Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes

Definitions

• the present invention relates to a flame retardant polyurethane resin and a flame retardant synthetic leather having a remarkably high flame retardant performance equal to or better than that of a halogen flame retardant and having good physical properties.
• polyurethane resin has been used for various uses such as clothing, bags, shoes, furniture, interior materials for vehicles, interior materials for aircraft, interior materials for ships, etc. as a synthetic leather, which is one main application.
• fields requiring high flame retardancy include furniture, vehicle interior materials / aircraft interior materials, marine interior materials, and the like.
• Synthetic leather is generally formed by impregnating or laminating a polyurethane resin on a fiber base material such as nonwoven fabric, woven fabric, or knitted fabric.
• a fiber base material such as nonwoven fabric, woven fabric, or knitted fabric.
• the synthetic leather is very difficult to be flame-retardant because the combustion mechanism of the polyurethane resin constituting the synthetic leather and the fiber base material are different.
• an additive-type flame retardant added to a polyurethane resin and imparting flame retardant performance is copolymerized as one of the resin components when the polyurethane resin is synthesized. Reactive flame retardants that have become flame retardant when incorporated have been reported.
• additive-type flame retardants that are cheaper in production cost can freely adjust the type and amount of flame retardants in the post-production process according to the application desired by the producer, and are more suitable for the production of a small variety of products. Due to its ease of use, it dominates the current market.
• a bromine-based halogen compound in particular, a combination formulation of decabromodiphenyl ether and antimony trioxide has been widely used since it exhibits excellent flame retardancy.
• halogen compounds generate toxic gases such as hydrogen halides and dioxins during combustion.
• non-halogen flame retardants particularly phosphorus flame retardants, and various phosphorus flame retardants have been developed.
• phosphorus flame retardant many flame retardants such as ammonium polyphosphate, melamine polyphosphate, red phosphorus, organic phosphorus metal salt, phosphate ester and phosphate amide are known.
• Patent Document 1 discloses a leather-like sheet-like product formed by attaching a polycarbonate-based polyurethane solution containing a red phosphorus flame retardant to a fiber base material.
• Patent Document 2 discloses the production of a flame retardant polyurethane resin composition containing a polyurethane resin, a phosphorus-nitrogen flame retardant (surface-treated ammonium polyphosphate), a polyhydric alcohol or derivative thereof, and a silicon compound (alkoxysiloxane). A method is disclosed.
• Patent Document 3 discloses a polyurethane synthetic leather composed of a polyurethane resin layer containing a fiber base material and a phosphate ester flame retardant.
• Patent Document 4 discloses a flame retardant polyurethane resin in which the phosphorus-containing chain extender in the polyurethane resin is a special phosphaphenanthrene derivative.
• Japanese Patent Laid-Open No. 5-163683 Japanese Patent No. 5246101 JP 2013-189736 A Japanese Patent No. 5405383
• the red phosphorus flame retardant used in the method of Patent Document 1 has a high phosphorus content and high flame retardancy, but has a unique red color, and therefore imparts an undesirable color to the product. There is a risk that.
• Patent Document 4 in a method of incorporating a phosphorus-containing chain extender composed of a special phosphaphenanthrene derivative as a reactive flame retardant into a polyurethane resin, the flame retardant is a strong chemical bond in the resin, so-called Since they are integrated by covalent bonding, the flame retardant does not bleed out even under high temperature and high humidity conditions.
• the flame retardant in order to synthesize the above-mentioned special flame retardant, a very complicated process of 10 hours at 150 ° C., 10 hours at 180 ° C., and further 10 hours at 200 ° C. Therefore, the increase in cost is unavoidable and has the disadvantage of being difficult to use in practice.
• the conventional technology has the problem to be solved as described above, that is, has extremely high flame retardant performance equivalent to or higher than that of the halogen-based flame retardant, does not impair the colorability of the product, There are no flame retardant polyurethane resins and flame retardant synthetic leathers that have hydrolysis resistance and bleed-out resistance even under wet conditions, and that can suppress the increase in cost. Yes.
