CN106574112A - Flame-retardant polyurethane resin and flame-retardant synthetic leather - Google Patents
Flame-retardant polyurethane resin and flame-retardant synthetic leather Download PDFInfo
- Publication number
- CN106574112A CN106574112A CN201580039843.5A CN201580039843A CN106574112A CN 106574112 A CN106574112 A CN 106574112A CN 201580039843 A CN201580039843 A CN 201580039843A CN 106574112 A CN106574112 A CN 106574112A
- Authority
- CN
- China
- Prior art keywords
- polyurethane resin
- fire
- retardant
- synthetic leather
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 61
- 239000002649 leather substitute Substances 0.000 title claims abstract description 51
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims description 29
- -1 amidophosphoric acid ester Chemical class 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims 1
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- 238000000034 method Methods 0.000 description 23
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 150000005846 sugar alcohols Polymers 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
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- 230000003301 hydrolyzing effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 2
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 2
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 238000002788 crimping Methods 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
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- 150000002527 isonitriles Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- OBNAOHSAPQWLGU-UHFFFAOYSA-N phthalic acid;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OC(=O)C1=CC=CC=C1C(O)=O OBNAOHSAPQWLGU-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- 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)
Abstract
Provided are: a flame-retardant polyurethane resin which exhibits extremely high flame retardancy, while having both hydrolysis resistance and bleed-out resistance even under high temperature and high humidity conditions without inhibiting coloring of a product, and which is able to suppress increase in the cost; and a flame-retardant synthetic leather. A flame-retardant polyurethane resin which is obtained by mixing (a) a metal phosphinate salt and (b) a polyurethane resin, and which is characterized in that the mixing ratio (a)/(b) in terms of a weight ratio is within the range from 5/95 to 50/50; and a flame-retardant synthetic leather which is formed of the flame-retardant polyurethane resin.
Description
Technical field
The present invention relates to fire-retardancy polyurethane resin and anti-flammability synthetic leather, the fire-retardancy polyurethane resin has and halogen
Flame retardant peer-level or the preferably fire resistance of notable height, and with good physical property.
Background technology
In the past, polyurethane resin, using the synthetic leather as one main usess, apply clothing, bag, footwear, furniture,
In the various uses such as internal decorative material for vehicle, aircraft interior material, ship interior material.Wherein, as requiring high fire-retardance
The field of performance, can enumerate furniture, internal decorative material for vehicle, aircraft interior material, ship interior material etc..
Polyurethane is generally impregnated with or is layered on the fiber base materials such as non-woven fabrics, textile, knitwear and shape by synthetic leather
Into.It is well known, however, that for synthetic leather, due to constituting the burning between its polyurethane resin and fiber base material
Mechanism is different, therefore flame-retarded extremely difficult.
As the fire retardant for synthetic leather as described above, it has been reported that be matched with polyurethane resin so as to give resistance
The additive flame retardant of combustion performance, and carry out copolymerization as one of resin constituent in synthesis of polyurethane resin and combine
Enter in resin to carry out flame-retarded reactive flame retardant.However, low production cost, can be according to the desired purposes of Producer
Species, the use level of fire retardant, and the addition of the production suitable for a small amount of multi items are freely adjusted in the subsequent handling of production
Type fire retardant, because its practicality is good, accounts for main flow in Vehicles Collected from Market.
As fire retardant, in the past, the combination formula of bromine class halogen compounds, especially deca-BDE and antimony trioxide by
In the fire resistance that performance is excellent, therefore it is widely used.However, having pointed out that halogen based compound can produce halogen in burning
Change hydrogen, twoThe toxic gas of English class.Therefore, for environmental protection, the non-halogen system to not using halogen based compound is fire-retardant
The demand of agent, especially phosphorus flame retardant is more, and exploitation has various phosphorus flame retardants.It is known to have poly- as phosphorus flame retardant
Various fire retardants such as ammonium phosphate, polyphosphoric acid melamine, red phosphorus, organophosphors system slaine, phosphate ester and phosphoamide.
There has been proposed using the various flame-retarded method of these phosphorus flame retardants.For example, it is following to Patent Document 1 discloses
Adhere to the leather-like sheet material of the polycarbonate-based polyurethane solutions containing red phosphorus flame retardant on fiber base material.
In addition, following Patent Document 2 discloses containing polyurethane resin, phosphorus-nitrogenated flame retardant (surface treatment polyphosphoric acid
Ammonium), the manufacturer of the flame retardant polyurethane resin compositionss of polyhydric alcohol or derivatives thereof and silicon compound (oxyalkylsiloxane)
Method.
It is following to Patent Document 3 discloses to be combined with the poly- of fiber base material and phosphate ester flame retardant as another example
The polyurethane synthetic leather that urethane resin bed is constituted.
