knitted fabric, nonwoven fabric, rope, and string.
• Components such as dyes, pigments, other flame retardants, ultraviolet absorbers and matting agents may be attached to the fiber material in advance.
• the dye include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, and the like, preferably disperse dyes and cationic dyes.
• a disperse dye is more preferable.
• the disperse dye is not particularly limited, and known dyes can be used. Examples include Sumikaron dyes, Kayalon Polyester dyes, Miketon Polyester dyes, Palanil dyes, Dianix dyes, TD dyes, Kiwalon Polyester dyes, Terasil dyes, Foron dyes, and Serilene dyes.
• flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, cresyl Dixylenyl phosphate, dicresyl xylenyl phosphate, triisopropylphenyl phosphate, diphenylxenyl phosphate, phenyldixenyl phosphate, diphenylorxenyl phosphate, phenyldiorxenyl phosphate, triorxenyl phosphate, trimetaxenyl Phosphate, triparaxenyl phosphate, trixenyl phosphate, ⁇ Naphthyl
• UV absorbers include 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole 2- ⁇ 2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetraphthalimidomethyl) -5′-methylphenyl ⁇ benzotriazole, 2- [2′-hydroxy, 4′- (2 ′′ -hydroxy) butoxyphenyl] -5-chlorobenzotriazole, 2- (2 ′, 4′-dihydroxy-5′-benzoylphenyl) -5-chlorobenzotriazole, 2- (2 ′, 4′-dihydroxy -3'-benzoylphenyl) -5-chlorobenzotriazole, 2- (3'-benzoyl-2'-hydroxy-5'-methylphenyl) benzotri Benzotriazole ultraviolet absorbers such as sol; benzophenones such
• the treatment step is a step of bringing the acid phosphate ester or salt thereof of the present invention into contact with the fiber material by bringing the flame retardant processing agent into contact with the fiber material.
• the fiber material is immersed in a flame-retardant processing agent or a bath obtained by diluting the flame-retardant processing agent with water (treatment bath), and the acidic phosphate ester or salt thereof of the present invention is adhered to the fiber.
• the material is heat treated and dried.
• the heat treatment temperature is preferably 20 to 230 ° C., more preferably 90 ° C. to 200 ° C.
• the heat treatment time is preferably 0.1 to 120 minutes.
• the adhesion can be performed by a padding method, a spray method, a coating method, or the like.
• the heat treatment may be either dry heat treatment or wet heat treatment. Examples of the adhesion heat treatment method include pad-dry, spray-dry, spray-dry-cure, pad-dry-steam, pad-steam, pad-dry-cure, and the like.
• the treatment step for example, by immersing the fiber material in a bath obtained by diluting a flame retardant processing agent with water, the acid phosphate ester or a salt thereof of the present invention is imparted to the fiber material, and the fiber material is used.
• heat treatment can be performed at 30 ° C. or higher for 2 to 120 minutes to impart durability.
• This processing step can be performed using, for example, a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.
• the pH of the treatment bath is preferably 1 to 9, and more preferably 3 to 7.
• the treatment bath in the treatment step may contain other components in addition to the above without impairing the effects of the present invention.
• the method for producing a flame-retardant fiber of the present invention preferably includes a step (scouring step) of scouring the fiber material before the treatment step of the flame-retardant processing chemical.
• scouring step By carrying out the scouring treatment, impurities such as spinning oil, spinning oil, knitting oil, weaving oil, glue and the like can be removed, and flame retardancy is improved.
• the scouring treatment method is not particularly limited, but heat treatment is performed at 50 ° C. or more for 1 to 120 minutes in a state where the fiber material is immersed in a bath diluted with water, and scouring, washing, rinsing, dehydration, drying and the like are performed. For example, it can be performed using a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.
• the method for producing a flame-retardant fiber of the present invention includes a processing step of processing a dye, the above-mentioned other flame retardant, an ultraviolet absorber, or the like on the fiber material before the processing step of the flame-retardant processing agent. It is preferable. In the case of a processing step accompanied by adhesion of other components, usually, flame retardancy, wrinkles, bleeding properties, etc. are reduced, but the method for producing flame retardant fibers of the present invention suppresses these performance degradations. Therefore, it is preferable to have other processing steps.