• An object of the present invention is to provide a flame-retardant polyurethane resin and a flame-retardant synthetic leather that have both hydrolysis resistance and bleed-out resistance even under high-humidity conditions and that can suppress an increase in cost.
• the inventors of the present invention imparted a flame retardant represented by the following formula (1) to synthetic leather, thereby achieving an extremely high level equivalent to or higher than that of a halogen flame retardant.
• Flame retardant polyurethane resin that has excellent flame retardant performance, does not hinder product coloration, has hydrolysis resistance and bleed out resistance even under high temperature and high humidity conditions, and can suppress cost increase
• R 1 is hydrogen, a phenyl group, or a linear alkyl group having 1 to 6 carbon atoms
• M is Mg, Al, Ca, Ti, or Zn
• m is 2, 3, or 4
• a flame retardant polyurethane resin obtained by mixing a flame retardant (a) represented by the following formula (1) and a polyurethane resin (b), wherein the mixing ratio is (a) / (b) Flame retardant polyurethane resin characterized by being in the range of 5/95 to 50/50, (Wherein R 1 is hydrogen, a phenyl group, or a linear alkyl group having 1 to 6 carbon atoms, M is Mg, Al, Ca, Ti, or Zn, and m is 2, 3, or 4) is there.) (2) Flame retardant represented by the above formula (1) (a) 100 parts by weight of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, ammonium polyphosphate, phosphate ester amide, melamine phthalate, melamine The total of one or more flame retardant aids (c) selected from the group consisting of melamine cyanurate, benzoguanamine, expandable graphite, aluminum hydroxide
• the present invention has remarkably high flame retardant performance equal to or better than that of halogen flame retardants, does not impair product colorability, and is resistant to hydrolysis and bleed out even under high temperature and high humidity conditions. Further, it is possible to provide a flame retardant polyurethane resin and a flame retardant synthetic leather capable of suppressing an increase in cost.
• the present invention uses a non-halogen phosphorus flame retardant, it is more environmentally friendly than conventional flame retardant synthetic leather using a halogen flame retardant.
• the flame retardant used in the present invention is a compound represented by the following formula (1). (Wherein R 1 is hydrogen, a phenyl group, or a linear alkyl group having 1 to 6 carbon atoms, M is Mg, Al, Ca, Ti, or Zn, and m is 2, 3, or 4) is there.)
• R 1 in the above formula (1) is preferably hydrogen, a phenyl group, a methyl group or an ethyl group, and M in the above formula (1) is preferably aluminum or zinc.
• the flame retardant represented by the above formula (1) include zinc phosphinate (phosphorus content 31.7%), zinc phenylphosphinate (phosphorus content 17.8%), and methyl methylphosphinate (phosphorus). Content 27.7%), zinc ethylphosphinate (phosphorus content 24.6%), aluminum phosphinate (phosphorus content 41.9%), phenyl phenylphosphinate (phosphorus content 20.6%), methyl Examples include aluminum phosphinate (phosphorus content 35.2%) and ethyl ethylphosphinate (phosphorus content 30.4%). Since these phosphinic acid metal salts are usually colorless or white powders, they can be used without impairing the colorability of the product. The phosphorus content will be described later.
• the flame retardant represented by the above formula (1) is any one of phosphinic acid, phenylphosphinic acid, methylphosphinic acid and ethylphosphinic acid, or an alkali metal salt of phosphinic acid, phenylphosphinic acid, methylphosphinic acid and ethylphosphinic acid.
• One and any one of aluminum, zinc nitrate, sulfate, carbonate and hydroxide are heated and reacted in an aqueous solution state. This is a kind of acid-base reaction or salt reaction in an aqueous solution. Since the reaction proceeds rapidly, the target compound is produced in a relatively short time of 1 to 3 hours, so that an increase in cost can be suppressed. It is similar to the manufacturing method.
• the average particle size of the flame retardant of the present invention is preferably 1 to 50 ⁇ m, particularly preferably 2 to 20 ⁇ m. If the average particle size exceeds 50 ⁇ m, the dispersion stability of the flame-retardant polyurethane resin composition may be deteriorated. If the average particle size is less than 1 ⁇ m, the generation of aggregates in the resin composition or extremely There is a risk of thickening of the film.
