CN106574112B - Flame-retardant polyurethane resin and flame-retardant synthetic leather - Google Patents
Flame-retardant polyurethane resin and flame-retardant synthetic leather Download PDFInfo
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- CN106574112B CN106574112B CN201580039843.5A CN201580039843A CN106574112B CN 106574112 B CN106574112 B CN 106574112B CN 201580039843 A CN201580039843 A CN 201580039843A CN 106574112 B CN106574112 B CN 106574112B
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- 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
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- 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
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- 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
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- Dispersion Chemistry (AREA)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
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Abstract
The invention provides a flame-retardant polyurethane resin and a flame-retardant synthetic leather, which have high flame-retardant performance, do not inhibit the coloring performance of products, have hydrolysis resistance and seepage resistance even under high-temperature and high-humidity conditions, and can inhibit the cost increase. The flame-retardant polyurethane resin is a flame-retardant polyurethane resin obtained by mixing a metal phosphinate (a) and a polyurethane resin (b), and the mixing ratio (a)/(b) is in the range of 5/95-50/50 by weight.
Description
Technical Field
The present invention relates to a flame-retardant polyurethane resin and a flame-retardant synthetic leather, wherein the flame-retardant polyurethane resin has a remarkably high flame-retardant property at the same level as or better than that of a halogen flame retardant and has good physical properties.
Background
Conventionally, polyurethane resins have been used in various applications such as clothing, bags, shoes, furniture, interior materials for vehicles, interior materials for airplanes, and interior materials for ships, as synthetic leathers, which are one of the main applications. Among them, as fields requiring high flame retardancy, furniture, interior materials for vehicles, interior materials for airplanes, interior materials for ships, and the like can be cited.
Synthetic leather is generally formed by impregnating or laminating polyurethane into a fibrous base material such as a nonwoven fabric, a woven fabric, or a knitted fabric. However, it is known that synthetic leather is very difficult to be flame-retardant because the combustion mechanism is different between the polyurethane resin and the fiber base material constituting the synthetic leather.
As a flame retardant for synthetic leather as described above, there have been reported an additive type flame retardant which is blended in a polyurethane resin to impart flame retardancy, and a reactive type flame retardant which is copolymerized as one of resin components and incorporated into a resin to be flame-retarded when a polyurethane resin is synthesized. However, an additive-type flame retardant which is low in production cost, can be freely adjusted in the subsequent steps of production according to the intended use of the producer, and is suitable for production of a small amount of many types has been in the mainstream in the market at present because of its good practicability.
As a flame retardant, conventionally, a combination formula of a bromine-based halogen compound, particularly decabromodiphenyl ether, and antimony trioxide has been widely used because it exhibits excellent flame retardant performance. However, it has been pointed out that halogen-based compounds generate hydrogen halide and hydrogen halide upon combustion
The english class of toxic gases. Therefore, in order to protect the environment, there is a great demand for non-halogen flame retardants, particularly phosphorus flame retardants, which do not use halogen compounds, and various phosphorus flame retardants have been developed. As the phosphorus flame retardant, various flame retardants such as ammonium polyphosphate, melamine polyphosphate, red phosphorus, organic phosphorus metal salts, phosphoric acid esters, and phosphoric acid amides are known.
Various flame retarding methods using these phosphorus flame retardants have been proposed. For example, patent document 1 below discloses a leather-like sheet material in which a polycarbonate-based polyurethane solution containing a red phosphorus-based flame retardant is attached to a fiber base material.
Patent document 2 below discloses a method for producing a flame-retardant polyurethane resin composition containing a polyurethane resin, a phosphorus-nitrogen flame retardant (surface-treated ammonium polyphosphate), a polyol or a derivative thereof, and a silicon compound (alkoxy siloxane).
As another example, patent document 3 below discloses a polyurethane synthetic leather composed of a polyurethane resin layer containing a fiber base material and a phosphate-based flame retardant.