Further, it is special phospho hetero phenanthrene in following phosphorous chain extenders that Patent Document 4 discloses in polyurethane resin
The fire-retardancy polyurethane resin of derivant.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 5-163683 publication
Patent documentation 2：No. 5246101 publications of Japanese Patent Publication No.
Patent documentation 3：Japanese Unexamined Patent Publication 2013-189736 publications
Patent documentation 4：No. 5405383 publications of Japanese Patent Publication No.
The content of the invention
Problems to be solved by the invention
However, the red phosphorus flame retardant used in the method for patent documentation 1, phosphorous rate is high, fire resistance is high, but has
There is the redness of uniqueness, it is possible to cause to add product undesirable coloring.In addition, suppressing coloring and anti-flammability to obtain
The balance of energy, it is sometimes desirable to add substantial amounts of depigmenting agent, it is possible to thus produce the light resistance of fire resistance decline or depigmenting agent
Bad the problems such as.
Using patent documentation 2 it is such in hydrolytic resistance in terms of there is a difficult problem APP method in, phosphorous rate
About 30% or so, comparison is high, fire resistance is easily played, even if being coated APP, in hot and humid condition
Under be also difficult to be substantially prevented from hydrolysis, as a result, because the polyphosphoric acid for being generated not only results in the deterioration of the physical property of product, and producing
Product surface produces the so-called albinism for being referred to as oozing out, tacky, it is possible to can reduce the quality of product.In fact, at this
In patent documentation, although for the fire resistance and mechanical performance of resin combination are evaluated, but do not enter for oozing out
Row checking.
In addition, though phosphate ester used in patent documentation 3, but as described above, be also phosphate ester to tackle
Problem points water-disintegrable and ooze out, limit the acid number and molecular weight of phosphate ester.But, under conditions of high temperature, high humidity, it is difficult to
It is substantially prevented from oozing out, and then for phosphate ester, in order to improve hydrolytic resistance, needs to increase molecular weight to condensed type etc., thus leads
The phosphorous rate in phosphate ester is caused to decline.As a result, it is such generally to there are problems that fire resistance declines.
On the other hand, as shown in patent documentation 4, special phospha phenanthrene derivative will included as reactive flame retardant
Phosphorous chain extender is incorporated in the method in polyurethane resin, because above-mentioned fire retardant passes through firm chemistry in resin
Key, i.e. so-called covalent bond and it is integrated, even if therefore with the fire retardant under conditions of hot and humid also will not ooze out it is excellent
Point.However, according to the embodiment of the patent documentation, due to containing above-mentioned special fire retardant, with 10 hours at 150 DEG C,
And then at 180 DEG C 10 hours and then very numerous and diverse as 10 hours operation at 200 DEG C, therefore, it is difficult to avoiding cost
Increase, have the shortcomings that to be difficult to practical application.Also, the phosphorus concentration that can contain in polyurethane resin is restricted, if exceeding it
Higher limit, then not only texture declines, and the evaluation of fire resistance is only limited oxygen index (LOI value), used as anti-flammability synthesis
Can leather give full play to the anti-flammability of height by contained phosphorus concentration, then be difficult to rightly judge.
As described above, in the prior art, fail to provide it is can solving the above problems, have it is equal with halogenated flame retardant
Even if the fire resistance of level or preferably significantly height, the coloring for not hindering product, also having concurrently under the conditions of hot and humid
Hydrolytic resistance and fire-retardancy polyurethane resin and anti-flammability synthetic leather resistance to exudative and then that can suppress cost increase, compel
Cut and wish its realizationization.
Therefore, the present invention allows for the problems referred to above and completes, i.e., purpose is to provide a kind of with fire-retardant with halogen system
Even if the fire resistance of agent peer-level or preferably significantly height, do not hinder the coloring of product, under the conditions of hot and humid
Also hydrolytic resistance and fire-retardancy polyurethane resin resistance to exudative and then that cost increase can be suppressed and anti-flammability synthesis skin are had concurrently
Leather.
For the method for solve problem
The present inventor etc. have made intensive studies to achieve these goals, as a result find, by paying to synthetic leather
Fire retardant shown in following formula (1), can obtain having fire-retardant with halogenated flame retardant peer-level or more preferable significantly height
Even if performance, the coloring for not hindering product, also having under the conditions of hot and humid hydrolytic resistance and resistance to exudative and then can press down concurrently
The fire-retardancy polyurethane resin and anti-flammability synthetic leather of this increase are made, the present invention is so far completed.