• the flame retardant of the present invention can exhibit extremely high flame retardant performance without using any other flame retardant or flame retardant aid.
• the following two points can be considered as the reason.
• phosphorus can achieve flame retardancy by suppressing the combustion of combustible materials such as synthetic resins and fiber base materials in both the gas phase and the solid phase.
• gas phase OH radicals that cause expansion of combustion are trapped by phosphorus-derived PO chemical species, and combustion is suppressed.
• solid phase polyphosphoric acid generated by thermal decomposition of phosphorus promotes carbonization of the resin and is dense. It is considered that the combustion is suppressed by blocking the resin from heat by forming a carbonized film. Therefore, from the above theory, it is considered that the higher the phosphorus content, the higher the flame retardant performance.
• the phosphorus content of the flame retardant of the present invention is preferably 30 to 50%.
• sodium phosphinate has a strong reducing ability and is widely used as a reducing agent for metal plating.
• high reducibility means high ability to bind to oxygen, and high reducibility is considered to contribute to flame retardancy.
• the P—H bond of the flame retardant of the present invention is combined with oxygen to form a P—OH bond, thereby reducing the surrounding oxygen concentration.
• This new theory for improving the flame retardant performance in the present invention is unique to the flame retardant of the present invention, and is different from the organophosphorus metal salts that are generally commercially available, ie, dialkylphosphinic acid metal salts. To do.
• melamine phosphate, melamine pyrophosphate, melamine polyphosphate, ammonium polyphosphate, phosphate ester amide, melamine phthalate, melamine, melamine cyanurate, benzoguanamine for further flame retardant performance improvement
• expansive graphite, aluminum hydroxide and magnesium hydroxide may optionally be used in combination as flame retardant aids. The amount used is 0 to 200 parts by weight of the total of at least one compound of the above flame retardant aid with respect to 100 parts by weight of the flame retardant of the present invention.
• the mixing ratio of the flame retardant of the present invention and the polyurethane resin is preferably 5/95 to 50/50, more preferably 10/90 to 35/65, by mass ratio.
• the mixing ratio of the total of the flame retardant of the present invention and the flame retardant aid and the polyurethane resin is preferably 5/95 to 50/50 by mass ratio. More preferably, it is 10/90 to 35/65. If the mixing ratio exceeds 50/50, the synthetic leather may have a texture hardening or a decrease in tensile strength, and if the mixing ratio is less than 5/95, sufficient flame retardancy may not be obtained.
• the flame-retardant synthetic leather of the present invention comprises a nonwoven fabric, a woven fabric, a fiber base material including a knitted fabric, and at least one polyurethane resin layer, and any one of the polyurethane resin layers is a flame-retardant material of the present invention. It is formed using a conductive polyurethane resin.
• Fiber base Nonwoven fabrics, woven fabrics, knitted fabrics and the like are used as the fiber base material used in the present invention.
• the type of fiber material is not particularly limited, and synthetic fibers such as polyester, nylon, polyacrylonitrile, polypropylene and aramid, semi-synthetic fibers such as diacetate and triacetate, and cellulosic fibers such as rayon, cotton and hemp Further, animal fibers such as wool, silk and feathers, or inorganic fibers such as glass fibers and carbon fibers may be used alone or in combination.
• polyurethane resin As the polyurethane resin used in the present invention, those synthesized from polyols, isocyanates, and chain extenders can be used.
• polystyrene resin examples include polycarbonate polyol, polyester polyol, polyether polyol, polycaprolactone polyol, polyolefin polyol, vegetable oil-based polyol, and the like. These polyols may be used alone or in combination of two or more.
• the number average molecular weight is preferably in the range of 1000 to 3000.
• polycarbonate polyol examples include one or two alkanediols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, and 1,12-dodecanediol.
• alkanediols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, and 1,12-dodecanediol.
• the above and the copolymer with 1 type, or 2 or more types of carbonate compounds, such as dialkyl carbonate, alkylene carbonate, and diphenyl carbonate are mentioned.