Further, patent document 4 below discloses a flame-retardant polyurethane resin in which a phosphorus-containing chain extender in the polyurethane resin is a specific phosphaphenanthrene derivative.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-163683
Patent document 2: japanese patent No. 5246101
Patent document 3: japanese patent laid-open publication No. 2013-189736
Patent document 4: japanese patent No. 5405383
Disclosure of Invention
Problems to be solved by the invention
However, 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 may impart undesirable coloring to the product. In addition, in order to obtain a balance between suppression of coloring and flame retardancy, it is sometimes necessary to add a large amount of a decolorizer, and there is a possibility that the flame retardancy is lowered or the light resistance of the decolorizer is poor.
In the method of using ammonium polyphosphate which is problematic in hydrolysis resistance as in patent document 2, the phosphorus content is about 30% and is relatively high, and flame retardant performance is easily exhibited, but even coated ammonium polyphosphate is difficult to sufficiently prevent hydrolysis under high temperature and high humidity conditions, and as a result, the produced ammonium polyphosphate not only deteriorates product properties, but also causes a whitening phenomenon called bleeding and stickiness on the product surface, and may reduce product quality. In fact, in this patent document, although the flame retardant performance and the mechanical properties of the resin composition are evaluated, no verification is made as to bleeding.
Further, although patent document 3 uses a phosphate ester, the acid value and molecular weight of the phosphate ester are limited in order to cope with the hydrolyzability and bleeding which are also problems of the phosphate ester, as described above. However, under high temperature and high humidity conditions, it is difficult to sufficiently prevent bleeding, and further, in order to improve hydrolysis resistance, it is necessary to increase the molecular weight of the phosphate ester to a condensed type, and the like, thereby decreasing the phosphorus content in the phosphate ester. As a result, there is a problem that the flame retardant performance is generally lowered.
On the other hand, as shown in patent document 4, in the method of incorporating a phosphorus-containing chain extender containing a specific phosphaphenanthrene derivative as a reactive flame retardant into a polyurethane resin, the above flame retardant is integrated into the resin by a strong chemical bond, that is, a so-called covalent bond, and therefore, there is an advantage that the flame retardant does not bleed out even under high-temperature and high-humidity conditions. However, the examples of the patent document contain the above-mentioned specific flame retardant and have a very complicated step of 10 hours at 150 ℃, further 10 hours at 180 ℃ and further 10 hours at 200 ℃, and thus have a disadvantage that it is difficult to avoid an increase in cost and to put it into practical use. Further, the concentration of phosphorus that can be contained in the polyurethane resin is limited, and if it exceeds the upper limit, not only the texture is degraded, but also the flame retardancy is evaluated only by the limiting oxygen index (LOI value), and it is difficult to appropriately judge whether or not the flame-retardant synthetic leather can sufficiently exhibit high flame retardancy by the concentration of phosphorus contained therein.
As described above, the conventional techniques have not provided a flame-retardant polyurethane resin and a flame-retardant synthetic leather which can solve the above-mentioned problems, that is, have a remarkably high flame-retardant performance at the same level as or better than that of a halogen-based flame retardant, do not inhibit coloring of products, have both hydrolysis resistance and bleeding resistance even under high-temperature and high-humidity conditions, and can suppress an increase in cost.
Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a flame-retardant polyurethane resin and a flame-retardant synthetic leather which have a remarkably high flame-retardant performance at the same level as or better than that of a halogen-based flame retardant, do not inhibit the coloring property of a product, and have both hydrolysis resistance and bleeding resistance even under high-temperature and high-humidity conditions, and further can suppress an increase in cost.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object and, as a result, have found that a flame-retardant polyurethane resin and a flame-retardant synthetic leather having a remarkably high flame-retardant performance equivalent to or better than that of a halogen-based flame retardant, not inhibiting the coloring property of a product, having both hydrolysis resistance and bleeding resistance even under high-temperature and high-humidity conditions, and further capable of suppressing an increase in cost can be obtained by providing a flame retardant represented by the following formula (1) to the synthetic leather, and have completed the present invention.