[chemical formula 1]
In formula, R1For the straight chained alkyl of hydrogen, phenyl or carbon number 1～6, M is Mg, Al, Ca, Ti or Zn, m be 2,3 or
4。
That is, idea of the invention is that：
(1) a kind of fire-retardancy polyurethane resin, it is characterised in that it is the fire retardant (a) and poly- ammonia shown in following formula (1)
The fire-retardancy polyurethane resin that ester resin (b) is mixed, mixed proportion is with weight ratio meter as (a)/(b)=5/95～50/50
Scope；
[chemical formula 1]
In formula, R1For the straight chained alkyl of hydrogen, phenyl or carbon number 1～6, M is Mg, Al, Ca, Ti or Zn, m be 2,3 or
4；
(2) fire-retardancy polyurethane resin according to claim 1, it is characterised in that relative to described in 100 weight portions
Fire retardant (a) shown in formula (1), flame retardant (c) adds up to 0～200 weight portion, and the flame retardant (c) is selected from phosphorus
Sour tripolycyanamide, melamine pyrophosphate, polyphosphoric acid melamine, APP, amidophosphoric acid ester, phthalic acid melamine
In the group of amine, tripolycyanamide, melamine cyanurate, benzoguanamine, expanded graphite, aluminium hydroxide and magnesium hydroxide composition
One or more, the fire retardant (a) shown in the formula (1) and polyurethane resin (b) are mixed with the flame retardant (c)
Scope of the composition and division in a proportion example with weight ratio meter as { (a)+(c) }/(b)=5/95～50/50；
(3) a kind of anti-flammability synthetic leather, it is characterised in that synthetic leather includes following composition, and it contains fiber base material
And least one layer of urethane resin layer, the fiber base material include non-woven fabrics, textile, knitwear, the polyurethane resin
Layer is formed using the fire-retardancy polyurethane resin described in above-mentioned (1) and/or (2).
Invention effect
In accordance with the invention it is possible to provide with the anti-flammability with halogenated flame retardant peer-level or more preferable significantly height
Even if, hindering the coloring of product, having under the conditions of hot and humid hydrolytic resistance concurrently and resistance to exudative and then can suppress yet
Fire-retardancy polyurethane resin and anti-flammability synthetic leather that cost increases.
Further, the present invention has been due to having used the phosphorus flame retardant of non-halogen system, with the existing resistance for having used halogenated flame retardant
Combustion property synthetic leather is compared, not to the worry of environment.
Specific embodiment
Hereinafter, to the present invention fire-retardancy polyurethane resin and the embodiment of anti-flammability synthetic leather is illustrated.
[fire retardant { following formula (1) }]
Fire retardant used in the present invention is the compound shown in following formula (1).
[chemical formula 1]
In formula, R1For the straight chained alkyl that hydrogen, phenyl or carbon number are 1～6, M is Mg, Al, Ca, Ti or Zn, and m is 2,3
Or 4；
As the R of above-mentioned formula (1)1, preferred hydrogen, phenyl, methyl or ethyl；As the M of above-mentioned formula (1), preferred aluminum or zinc.
As the concrete example of the fire retardant shown in above-mentioned formula (1), phosphinic acid zinc (phosphorous rate 31.7%), phenyl can be enumerated
Phosphinic acid zinc (phosphorous rate 17.8%), methyl-phosphinic acid zinc (phosphorous rate 27.7%), ethylphosphinic acid zinc (phosphorous rate 24.6%),
Phosphinic acid aluminum (phosphorous rate 41.9%), aluminum phenylphosphinate (phosphorous rate 20.6%), methyl-phosphinic acid aluminum (phosphorous rate 35.2%)
And ethylphosphinic acid aluminum (phosphorous rate 30.4%).These metal phosphinates are usually colourless or white powder, therefore can
Used with not damaging the coloring of product.It is aftermentioned with regard to phosphorous rate.
Fire retardant shown in above-mentioned formula (1), can be by secondary by phosphinic acid, phenyl phosphinic acid, methyl-phosphinic acid and ethyl
Any one in the alkali metal salt of phosphonic acids or phosphinic acid, phenyl phosphinic acid, methyl-phosphinic acid and ethylphosphinic acid and aluminum or
Any one in the nitrate of zinc, sulfate, carbonate and hydroxide, heats under aqueous solution state so as to reaction and
Obtain.This is one kind of the acid-base reaction in aqueous solution or reactant salt, by being swift in response is carried out, so as to can be at 1～3 hour
Target compound is generated in such shorter time, the manufacture method that cost can be suppressed to increase is consequently belonging to.
Preferably 1～50 μm, particularly preferred 2～20 μm of the mean diameter of the fire retardant of the present invention.If particle diameter is more than 50 μm,
The dispersion stabilization of fire-retardancy polyurethane resin compositionss is possible to deteriorate, if mean diameter is less than 1 μm, it is likely that occur
Condensation product is produced in above-mentioned resin combination or is extremely viscosified.