• polyester polyol examples include one or two low molecular diols such as ethylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and diethylene glycol.
• low molecular diols such as ethylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and diethylene glycol.
• low-molecular dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and phthalic acid.
• polyether polyol examples include polypropylene ether polyol, polytetramethylene ether polyol, hexamethylene ether polyol, and the like.
• Examples of the vegetable oil-based polyol include castor oil-modified polyol, dimer acid-modified polyol, soybean oil-modified polyol, and the like.
• isocyanate used examples include aliphatic diisocyanates such as methylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, and alicyclic groups such as 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and norbornene diisocyanate.
• Aromatic diisocyanates such as diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5-naphthalene diisocyanate and the like can be mentioned. These isocyanates can be used alone or in combination of two or more.
• a low molecular weight diol having 2 to 10 carbon atoms used as a chain extender is preferable, such as ethylene glycol, diethylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Examples thereof include aliphatic glycols such as neopentyl glycol and low-molecular alicyclic diols such as cyclohexanediol. These polyols can be used alone or in combination of two or more. These polyols preferably have an average number of functional groups of 2 or more and an average molecular weight in the range of 50 to 400.
• the polyurethane resin used for the synthetic leather is not particularly limited, and examples thereof include a polyether-based polyurethane resin, a polyester-based polyurethane resin, and a polycarbonate-based polyurethane resin. These may be used alone or in combination of two or more. They can be used in combination. Especially, it is preferable to use a polycarbonate-type polyurethane resin at the point which is excellent in durability, heat resistance, and a weather resistance of the polyurethane resin obtained.
• the method for producing the flame-retardant synthetic leather of the present invention is not particularly limited, and can be produced by either a wet method or a dry method.
• the wet method is a method in which a base polyurethane resin mixed with a water-soluble solvent (hereinafter referred to as a base resin) is coated on a fiber base material and immersed in a coagulation bath containing water.
• a base resin a water-soluble solvent
• the water-soluble solvent is eluted, the polyurethane resin is precipitated and solidified to form a porous microporous layer having a large number of voids, and the product is then washed and dried to obtain a product.
• a flame retardant may be blended in the base resin, and a skin layer containing a pigment that has been embossed or the like may be laminated on the base resin.
• the dry method is a direct coating method in which a polyurethane resin mixed with a solvent is directly coated on a fiber substrate, and the solvent is evaporated by a dryer to cure, or for a skin layer containing a pigment on a release paper.
• a polyurethane resin is coated and dried to form a skin resin layer, and then a polyurethane resin for an adhesive layer is coated on the skin resin layer, bonded and bonded to a fiber substrate, and dried to obtain a product. is there.
• an aging treatment may be performed to complete the curing reaction.
• the release paper is peeled off to complete.
• a flame retardant may be blended in the polyurethane resin for the adhesive layer.
• a composition containing the polyurethane resin for the skin layer is coated on the release paper, and if necessary, heat treatment is performed to form the skin layer.
• a composition containing a flame retardant polyurethane resin in which the flame retardant of the present invention is blended in advance as an adhesive layer is coated on the skin layer, and the fiber base material and the roll are in a state where the composition has adhesiveness.
• they are bonded together by pressure bonding such as a hot roll, cooled to room temperature, and subjected to aging treatment to form an adhesive layer.
• the release paper is peeled to obtain the flame-retardant synthetic leather of the present invention.
• various conventionally known methods can be employed and are not particularly limited. Examples thereof include a method using an apparatus such as a reverse roll coater, spray coater, roll coater, gravure coater, kiss roll coater, knife coater, comma coater, or T-die coater.
• the thickness of the adhesive layer is preferably 50 to 400 ⁇ m, more preferably 100 to 300 ⁇ m, in a wet state immediately after coating. If it is less than 50 ⁇ m, the adhesive strength may not be sufficient, and if it exceeds 400 ⁇ m, the texture of the synthetic leather may become hard.