[ chemical formula 1]
In the formula, R1Is hydrogen, phenyl or straight-chain alkyl with 1-6 carbon atoms, M is Mg, Al, Ca, Ti or Zn, and M is 2, 3 or 4.
That is, the gist of the present invention is:
(1) a flame-retardant urethane resin, which is obtained by mixing a flame retardant (a) represented by the following formula (1) with a urethane resin (b) at a mixing ratio (a)/(b) of 5/95-50/50 by weight;
[ chemical formula 1]
In the formula, R1Hydrogen, phenyl or straight-chain alkyl with 1-6 carbon atoms, M is Mg, Al, Ca, Ti or Zn, and M is 2, 3 or 4;
(2) the flame-retardant urethane resin according to the above (1), wherein the total amount of the flame-retardant auxiliary (c) is 0 to 200 parts by weight based on 100 parts by weight of the flame retardant (a) represented by the formula (1), the flame-retardant auxiliary (c) is one or more selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, ammonium polyphosphate, amide phosphate, melamine phthalate, melamine cyanurate, benzoguanamine, expanded graphite, aluminum hydroxide and magnesium hydroxide, and the mixing ratio of the flame retardant (a) represented by the formula (1) to the urethane resin (b) and the flame-retardant auxiliary (c) is in the range of { (a) + (c) }/(b) { (5/95 to 50/50 in terms of a weight ratio;
(3) a flame-retardant synthetic leather characterized by comprising a fiber base material comprising a nonwoven fabric, a woven fabric or a knit fabric and at least one polyurethane resin layer formed using the flame-retardant polyurethane resin according to the above (1) and/or (2).
Effects of the invention
According to the present invention, it is possible to provide a flame-retardant polyurethane resin and a flame-retardant synthetic leather which have a remarkably high flame-retardant performance equivalent to or better than that of a halogen-based flame retardant, do not inhibit the coloring property of the product, have both hydrolysis resistance and bleeding resistance even under high-temperature and high-humidity conditions, and can suppress an increase in cost.
Further, the present invention uses a non-halogen phosphorus flame retardant, and thus has no concern about the environment as compared with conventional flame-retardant synthetic leather using a halogen flame retardant.
Detailed Description
Hereinafter, embodiments of the flame-retardant polyurethane resin and the flame-retardant synthetic leather of the present invention will be described.
[ flame retardant { the following formula (1) } ]
The flame retardant used in the present invention is a compound represented by the following formula (1).
[ chemical formula 1]
In the formula, R1Hydrogen, phenyl or straight-chain alkyl with 1-6 carbon atoms, M is Mg, Al, Ca, Ti or Zn, and M is 2, 3 or 4;
r as the above formula (1)1Preferably hydrogen, phenyl, methyl or ethyl; as M in the above formula (1), aluminum or zinc is preferred.
Specific examples of the flame retardant represented by the formula (1) include zinc phosphinate (phosphorus content rate of 31.7%), zinc phenylphosphinate (phosphorus content rate of 17.8%), zinc methylphosphinate (phosphorus content rate of 27.7%), zinc ethylphosphinate (phosphorus content rate of 24.6%), aluminum phosphinate (phosphorus content rate of 41.9%), aluminum phenylphosphinate (phosphorus content rate of 20.6%), aluminum methylphosphinate (phosphorus content rate of 35.2%) and aluminum ethylphosphinate (phosphorus content rate of 30.4%). These phosphinic acid metal salts are usually colorless or white powders, and therefore can be used without impairing the coloring properties of the products. The phosphorus content is described later.
The flame retardant represented by the above formula (1) can be obtained by heating and reacting 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 with any one of nitrate, sulfate, carbonate, and hydroxide of aluminum or zinc in the state of an aqueous solution. This is one of an acid-base reaction and a salt reaction in an aqueous solution, and the reaction proceeds rapidly, so that the target compound can be produced in a short time of 1 to 3 hours, and thus, this method is a production method capable of suppressing an increase in cost.