Even if the fire retardant of the present invention is not used in combination with other fire retardants or flame retardant, it is also possible to play the resistance of notable height
Combustion performance.Its reason is believed that to be at following 2 points.
(A) phosphorous rate is high
(B) there is the reduction that P-H keys bring
It is high with regard to (A) phosphorous rate, it is well known that it is one of key element of raising fire resistance.That is, phosphorus by with gas phase and
The aspect of solid phase two suppresses for the burning of the combustibles such as synthetic resin and fiber base material, flame-retarded so as to realize.It is believed that right
For gas phase, by come from the PO chemical substances of phosphorus be captured as burn expand reason OH free radicals come suppress burning；
For solid phase, the carbonization of resin is promoted by the polyphosphoric acid for thermally decomposing to generate of phosphorus, by the fine and close carbonization envelope of formation
Resin is separated from thermal source, so as to suppress burning.Therefore, by above-mentioned theory it is considered that phosphorous rate is higher, height can more be played
Fire resistance.As the present invention fire retardant phosphorous rate, preferably 30～50%.
With regard to the reduction that (B) brings with P-H keys, without departing from the scope that the author speculates, but it is regarded as this
The new theory of the raising fire resistance in invention.That is, by with P-H keys, energetically be present in the combustibles such as synthetic resin
The oxygen on surface of pole close limit combine, so as to reduce the oxygen concentration of surrounding, suppress to burn.So why P-H keys are energetically
Combined with oxygenIt is regarded as because the reproducibility of P-H keys is high.Reproducibility is to represent that itself is combined with oxygen and is oxidized, from
And the yardstick of the degree for reducing object, generally it is well known with oxidation-reduction potential.In fact, phosphinic acid sodium has by force
The reproducibility of power, is widely used as the reducing agent of metal deposition.I.e., it is believed that reproducibility height means what is combined with oxygen
Ability is high, and reproducibility height contributes to fire resistance.In such a case, it is possible to think, the P-H keys and oxygen of the fire retardant of the present invention
With reference to and formed P-OH keys, so as to reduce the oxygen concentration of surrounding.The new theory of the raising fire resistance that this is used in the present invention, be
It is different from generally commercially available organophosphors system slaine, i.e. dialkyl metal phosphinate specific to the fire retardant of the present invention.
Used as supplement, common theory thinks more to be oxidized easily (reducing agent of strength) easier burning, but it is
Refer to the situation of the material individualism, in the present invention, due to the fire retardant and polyurethane resin or synthetic leather composition into
Divide and coexist, it is taken as that it is appropriate that can not be suitable for the theory.In fact, will also realize that as described in Example 1, conduct is being implemented
During the flammability test of synthetic leather, the performance of notable height has been given play to.
In addition to the fire retardant of the present invention, in order to further improve fire resistance, it is also possible to by melamine phosphate, burnt phosphorus
Sour tripolycyanamide, polyphosphoric acid melamine, APP, amidophosphoric acid ester, phthalic acid tripolycyanamide, tripolycyanamide, cyanogen
Uric acid tripolycyanamide, benzoguanamine, expanded graphite, aluminium hydroxide and magnesium hydroxide are arbitrarily used in combination as flame retardant.
As consumption, relative to the weight portion of fire retardant 100 of the present invention, at least one compound in above-mentioned flame retardant it is total
For 0～200 weight portion.
The fire retardant of the present invention and the mixed proportion of polyurethane resin, by quality ratio, preferably 5/95～50/50, more
Preferably 10/90～35/65.In addition, in the case of containing flame retardant, the fire retardant and above-mentioned flame retardant of the present invention
It is total, the mixed proportion with polyurethane resin, by quality ratio, preferably 5/95～50/50, more preferably 10/90～35/
65.If mixed proportion is more than 50/50, it is likely that the texture for causing synthetic leather is hardened, tensile strength declines, if mixed proportion
Less than 5/95, it is likely that be difficult to obtain sufficient fire resistance.
[anti-flammability synthetic leather]
The anti-flammability synthetic leather of the present invention includes following composition, and it contains fiber base material and least one layer of polyurethane tree
Lipid layer, the fiber base material includes non-woven fabrics, textile, knitwear, any one layer of use of above-mentioned urethane resin layer this
Bright fire-retardancy polyurethane resin and formed.
[fiber base material]
As the fiber base material used in the present invention, it is possible to use non-woven fabrics, textile, knitwear etc..As fiber
The species of raw material, is not particularly limited, and can be the synthetic fibers such as polyester, nylon, polyacrylonitrile, polypropylene, aramid fiber；Two vinegar
The semisynthetic fibres such as ester fiber, triacetate；The cellulose fibres such as artificial silk, cotton, fiber crops；The animals such as Pilus Caprae seu Oviss, silkworm silk, feather
Fiber；Or the inorfil such as glass fibre, carbon fiber is individually or the fiber that is composited.