• the thickness of the skin layer is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, in a wet state immediately after coating. If it is less than 5 ⁇ m, the abrasion resistance may not be sufficient, and if it exceeds 200 ⁇ m, the texture of the synthetic leather may become hard.
• the usage application of the flame-retardant polyurethane resin obtained in the present invention is not particularly limited.
• a seat sheet material, a floor carpet, and a ceiling material used as interior materials for vehicles, railways, aircrafts, and ships.
• a ceiling material used as interior materials for vehicles, railways, aircrafts, and ships.
• flame retardance performance is high in the order of “NB”>“SE”> “slow flame retardance”, and all three points pass. Furthermore, in order to make it easy to compare the difference in flame retardant performance, the combustion distance from the flame contact portion in each sample was represented by an average value of four points. The smaller the value of the combustion distance, the better the tendency.
• Example 1 A polyurethane resin composition for the skin layer was prepared according to the following formulation. ⁇ Prescription 1> -Polycarbonate polyurethane resin (solid content 25%, solvent DMF) 100 parts-Dimethylformamide (DMF) 40 parts-Carbon black pigment 12 parts
• a polyurethane resin composition for the adhesive layer was prepared according to the following formulation.
• ⁇ Prescription 2> ⁇ Polycarbonate polyurethane resin (solid content 70%, solvent MEK) 100 parts ⁇ Methyl ethyl ketone (MEK) 50 parts ⁇ Urethane curing agent (polyisocyanate) 10 parts ⁇ Urethane catalyst 2 parts ⁇ Ethylphosphinic acid aluminum (average particle size 5 ⁇ m) 15 copies
• the resin composition for skin layer of the above formulation 1 was coated on a release paper so as to have a thickness of 150 ⁇ m, and dried for 2 minutes with a dryer at 100 ° C. to form a skin layer.
• the resin composition for the adhesive layer of the above formulation 2 is coated to a thickness of 250 ⁇ m, dried for 3 minutes in a dryer at 120 ° C., bonded to a polyester tricot cloth, and pressed with a mangle.
• the flame-retardant synthetic leather of Example 1 was obtained by aging at 40 ° C. for 72 hours and peeling off the release paper.
• Example 2 Flame retardant in the same manner as in Example 1 except that the flame retardant of ⁇ Prescription 2> of Example 1 was a mixture of 10 parts of aluminum ethylphosphinate (average particle diameter 5 ⁇ m) and 5 parts of benzoguanamine (average particle diameter 10 ⁇ m). Sexual synthetic leather was obtained.
• Example 1 A flame retardant synthetic leather was obtained in the same manner as in Example 1 except that no flame retardant was added to the adhesive layer.
• Example 2 A flame-retardant synthetic leather was obtained in the same manner as in Example 1 except that the flame retardant of ⁇ Prescription 2> in Example 1 was changed to 15 parts of a mixture of decabromodiphenyl ether and antimony trioxide (average particle size: 4 ⁇ m).
• Example 3 A flame-retardant synthetic leather was obtained in the same manner as in Example 1 except that 15 parts of the flame retardant of ⁇ Prescription 2> in Example 1 was changed to 15 parts of ammonium polyphosphate (average particle size: 15 ⁇ m).
• Table 1 shows the evaluation results of the synthetic leathers of Examples and Comparative Examples for the flame retardant performance test.
• Table 2 shows the evaluation results of the synthetic leathers of Examples and Comparative Examples for other evaluation items. Since the hydrolysis resistance test and the bleed resistance test of Comparative Example 1 did not contain a flame retardant, the wet heat aging test was originally rejected because the flame retardant performance was originally unacceptable.
• the flame retardant synthetic leather made of polyurethane resin using the flame retardant of the present invention has the same or better advanced flame retardant performance than the synthetic leather using halogenated flame retardant, but synthetic leather. As a result, various physical properties were maintained in good condition.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2014
  • 2014-10-15 JP JP2014223625A patent/JP6151678B2/ja active Active
• 2015
  • 2015-08-26 CN CN201580039843.5A patent/CN106574112B/zh active Active
  • 2015-08-26 WO PCT/JP2015/074033 patent/WO2016059882A1/ja not_active Ceased

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