The average particle size of the flame retardant of the present invention is preferably 1 to 50 μm, and particularly preferably 2 to 20 μm. If the particle diameter exceeds 50 μm, the dispersion stability of the flame-retardant polyurethane resin composition may be deteriorated, and if the average particle diameter is less than 1 μm, aggregates may be generated in the resin composition or the resin composition may be extremely thickened.
The flame retardant of the present invention can exhibit a remarkably high flame retardancy without being used in combination with other flame retardants or flame retardant auxiliaries. The reason for this is considered to be the following two points.
(A) High phosphorus content
(B) Having a reducing action by a P-H bond
The high phosphorus content of (A) is known to be one of the factors for improving flame retardancy. That is, phosphorus suppresses combustion of combustible materials such as synthetic resins and fiber substrates in both gas phase and solid phase, thereby achieving flame retardancy. It is considered that, in the gas phase, the combustion is suppressed by capturing PO chemical substances derived from phosphorus as OH radicals which are a cause of combustion expansion; in the solid phase, polyphosphoric acid generated by thermal decomposition of phosphorus promotes carbonization of the resin, and a dense carbonized film is formed to block the resin from a heat source, thereby suppressing combustion. Therefore, it is considered from the above theory that the higher the phosphorus content, the higher the flame retardancy can be exhibited. The flame retardant of the present invention preferably contains 30 to 50% of phosphorus.
The reduction action of (B) having a P-H bond is not beyond the range presumed by the inventor, but is considered as a new theory for improving flame retardancy used in the present invention. That is, the P-H bond positively bonds to oxygen present on the surface of a combustible material such as a synthetic resin in a very narrow range, thereby reducing the concentration of oxygen in the surrounding area and suppressing combustion. Why is the P-H bond positively bound to oxygen? This is considered to be due to the high reducibility of the P-H bond. Reducibility is a measure indicating the degree of reduction of an object by itself being oxidized by binding to oxygen, and is generally known as an oxidation-reduction potential. In fact, sodium phosphinate has a strong reducing property and is widely used as a reducing agent for metal plating. That is, it is considered that the high reducibility means a high ability to bind oxygen, and the high reducibility contributes to the flame retardant performance. In this case, it is considered that the P-H bond of the flame retardant of the present invention combines with oxygen to form a P-OH bond, thereby decreasing the ambient oxygen concentration. The new theory of improving the flame retardancy used in the present invention is peculiar to the flame retardant of the present invention, and is different from a metal dialkylphosphinate which is a commonly commercially available organic phosphorus metal salt.
In addition, the ordinary theory is that the more easily the flame retardant is oxidized (strong reducing agent), the more easily the flame retardant is burned, but it means that the flame retardant is present alone, and in the present invention, the theory is not considered to be applicable because the flame retardant coexists with the constituent components of the polyurethane resin or the synthetic leather. In fact, as shown in example 1, it is also found that the synthetic leather exhibits a remarkably high level of performance when subjected to a flame retardant performance test.
In addition to the flame retardant of the present invention, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, ammonium polyphosphate, amide phosphate, melamine phthalate, melamine cyanurate, benzoguanamine, expanded graphite, aluminum hydroxide, and magnesium hydroxide may be optionally used in combination as a flame retardant aid in order to further improve the flame retardancy. The total amount of at least one compound of the flame retardant auxiliary is 0 to 200 parts by weight based on 100 parts by weight of the flame retardant of the present invention.
The mixing proportion of the flame retardant and the polyurethane resin is preferably 5/95-50/50, and more preferably 10/90-35/65 in terms of weight ratio. When a flame retardant aid is contained, the mixing ratio of the total of the flame retardant of the present invention and the flame retardant aid to the polyurethane resin is preferably 5/95 to 50/50, more preferably 10/90 to 35/65 in terms of weight ratio. If the blending ratio exceeds 50/50, the texture of the synthetic leather may be hardened and the tensile strength may be reduced, and if the blending ratio is less than 5/95, it may be difficult to obtain sufficient flame retardant performance.