• the flame-retardant processing chemical treatment process is performed after these processing steps, thereby inhibiting dyeing and changing the color, as well as stains on fabric materials (spec stains) and kettle stains (can body contamination). Can solve the problem.
• the fiber material is immersed in a bath diluted with water to impart them, and heat treatment is performed at 80 ° C. or higher for 2 to 120 minutes in the state where the fiber material is immersed. Impart durability. For example, it can be performed using a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.
• the processing step may be performed in the same bath as the above-described scouring step.
• a synthetic resin emulsion such as an acrylic resin or a urethane resin or a synthetic resin solution may be processed after the processing step of the flame-retardant processing chemical.
• a coating, a pad, spray processing etc. can be mentioned.
• an air knife coater, a roll coater, a blade coater, a bar coater, a brush coater, a gravure coater or the like can be used.
• the synthetic resin emulsion or the synthetic resin solution may contain other components such as other flame retardants.
• the flame-retardant fiber of the present invention is obtained by the method for producing a flame-retardant fiber of the present invention.
• the amount of the acid phosphate ester or salt thereof of the present invention attached to the fiber material is the type and structure of the fiber material, the type and amount of other fiber processing agents attached to the fiber material. However, it is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 20% by weight, more preferably from 0.1% to 20% by weight based on the flame retardant fiber (whole fiber including deposits). 5 to 10% by weight is more preferable.
• the adhesion amount is less than 0.01% by weight, sufficient flame retardancy may not be imparted to the fiber material.
• the amount of adhesion exceeds 30% by weight, the resulting flame-retardant fiber may have a poor texture and may not be economical.
• the flame retardant fiber of the present invention preferably contains a dye.
• the dye include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, and the like, preferably disperse dyes and cationic dyes.
• a disperse dye is more preferable.
• the attached amount of the dye is preferably 0.001 to 50% by weight, more preferably 0.01 to 20% by weight, and further preferably 0.1 to 10% by weight with respect to the flame-retardant fiber.
• the flame retardant fiber of the present invention preferably contains an ultraviolet absorber.
• the content of the ultraviolet absorber is preferably from 0.01 to 10% by weight, more preferably from 0.01 to 3% by weight, even more preferably from 0.05 to 1% by weight, based on the flame retardant fiber.
• the flame retardant fiber of the present invention may contain other flame retardants other than the acidic phosphate ester of the present invention or a salt thereof as long as the effects of the present invention are not impaired.
• the flame retardant fiber of the present invention preferably contains an acidic phosphate ester or salt thereof other than the acidic phosphate ester or salt thereof of the present invention.
• Salts such as methyl phosphate and dimethyl phosphate are preferred, and examples thereof include methyl guanidine phosphate and dimethyl guanidine phosphate.
• the content of the acidic phosphate ester or salt thereof other than the acidic phosphate ester or salt thereof of the present invention is preferably 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the flame-retardant fiber. More preferred is 0.05 to 3% by weight.
• the flame-retardant fiber of the present invention is excellent in flame retardancy, and is a vehicle interior material for automobiles, airplanes, railways, ships, etc .; bedding such as futons, mattresses, sheets, pillows, covers, blankets, towels; Clothing such as fire clothes; Curtains, blinds, sofas, chairs, paper bags, carpets, carpets, table cloths, cushions, shoji screens, bran, etc .; display plywood, fiberboards, books, black curtains, construction sheets, It can be used for many applications such as industrial materials such as tents and filters.
• the flame-retardant fiber of the present invention does not react with a snow melting agent, it is suitably used for vehicle interior materials such as automobiles that are required not to react with the snow melting agent as well as flame retardancy and resistance to flaking. be able to.