[polyurethane resin]
As the polyurethane resin used in the present invention, it is possible to use closed by polyhydric alcohol, isocyanates and chain extender
Into resin.
As polyhydric alcohol, for example, can enumerate polycarbonate polyol, PEPA, polyether polyol, polycaprolactone many
First alcohol, polyolefin polyhydric alcohol, vegetable oil system polyhydric alcohol etc..These polyhydric alcohol may be used alone, used in two or more.
As number-average molecular weight, preferably 1000～3000 scope.
As polycarbonate polyol, for example, can enumerate BDO, 1,5-PD, 1,6- hexanediol, 3- methyl
One or more in the alkane glycol such as pentanediol, 1,12- dodecanediols are with dialkyl carbonate, alkylene carbonate,
One or more copolymer in the carbonate products such as diphenyl carbonate.
As PEPA, for example, can enumerate ethylene glycol, BDO, 1,6- hexanediol, neopentyl glycol, 3- first
One or more and succinic acid, adipic acid, decanedioic acid, neighbour in the low-molecular-weight diols such as base -1,5- pentanediols, diethylene glycol
One or more condensation polymer in the low molecule dicarboxylic acids such as phthalic acid.
As polyether polyol, for example, can enumerate polypropylene ether polyols, polytetramethylene ethoxylated polyhydric alcohol, hexa-methylene
Ethoxylated polyhydric alcohol etc..
As vegetable oil system polyhydric alcohol, for example, can enumerate castor oil modified polyhydric alcohol, dimer acid modified polyhydric alcohol, soybean oil
Modified polyalcohol etc..
As the isocyanates for being used, for example, can enumerate methylene diisocyanate, hexamethylene diisocyanate, rely
The aliphatic diisocyanates such as propylhomoserin diisocyanate, trimethyl hexamethylene diisocyanate；4,4 '-dicyclohexyl methyl hydride two
The alicyclic diisocyanates such as isocyanates, isophorone diisocyanate, norborene diisocyanate；4,4 '-diphenyl
Aromatic diisocyanates such as methane diisocyanate, toluene di-isocyanate(TDI), 1,5- naphthalene diisocyanates etc..These two isocyanides
Acid esters can be used alone, it is also possible to be used in combination.
Be preferably used as chain extender is the low molecular weight diols of carbon number 2～10, for example, can enumerate ethylene glycol, diethyl
The aliphatic diol classes such as glycol, 1,4- butanediols, 1,6-HD, 3- methyl isophthalic acids, 5- pentanediols, neopentyl glycol；Cyclohexanediol
Deng low molecule alicyclic diol class etc..These polyhydric alcohol may be used alone, used in two or more.These polyhydric alcohol
Average functional group number is preferably more than 2, the scope of mean molecule quantity preferably 50～400.
Polyurethane resin used in synthetic leather is not particularly limited, for example can enumerate polyethers system polyurethane resin,
Polyester polyurethane resin, polycarbonate-based polyurethane resin etc..These can be used alone one kind, it is also possible to it is two or more simultaneously
With.Wherein, from resulting polyurethane resin durability, thermostability, have excellent weather resistance from the aspect of, particularly preferably using poly-
Carbonic ester system polyurethane resin.
[manufacture method of anti-flammability synthetic leather]
The manufacture method of the anti-flammability synthetic leather of the present invention is not particularly limited, can be by damp process or dry process
Any means manufactured.
Damp process refers to, the coating on fiber base material is mixed with the primary coat of water-soluble solvent with polyurethane resin (hereinafter referred to as
Make bottom coating resin) so as in impregnated in the coagulating bath containing water, water-soluble solvent dissolution from bottom coating resin, polyurethane resin
Separate out, solidification, form the Porous microporous layers with a large amount of spaces, then Jing washings and drying process are so as to forming the side of product
Method.Fire retardant can be coordinated in above-mentioned bottom coating resin, it is also possible to be laminated on above-mentioned bottom coating resin for example implement embossing plus
Work etc. and the epidermal area containing pigment.
Dry process refers to that directly coating is suitably mixed with the polyurethane resin of solvent on fiber base material, by drying
Machine makes solvent volatilize so that the direct rubbing method of its solidification；Or it is coated with the poly- ammonia of the epidermal area containing pigment on processing release paper
Ester resin, is dried and forms it into skin resin layer, and adhesive linkage is then coated with above-mentioned skin resin layer with polyurethane tree
Fat, fits with fiber base material crimping, is dried the composite algorithm to form product.In addition, for the curing reaction that terminates, it is also possible to real
Apply burin-in process.Finally, processing release paper is peeled off, so as to complete.Can also coordinate fire-retardant in above-mentioned adhesive linkage polyurethane resin
Agent.