[ flame-retardant synthetic leather ]
The flame-retardant synthetic leather of the present invention comprises a fiber base material including a nonwoven fabric, a woven fabric, and a knit fabric, and at least one polyurethane resin layer, wherein any one of the polyurethane resin layers is formed using the flame-retardant polyurethane resin of the present invention.
[ fiber base Material ]
As the fiber base material used in the present invention, nonwoven fabric, woven fabric, knitted fabric, and the like can be used. The type of the fiber material is not particularly limited, and may be a synthetic fiber such as polyester, nylon, polyacrylonitrile, polypropylene, aramid, or the like; semi-synthetic fibers such as diacetate fibers and triacetate fibers; cellulose fibers such as rayon, cotton, and hemp; animal fibers such as wool, silk, feather, etc.; or inorganic fibers such as glass fibers and carbon fibers alone or in combination.
[ polyurethane resin ]
As the polyurethane resin used in the present invention, a resin synthesized from a polyol, an isocyanate and a chain extender can be used.
Examples of the polyol include polycarbonate polyol, polyester polyol, polyether polyol, polycaprolactone polyol, polyolefin polyol, and vegetable oil polyol. These polyhydric alcohols 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.
Examples of the polycarbonate polyol include copolymers of one or more types of alkanediol such as 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methylpentanediol, and 1, 12-dodecanediol, and one or more types of carbonate compounds such as dialkyl carbonate, alkylene carbonate, and diphenyl carbonate.
Examples of the polyester polyol include polycondensates of one or more low-molecular weight diols such as ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol and diethylene glycol, and one or more low-molecular weight dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and phthalic acid.
Examples of the polyether polyol include polypropylene ether polyol, polytetramethylene ether polyol and hexamethylene ether polyol.
Examples of the vegetable oil-based polyol include castor oil-modified polyol, dimer acid-modified polyol, and soybean oil-modified polyol.
Examples of the isocyanate to be used include aliphatic diisocyanates such as methylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as 4, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, and norbornene diisocyanate; and aromatic diisocyanates such as 4, 4' -diphenylmethane diisocyanate, tolylene diisocyanate, and 1, 5-naphthalene diisocyanate. These diisocyanates may be used alone or in combination of two or more.
Preferred chain extenders include low molecular weight diols having 2 to 10 carbon atoms, for example, aliphatic diols such as ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol and neopentyl glycol; low molecular alicyclic diols such as cyclohexanediol, and the like. These polyhydric alcohols may be used alone or in combination of two or more. The average number of functional groups of these polyols is preferably 2 or more, and the average molecular weight is preferably in the range of 50 to 400.
The polyurethane resin used for the synthetic leather is not particularly limited, and examples thereof include polyether polyurethane resin, polyester polyurethane resin, and polycarbonate polyurethane resin. These may be used alone or in combination of two or more. Among these, polycarbonate-based polyurethane resins are particularly preferably used in view of excellent durability, heat resistance and weather resistance of the resulting polyurethane resin.
[ method for producing flame-retardant synthetic leather ]
The method for producing the flame-retardant synthetic leather of the present invention is not particularly limited, and the flame-retardant synthetic leather can be produced by any method of a wet method and a dry method.
The wet method is a method in which a polyurethane resin for undercoating (hereinafter referred to as an undercoating resin) mixed with a water-soluble solvent is applied to a fiber base material, and the fiber base material is immersed in a coagulation bath containing water, whereby the water-soluble solvent is eluted from the undercoating resin, the polyurethane resin is precipitated and coagulated to form a porous microporous layer having a large number of voids, and then the resultant is subjected to washing with water and drying steps to form a product. The undercoat resin may contain a flame retardant, or a pigment-containing skin-like layer that has been subjected to embossing or the like may be laminated on the undercoat resin.