• vehicle interior materials such as automobiles that are required not to react with the snow melting agent as well as flame retardancy and resistance to flaking.
• the automobile interior material include a seat back, a door panel, a head lining, a seat cushion, an armrest, a curtain, a mattress, a sun visor, a seat belt, a front panel, a floor cover, and a side panel.
• the flame-retardant fiber of the present invention includes UL-94 vertical combustion test, UL-94 thin material vertical combustion test, JIS-L-1091 method A (microburner method, Meckel burner method, horizontal method, vertical method), B Method (surface combustion test), method C (burning rate test), method D (flame contact test), method E (oxygen index method test), JIS-D-1201, FMVSS-302 method (combustion test of automotive interior materials) It is preferably used for applications that are applied to combustion tests such as
• ⁇ Scouring dyeing processing> In a mini-color dyeing pot of the mini-color dyeing machine (manufactured by Tecsum Giken), water, scouring agent Marpon ISD-1 (1 g / L, Matsumoto Yushi Seiyaku Co., Ltd.), Kayalon Polyester Black RV-SF300 (3 Weight% owf (manufactured by Nippon Kayaku Co., Ltd.) was added while dissolving in water at 30 to 35 ° C., and then adjusted to pH 4.5 with an acetic acid / sodium acetate buffer to prepare a dyeing bath. Next, the polyester tropical living machine was put into the prepared dyeing bath and treated with a mini color. The bath ratio at that time was 1:20.
• the temperature was raised to 135 ° C. at a rate of 2 ° C. per minute and maintained at 135 ° C. for 40 minutes. Then, when it cooled and became 70 degreeC, the dyeing bath was discarded and it washed with water for 5 minutes.
• ⁇ Flame retardant processing> Immerse the polyester fiber for flame-retardant processing into a treatment solution containing 5% by weight of the flame-retardant processing agent and 3% by weight of Matsumoto Silicone Softener N-20 (silicone softener, Matsumoto Yushi Seiyaku Co., Ltd.) and squeeze with mangle ( The drawing rate was 90%), drying was performed at 110 ° C. for 3 minutes, and curing was performed at 160 ° C. for 1 minute to obtain a flame-retardant processed cloth.
• Matsumoto Silicone Softener N-20 silicone softener, Matsumoto Yushi Seiyaku Co., Ltd.
• Example 1 About the said flame-retardant processing polyester fiber which carried out the scouring dyeing
• Example 2 to 22 Evaluation was performed in the same manner as in Example 1 except that the flame retardant processing chemical 1 was changed to the flame retardant processing chemicals 2 to 22 shown in Production Examples 2 to 22, respectively. The results are shown in Table 1.
• Example 1 Evaluation was performed in the same manner as in Example 1 except that the flame retardant processing chemical 1 was changed to Apinon 307 (manufactured by Sanwa Chemical Co., Ltd.), which is a 50% by weight aqueous solution of guanidine phosphate. The results are shown in Table 1.
• Example 2 Evaluation was performed in the same manner as in Example 1 except that the flame retardant processing chemical 1 was changed to Apinon 145 (manufactured by Sanwa Chemical Co., Ltd.), which is a 45% by weight aqueous solution of guanidine sulfamate. The results are shown in Table 1.
• Examples 1 to 22 used as flame retardant processing chemicals of the present invention are excellent in all of flame retardancy, resistance to flaking, bleeding, and reactivity with a snow melting agent.
• Comparative Examples 1 to 5 are inferior in any of flame retardancy, fluff resistance, bleed property, and reactivity with a snow melting agent.
• the flame retardant processing agent for fibers of the present invention can be suitably used when imparting flame retardancy to a fiber material.
• the flame-retardant fiber of the present invention can be used in many applications such as vehicle interior materials, bedding, clothing, interiors, and industrial materials.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Fireproofing Substances (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=49915848

Family Applications (1)

Country Status (2)

Cited By (2)

Citations (3)

Family Cites Families (1)

• 2013
  • 2013-06-19 JP JP2014524707A patent/JP6271424B2/ja active Active
  • 2013-06-19 WO PCT/JP2013/066787 patent/WO2014010380A1/fr not_active Ceased

Patent Citations (3)

Also Published As

Similar Documents

Legal Events