Specifically, can by the following method be manufactured, but be not limited to this.
The compositionss containing epidermal area polyurethane resin are coated with processing release paper, as needed, implement heat treatment is formed
Epidermal area.Then, the compositionss containing fire-retardancy polyurethane resin are coated with epidermal area as adhesive linkage, the flame retardance poly
Urethane resin is combined with advance the fire retardant of the present invention, in the state of above-mentioned composition has cohesiveness, by roller or hot-rolling
Deng crimping and fit with fiber base material, be cooled to room temperature, implement burin-in process, form adhesive linkage.Finally, processing release paper is peeled off,
Obtain the anti-flammability synthetic leather of the present invention.
Method as above-mentioned fire-retardancy polyurethane resin compositionss are coated with, it is possible to use existing known various methods,
It is not particularly limited.For example can enumerate using reverse coating machine, flush coater, roll coater, gravure coater, identical print roll coating
The method of the devices such as machine, knife type coater, comma roll-coater or T- mould coating machines.
The thickness of adhesive linkage, under the moisture state after being just coated with, preferably 50～400 μm, more preferably 100～
300μm.If being less than 50 μm, adhesive strength is possible to not enough fully, if more than 400 μm, it is likely that cause synthetic leather
Texture is hardened.
The thickness of epidermal area, under the moisture state after being just coated with, preferably 5～200 μm, more preferably 10～100 μ
m.If being less than 5 μm, abrasion performance is possible to not enough fully, if more than 200 μm, it is likely that the texture for causing synthetic leather becomes
Firmly.
[other additives]
In the anti-flammability synthetic leather of the present invention, in the range of the physical property and fire resistance for not damaging synthetic leather,
Other additives can also be added.Antibacterial mildew inhibitor, antistatic additive, lubricant, UV absorbent, hindered amine can for example be enumerated
System etc. light stabilizer, antioxidant, water-repelling agent, plasticizer, coloring agent, foaming agent, defoamer, urethanation catalyst,
Surface conditioning agent etc..
The use of the fire-retardancy polyurethane resin obtained in the present invention is not particularly limited, for example, can enumerate and be used as
Vehicle use, railway use, aircraft use, seat sheet material, ground cushion, the ceiling tile materials of the interior material of ship etc.；The table of furniture
Blanket, the attending a banquet of chair, curtain, blind, valance etc.；Tent, vehicle cover of outdoor etc..
Embodiment
Hereinafter, enumerate embodiment and comparative example is specifically described to the present invention, but the technical scope of the present invention is not limited
Due to below example.In addition, below in an example, as long as without specified otherwise, " % " refers to weight %, and " part " refers to
Weight portion.The evaluation of each synthetic leather is carried out by the following method.
[flammability test]
According to FMVSS (american car security legislation) No.302 inner decoration material for automobile combustion testing standard, according to
Under determinating reference, fire resistance is evaluated.
The situation of self-extinguishment before A normal lines are reached, will judge that grade is designated as " NB (Non Burning, without combustion
Burn)；
When more than A normal line self-extinguishments, burning extent is that and burning time is the situation within 60 seconds within 50mm,
To judge that grade is designated as " SE (Self-Extinction, self-extinguishment) "；
Burning velocity between normal line is the situation of below 102mm/ minutes, will judge that grade is designated as " lingering "；
Burning velocity between normal line is, more than the situation of 102mm/ minutes, will to judge that grade is designated as " unqualified ".
In addition, high with the order fire resistance of " NB " >=" SE " >=" lingering ", Three Estate is qualified.
Further, for ease of comparing the gap of fire resistance, represent each sample from contact flame portion with 4 meansigma methodss
The burning extent of beginning.The more little better tendency of numerical value with burning extent.
[hydrolytic resistance test]
Carry out the evaluation to fire-retardant powder (hereinafter referred to as powder).As test method, about 5g powder is added into beaker
End, does not add a cover, and is being adjusted to 70 DEG C, is placing 500 hours in the constant temperature and humidity cabinet of relative humidity 90%, and (change is whether there is by outward appearance
Color) and FT-IR (fourier transform infrared spectroscopy) and TGA (thermogravimetric analysiss) come pulverulence before and after evaluation test whether there is change
Change, judged according to following benchmark.
○：In three evaluation methodologys of above-mentioned whole, the powder before and after test does not find clearly change；
×：In any one of above three evaluation methodology, the clear and definite change of the powder before and after test is observed
(in the case where discoloration or the different crests of FT-IR or the difference of TGA heat decomposition curves is observed, point out fire retardant
Hydrolysis, chemical constitution change.)