The dry method is a direct coating method in which a polyurethane resin mixed with a solvent as appropriate is directly coated on a fiber base material, and the solvent is volatilized by a dryer to be cured; or a composite method in which a polyurethane resin for a skin layer containing a pigment is applied to a release paper, dried to form a skin resin layer, then a polyurethane resin for an adhesive layer is applied to the skin resin layer, and pressure-bonded to a fiber base material, and dried to form a product. In addition, aging treatment may be performed to terminate the curing reaction. Finally, the release paper is peeled off, thereby completing. A flame retardant may be added to the polyurethane resin for an adhesive layer.
Specifically, the production can be carried out by the following method, but is not limited thereto.
The composition containing the polyurethane resin for skin-like layer is applied to a release paper, and if necessary, heat treatment is performed to form a skin-like layer. Next, a composition containing a flame-retardant urethane resin, which is blended with the flame retardant of the present invention in advance, is applied as an adhesive layer on the skin layer, and the composition is bonded to a fiber substrate by pressure bonding with a roller, a hot roller, or the like in a state where the composition has adhesiveness, cooled to room temperature, and subjected to aging treatment to form an adhesive layer. Finally, the release paper is peeled off to obtain the flame-retardant synthetic leather of the present invention.
The method for applying the flame-retardant urethane resin composition may be any of various conventionally known methods, and is not particularly limited. For example, a method using an apparatus such as a reverse coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater, a comma roll coater or a T-die coater may be mentioned.
The thickness of the adhesive layer is preferably 50 to 400 μm, more preferably 100 to 300 μm in a wet state immediately after application. If the thickness is less than 50 μm, the adhesive strength may be insufficient, and if the thickness exceeds 400 μm, the texture of the synthetic leather may be hard.
The thickness of the skin layer is preferably 5 to 200 μm, more preferably 10 to 100 μm in a wet state immediately after application. If the particle size is less than 5 μm, the abrasion resistance may be insufficient, and if it exceeds 200 μm, the texture of the synthetic leather may be hard.
[ other additives ]
The flame-retardant synthetic leather of the present invention may be added with other additives within a range that does not impair the physical properties and flame-retardant properties of the synthetic leather. Examples thereof include antibacterial and antifungal agents, antistatic agents, lubricants, ultraviolet absorbers, light stabilizers such as hindered amine-based light stabilizers, antioxidants, hydrophobizing agents, plasticizers, colorants, foaming agents, antifoaming agents, urethane catalysts, and surface treatment agents.
The use of the flame-retardant urethane resin obtained in the present invention is not particularly limited, and examples thereof include seat sheets, floor mats, ceiling materials, and the like, which are used as interior materials for vehicles, railways, airplanes, and ships; table blankets for furniture, seats for chairs, curtains, blinds, draperies, etc.; outdoor tent, car cover, etc.
Examples
The present invention will be specifically described below by way of examples and comparative examples, but the technical scope of the present invention is not limited to the following examples. In the following examples, "%" and "parts" mean% by weight and parts by weight, respectively, unless otherwise specified. Each synthetic leather was evaluated by the following method.
[ flame retardancy test ]
The flame retardant performance was evaluated according to the following criteria under the automotive interior material combustion test standard of FMVSS (united states automobile safety regulation) No. 302.
In the case of self-extinguishing before reaching the a standard line, the judgment level is denoted as "NB (Non Burning, no combustion);
when the combustion time is within 60 seconds while the combustion distance is within 50mm when the Self-extinguishing is performed beyond the a standard line, the determination level is designated as "SE (Self-extinguishing)";
when the combustion speed between the standard lines is 102 mm/min or less, the judgment level is referred to as "slow flammability";
when the combustion speed between the reference lines exceeded 102 mm/min, the judgment level was regarded as "failed".
In addition, the flame retardant performance is high in the sequence of "NB" ≧ SE "≧ slow flame retardancy", and the three grades are all qualified.
Further, in order to easily compare the difference in flame retardancy, the combustion distance from the portion where each sample contacts the flame was represented by an average of four points. The smaller the value of the combustion distance, the better the value.