[resistance to oozing property test]
Synthetic leather is evaluated.As test method, the synthetic leather for being cut into 18 × 25cm is put into and is adjusted to
70 DEG C, in the constant temperature and humidity cabinet of relative humidity 90%, the state on synthetic leather surface of the visual observations after 500 hours is pressed
Judged according to following benchmark.
○：The completely non-albefaction in synthetic leather surface
△：The albefaction slightly of synthetic leather surface
×：The obvious albefaction in synthetic leather surface
[hydrothermal aging test]
Synthetic leather is evaluated.As test method, the synthetic leather for being cut into 18 × 25cm is put into and is adjusted to
70 DEG C, in the constant temperature and humidity cabinet of relative humidity 90%, above-mentioned fire resistance examination is carried out to the synthetic leather after 500 hours
Test, judged according to following benchmark.
○：After hydrothermal aging test, compared with before experiment, do not it is found that fire resistance declines.
×：After hydrothermal aging test, compared with before experiment, it is found that fire resistance is decreased obviously.
[embodiment 1]
Epidermal area polyurethane resin composition is modulated by formula as below.
<Formula 1>
Polycarbonate-based 100 parts of polyurethane resin (solid state component 25%, solvent DMF)
40 parts of dimethylformamide (DMF)
12 parts of charcoal blacks
Adhesive linkage polyurethane resin composition is modulated by formula as below.
<Formula 2>
Polycarbonate-based 100 parts of polyurethane resin (solid state component 70%, solvent MEK)
50 parts of methyl ethyl ketone (MEK)
10 parts of carbamate firming agent (polyisocyanate)
2 parts of urethanation catalyst
15 parts of ethylphosphinic acid aluminum (5 μm of mean diameter)
The epidermal area resin combination of above-mentioned formula 1 is coated with processing release paper makes thickness for 150 μm, in 100 DEG C do
It is dried 2 minutes in dry machine, forms epidermal area.Then, the adhesive linkage resin combination of above-mentioned formula 2 is coated with the epidermal area
Thickness is made for 250 μm, after being dried 3 minutes in 120 DEG C of drying machine, is fitted on polyester warp knit (tricot) cloth, to prick cloth
Machine pressure is pricked, and 72 hours aging, stripping processing release papers are carried out at 40 DEG C, obtains the anti-flammability synthetic leather of embodiment 1.
[embodiment 2]
Except making embodiment 1<Formula 2>Fire retardant be 10 parts of ethylphosphinic acid aluminum (mean diameter is 5 μm) and 5 parts
Outside the mixture of benzoguanamine (mean diameter is 10 μm), operate similarly to Example 1, obtain anti-flammability synthesis skin
Leather.
[comparative example 1]
Fire retardant is mismatched in adhesive linkage, is in addition operated similarly to Example 1, obtain anti-flammability synthesis skin
Leather.
[comparative example 2]
Except making embodiment 1<Formula 2>Fire retardant be deca-BDE and antimony trioxide mixture (mean diameter
For 4 μm) outside 15 parts, operate similarly to Example 1, obtain anti-flammability synthetic leather.
[comparative example 3]
Except making embodiment 1<Formula 2>Fire retardant be outside 15 parts of APP (mean diameter be 15 μm), with reality
Apply example 1 similarly to operate, obtain anti-flammability synthetic leather.
With regard to flammability test, the evaluation result of embodiment and the synthetic leather of comparative example is shown in into table 1.
Table 1
With regard to other assessment items, the evaluation result of embodiment and the synthetic leather of comparative example is shown in into table 2.
Table 2
| Hydrolytic resistance | It is resistance to exudative | Hydrothermal aging is tested | |
| Embodiment 1 | ○ | ○ | ○ |
| Embodiment 2 | ○ | ○ | ○ |
| Comparative example 1 | - | - | - |
| Comparative example 2 | ○ | ○ | ○ |
| Comparative example 3 | × | △ | ○ |
Due to not containing fire retardant, the hydrolytic resistance test of comparative example 1 and resistance to exudative test are omitted in table and recorded, separately
Outward, because fire resistance itself is unqualified, hydrothermal aging is tested to be omitted in table and recorded.
From Tables 1 and 2, the polyurethane resin synthetic leather of the fire retardant of the present invention is used, and used halogen
The synthetic leather of flame retardant is compared, the fire resistance with peer-level or more preferable height, while as synthetic leather
Each physical property is also able to maintain that in good state.
Claims (3)
1. a kind of fire-retardancy polyurethane resin, it is characterised in that it is the fire retardant (a) shown in following formula (1) and polyurethane tree
The fire-retardancy polyurethane resin that fat (b) is mixed, model of the mixed proportion with weight ratio meter as (a)/(b)=5/95～50/50
Enclose,
[chemical formula 1]
In formula, R1For the straight chained alkyl of hydrogen, phenyl or carbon number 1～6, M is Mg, Al, Ca, Ti or Zn, and m is 2,3 or 4.
2. fire-retardancy polyurethane resin according to claim 1, it is characterised in that relative to formula (1) described in 100 weight portions
Shown fire retardant (a), flame retardant (c) adds up to 0～200 weight portion, and the flame retardant (c) is selected from tricresyl phosphate
Poly cyanamid, melamine pyrophosphate, polyphosphoric acid melamine, APP, amidophosphoric acid ester, phthalic acid tripolycyanamide,
In the group of tripolycyanamide, melamine cyanurate, benzoguanamine, expanded graphite, aluminium hydroxide and magnesium hydroxide composition
One or more, the mixing of the fire retardant (a) shown in the formula (1) and polyurethane resin (b) and the flame retardant (c)
Scope of the ratio with weight ratio meter as { (a)+(c) }/(b)=5/95～50/50.
3. a kind of anti-flammability synthetic leather, it is characterised in that synthetic leather includes following composition, it contains fiber base material and at least
One layer of urethane resin layer, the fiber base material includes non-woven fabrics, textile, knitwear, in the urethane resin layer
Any one layer of usage right requires the fire-retardancy polyurethane resin described in 1 and/or 2 and is formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-223625 | 2014-10-15 | ||
| JP2014223625A JP6151678B2 (en) | 2014-10-15 | 2014-10-15 | Flame retardant polyurethane resin and flame retardant synthetic leather |
| PCT/JP2015/074033 WO2016059882A1 (en) | 2014-10-15 | 2015-08-26 | Flame-retardant polyurethane resin and flame-retardant synthetic leather |
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| CN106574112A true CN106574112A (en) | 2017-04-19 |
| CN106574112B CN106574112B (en) | 2020-06-19 |
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| Country | Link |
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| JP (1) | JP6151678B2 (en) |
| CN (1) | CN106574112B (en) |
| WO (1) | WO2016059882A1 (en) |
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| CN111501371A (en) * | 2019-01-30 | 2020-08-07 | 阿基里斯株式会社 | Synthetic leather |
| CN114381948A (en) * | 2022-01-18 | 2022-04-22 | 太仓维龙化工有限公司 | A halogen-free flame retardant and anti-melting drop water-based polyurethane resin and its preparation method and application |
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| CN107776147B (en) * | 2016-07-30 | 2019-10-08 | 安徽创显电子科技有限公司 | A kind of fire retarding polyurethane synthetic leather |
| KR102286926B1 (en) * | 2017-02-17 | 2021-08-06 | 현대자동차주식회사 | Flame retardant polyurethane artificial leather and manufacturing method thereof |
| WO2019083046A1 (en) | 2017-10-27 | 2019-05-02 | 共和レザー株式会社 | Synthetic leather |
| JP7238889B2 (en) * | 2018-03-29 | 2023-03-14 | 日本ゼオン株式会社 | Laminated sheets and laminates for automobile interior materials |
| WO2019189247A1 (en) * | 2018-03-30 | 2019-10-03 | 日本ゼオン株式会社 | Laminated sheet for automobile interior material, production method for laminated sheet for automobile interior material, and laminated body |
| JP2020037681A (en) * | 2018-08-31 | 2020-03-12 | 株式会社エフコンサルタント | Curable composition |
| JP2020122252A (en) * | 2019-01-30 | 2020-08-13 | アキレス株式会社 | Synthetic leather |
| JP7400156B2 (en) * | 2019-03-05 | 2023-12-19 | 大和化学工業株式会社 | Flame retardant polyurethane resin composition |
| JP2021130801A (en) * | 2019-04-01 | 2021-09-09 | 大和化学工業株式会社 | Flame retardant composition for polyurethane foam and flame retardant polyurethane foam containing it |
| US20220073691A1 (en) * | 2019-04-01 | 2022-03-10 | Daiwa Chemical Industries Co., Ltd. | Flame retardant composition for polyurethane foam and flame-retarded polyurethane foam containing the same |
| CN111455685A (en) * | 2020-04-07 | 2020-07-28 | 浙江泰鑫合成革有限公司 | Production process and preparation equipment of modified flame-retardant antibacterial PU synthetic leather |
| CN113736355B (en) * | 2021-09-03 | 2022-09-23 | 齐鲁工业大学 | Preparation method of hydrolysis-resistant flame-retardant breathable moisture-permeable polyurethane porous coating |
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| Publication number | Publication date |
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| WO2016059882A1 (en) | 2016-04-21 |
| JP6151678B2 (en) | 2017-06-21 |
| JP2016079375A (en) | 2016-05-16 |
| CN106574112B (en) | 2020-06-19 |
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