[ hydrolysis resistance test ]
Evaluation of the flame retardant powder (hereinafter referred to as powder) was performed. As a test method, about 5g of the powder was charged into a beaker, and left to stand in a constant temperature and humidity cell adjusted to 70 ℃ and 90% relative humidity without covering for 500 hours, and the presence or absence of change in the powder state before and after the test was evaluated by the appearance (presence or absence of discoloration), FT-IR (Fourier transform infrared spectroscopy) and TGA (thermal gravimetric analysis), and the evaluation was made according to the following criteria.
○ No clear change was observed in the powder before and after the test in all of the three evaluation methods;
x: in any of the three evaluation methods described above, a clear change in the powder before and after the test was observed (when discoloration, a different peak in FT-IR, or a difference in TGA thermal decomposition curve was observed, hydrolysis of the flame retardant or a change in the chemical structure was suggested)
[ penetration resistance test ]
The synthetic leather was evaluated. As a test method, a synthetic leather cut to 18X 25cm was placed in a constant temperature and humidity chamber adjusted to 70 ℃ and a relative humidity of 90%, and the state of the surface of the synthetic leather after 500 hours had passed was visually observed and judged according to the following criteria.
○ synthetic leather surface is not whitened at all
△ slight whitening of the surface of the synthetic leather
X: the surface of the synthetic leather is obviously whitened
[ Damp-Heat aging test ]
The synthetic leather was evaluated. As a test method, a synthetic leather cut to 18X 25cm was placed in a constant temperature and humidity chamber adjusted to 70 ℃ and a relative humidity of 90%, and the above-mentioned flame retardancy test was performed on the synthetic leather after 500 hours, and the judgment was made according to the following criteria.
○ after the humid heat aging test, no decrease in flame retardant properties was observed compared with that before the test.
X: after the damp-heat aging test, the flame retardant performance is found to be obviously reduced compared with that before the test.
[ example 1]
The polyurethane resin composition for skin-like layer was prepared according to the following formulation.
< formulation 1>
100 parts of polycarbonate-based polyurethane resin (solid content 25%, solvent DMF)
Dimethylformamide (DMF)40 parts
12 parts of carbon black pigment
The urethane resin composition for adhesive layer was prepared according to the following formulation.
< formulation 2>
100 parts of polycarbonate-based polyurethane resin (solid content 70%, solvent MEK)
50 parts of Methyl Ethyl Ketone (MEK)
10 parts of urethane curing agent (polyisocyanate)
2 parts of carbamation catalyst
Ethyl aluminum phosphinate (average particle size 5 μm)15 parts
The resin composition for skin-like layer of the above formulation 1 was applied to a release paper to a thickness of 150 μm, and dried in a dryer at 100 ℃ for 2 minutes to form a skin-like layer. Then, the resin composition for an adhesive layer of the above formulation 2 was applied to the skin layer to a thickness of 250 μm, dried in a dryer at 120 ℃ for 3 minutes, attached to a polyester warp knitted (tricot) fabric, pressed with a binder, aged at 40 ℃ for 72 hours, and peeled off from the release paper, thereby obtaining a flame-retardant synthetic leather of example 1.
[ example 2]
A flame-retardant synthetic leather was obtained in the same manner as in example 1 except that the flame retardant in < formulation 2> in example 1 was a mixture of 10 parts of aluminum ethylphosphinate (average particle diameter: 5 μm) and 5 parts of benzoguanamine (average particle diameter: 10 μm).
Comparative 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.
Comparative example 2
Flame-retardant synthetic leather was obtained in the same manner as in example 1 except that 15 parts of a mixture (average particle diameter: 4 μm) of decabromodiphenyl ether and antimony trioxide was used as the flame retardant in < formulation 2> of example 1.
Comparative example 3
A flame-retardant synthetic leather was obtained in the same manner as in example 1, except that 15 parts of ammonium polyphosphate (average particle size 15 μm) was used as the flame retardant in < formulation 2> of example 1.
The evaluation results of the synthetic leathers of examples and comparative examples are shown in table 1.
TABLE 1
The evaluation results of the synthetic leathers of examples and comparative examples are shown in table 2 for other evaluation items.
TABLE 2
| Resistance to hydrolysis | Resistance to bleed-out | Humid heat aging test | |
| Example 1 | ○ | ○ | ○ |
| Example 2 | ○ | ○ | ○ |
| Comparative example 1 | - | - | - |
| Comparative example 2 | ○ | ○ | ○ |
| Comparative example 3 | × | △ | ○ |
Since no flame retardant was contained, the hydrolysis resistance test and the bleeding resistance test of comparative example 1 are omitted from the table, and the wet heat aging test is omitted from the table because the flame retardant performance itself is not satisfactory.
As is apparent from tables 1 and 2, the synthetic leather made of the polyurethane resin using the flame retardant of the present invention has a high flame retardant performance at the same level or better than that of the synthetic leather using the halogen-based flame retardant, and the respective physical properties of the synthetic leather can be maintained in a good state.
Claims (2)
1. A flame-retardant synthetic leather characterized by comprising (1) a fiber base material layer comprising a nonwoven fabric, a woven fabric or a knit fabric and (2) at least one flame-retardant polyurethane resin layer,
the flame-retardant polyurethane resin layer is a flame-retardant polyurethane resin containing the following components (a) - (c), wherein the mixing ratio of the components (a) - (c) is (a)/(b) ═ 5/95-50/50, { (a) + (c) }/(b) { (5/95-50/50) and (c)/(a) } 0-200/100 in a weight ratio, wherein (c) ≠ 0;
(a) a flame retardant represented by formula (1), (b) a polyurethane resin, (c) a flame retardant aid, wherein the flame retardant aid (c) is one or more selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine phthalate, melamine cyanurate, and benzoguanamine;
[ chemical formula 1]
In the formula, R1Is hydrogen or straight-chain alkyl with 1-6 carbon atoms, M is Al or Zn, M is 2 or 3,
wherein the flame-retardant synthetic leather comprises a polyurethane skin layer and a polyurethane adhesive layer, the polyurethane adhesive layer is a flame-retardant polyurethane resin layer,
the thickness of the skin layer is 5 to 200 μm in a wet state immediately after coating.
2. The flame-retardant synthetic leather according to claim 1, wherein the average particle diameter of the flame retardant (a) represented by the formula (1) is 1 to 50 μm.
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| 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 CN106574112A (en) | 2017-04-19 |
| CN106574112B true CN106574112B (en) | 2020-06-19 |
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| CN106273997B (en) * | 2016-07-30 | 2018-01-09 | 刘秀兰 | A kind of preparation method of fire retarding polyurethane synthetic leather |
| KR102286926B1 (en) * | 2017-02-17 | 2021-08-06 | 현대자동차주식회사 | Flame retardant polyurethane artificial leather and manufacturing method thereof |
| US11434602B2 (en) | 2017-10-27 | 2022-09-06 | Kyowa Leather Cloth Co., Ltd. | 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 |
| CN111501371A (en) * | 2019-01-30 | 2020-08-07 | 阿基里斯株式会社 | 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 having the same mixed therein |
| 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 |
| CN114381948A (en) * | 2022-01-18 | 2022-04-22 | 太仓维龙化工有限公司 | Halogen-free flame-retardant melting and dripping-resistant polyurethane resin and preparation method and application thereof |
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| JP2007297757A (en) * | 2006-05-02 | 2007-11-15 | Daiwa Kagaku Kogyo Kk | Method for processing fiber and paper |
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| JP4989522B2 (en) * | 2008-03-05 | 2012-08-01 | セーレン株式会社 | Flame retardant synthetic leather |
| DE102010018682A1 (en) * | 2010-04-29 | 2011-11-03 | Clariant International Ltd. | Process for the preparation of alkylphosphonous acid salts |
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| JP2007297757A (en) * | 2006-05-02 | 2007-11-15 | Daiwa Kagaku Kogyo Kk | Method for processing fiber and paper |
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| CN106574112A (en) | 2017-04-19 |
| WO2016059882A1 (en) | 2016-04-21 |
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