JPH02264081A - Flame-retardant synthetic leather - Google Patents

Abstract

PURPOSE:To obtain flame-retardant synthetic leather having excellent light resistance and hydrolysis resistance and durative flame retardancy, laminating a flame-retardant fiber based material or a fiber based material treated with a flame retarder and a urethane resin layer through an adhesive containing a phosphorus-containing and bromine-containing urethane compound with a polyurethane resin layer. CONSTITUTION:Said polyurethane layer is formed by coating a mold-releasing paper with a polyurethane solution, preferably a polycarbonate polyurethane solution followed by drying. Then, the urethane layer is coated with an adhesive solution containing phosphorus and bromine-containing urethane compound and a fiber basic material, especially a flame-retardant fiber basic material or a fiber basic material treated with flame retardant is laminated on the adhesive layer and the adhesive layer is cured, and the product is released form the paper to give a flame-retardant synthetic leather without reduction in light resistance and hydrolysis resistance, further without migration of the flame retarder on the leather surface.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flame-retardant synthetic leather that has excellent light resistance, hydrolysis resistance, and long-lasting flame-retardant effect.

[Conventional technology and Problems that the invention seeks to solve]

Wet methods and dry methods are known as methods for producing synthetic leather, and the dry method is a method in which a polyurethane resin layer is laminated on a fiber base material via an adhesive to produce synthetic leather. Conventionally, in order to impart flame retardancy to these synthetic leathers, the fiber base material has been subjected to flame retardant treatment, and in the dry method, a flame retardant has been added to the adhesive layer. Conventionally, flame retardants added to such an adhesive layer include hexachlorobenzene, hexachlorocyclohexane, hexabromobenzene, pentabromoethylbenzene, 1, 2-dibromoethylene, 1,
2. Halogen compounds such as 3-tetrabromobutane, phosphate ester compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (dichloropropyl) phosphate,
Tris (2,3-dibromopropyl) phosphate, tris (2-bromoethyl) phosphate, tris (chlorophenyl) phosphate, 1. 2. Halogen-containing phosphate ester compounds such as 4-tribromophosphate, tris(chloropropyl)phosphate, tetrakis(2-chloroethyl)ethylene diphosphate, antimony trioxide, antimony pentoxide, aluminum hydroxide, calcium carbonate, clay, barium sulfate Inorganic compounds such as

However, when these compounds are added, the hydrolysis resistance and light resistance of the polyurethane that makes up the synthetic leather decreases, and the resin becomes brittle and deteriorates, which are disadvantageous.Furthermore, flame retardants tend to ooze out onto the surface. There was also.

[Means to solve the problem]

An object of the present invention is to provide a flame-retardant synthetic leather that solves the above-mentioned conventional drawbacks.

That is, the present invention provides: (1) a flame-retardant fiber base material or a fiber base material that has been subjected to flame-retardant treatment; A flame-retardant synthetic leather characterized by consisting of a polyurethane resin layer.

(2) The flame-retardant synthetic leather according to claim 1, wherein the adhesive layer is made of a polyurethane adhesive.

The main points are as follows.

〔Example〕

Hereinafter, one embodiment of the present invention will be described based on the drawings.

FIG. 1 shows one embodiment of the flame-retardant synthetic leather 1 of the present invention, which has a structure in which a polyurethane resin layer 4 is laminated on the surface of a fiber base material 2 via an adhesive layer 3. are doing.

Examples of the fibers constituting the fiber base material 2 include natural fibers such as cotton and linen, recycled fibers such as rayon, cotton wool, and acetate, and synthetic fibers such as polyester, polyamide, and polyacrylonitrile, either alone or in various blends. The fiber base material 2 can be composed of a knitted fabric, a woven fabric, a non-woven fabric, etc. in which these fibers are knitted, woven or entangled.In the present invention, these fiber base materials 1 have flame retardancy. The method for making the fiber base material 2 flame retardant is as follows:
Examples include a method in which the fiber base material 2 is constructed using flame-retardant fibers, and (2) a method in which the fiber base material 1 is post-treated with a flame retardant to impart flame retardancy. When flame retardant properties are imparted by method (2), flame retardant fibers may be obtained by copolymerizing polyester with flame retardants such as phosphorus compounds and halogen compounds, or by spinning a mixture of these flame retardants. Polyester spun yarn or filament alone or blended with other fibers, modacrylic synthetic fiber made of vinyl chloride-acrylonitrile copolymer fiber, voriclar synthetic fiber made of vinyl chloride-polyvinyl alcohol copolymer fiber, etc. alone Alternatively, the fiber base material 2 is constructed by knitting, weaving, and intertwining using blended fibers. Further, in order to impart flame retardancy by the method (2), the fiber base material 2 may be post-treated with a halogen compound, a halogenated phosphate compound, a phosphorus-containing nitrogen-containing compound, etc., or a mixture thereof. As a treatment method, methods such as an impregnation method, a coating method, and a gravure method can be adopted. If these flame retardants are attached in excess, there is a risk that they will migrate to the polyurethane resin layer 4 and deteriorate the polyurethane resin layer 4, so the amount of flame retardant attached to the fiber base material 2 is set at 5 to 20% by weight. It is preferable.

The surface of the fiber base material 2 may or may not be brushed, but if it is brushed, the texture of the synthetic leather will be softer,
In addition, it provides a rich sense of volume, which is preferable.

The adhesive constituting the adhesive layer 3 may be any adhesive as long as it has adhesive properties between the fiber base material 2 and the polyurethane resin N4. It is preferable to use an excellent urethane adhesive, and when a urethane adhesive is used, the effect of preventing the phosphorus-containing bromine urethane compound from seeping out from the adhesive layer 3 is most excellent. 100% urethane adhesive
It is preferable to use polyurethane having a modulus of 10 to 60 kg/84. Examples of the above polyurethane include polycarbonate polyurethane, polytetramethylene ether polyurethane, polypropylene ether polyurethane, polyester-ether polyurethane, polymethylvalerolactone ester polyurethane, etc. Two-component adhesives made of these polyurethanes may be used. I can do it. The polycarbonate-based polyurethane is a polymer of a polycarbonate-based polyol, a diisocyanate compound, and a chain extender, and the polycarbonate-based polyol is generally preferably a polyalkylene polycarbonate-based polyol, particularly preferably a 1.6-hexane polycarbonate-based polyol. . Also usable are copolymers in which part of the polyalkylene polycarbonate polyol is replaced with a polyoxyalkylene polyol, for example a modified polycarbonate such as polypropylene glycol or polytetramethylene glycol. Also,
The diisocyanate compound to be reacted with this polycarbonate polyol is tolylene diisocyanate (TDI).
), diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMD I ), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, and the like can be used. Chain extenders include low molecular weight glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, or piperazine, ethylenediamine, hexamethylenediamine, and propylene-1
, 2-diamine, N-methyl-bis(3-aminopropyl)amine, 1゜4-diaminocyclohexane, 1-amino-3-aminomethyl-3,5,5-1-limethylcyclohexane, etc. Alternatively, a secondary aliphatic amine can be used. Polytetramethylene ether-based polyurethanes include those that use polytetramethylene ether glycol as a polyol component, and polypropylene ether-based polyurethanes use polytetramethylene ether glycol as a polyol component.
For example, those using polypropylene ether glycol can be mentioned.

Polyester-ether polyurethanes include those using a mixture of polyester glycol consisting of a glycol having 4 or more carbon atoms and dicarboxylic acid, and polytetramethylene ether glycol or polypropylene ether glycol as a polyol component, such as polymethyl valerolactone. Examples of ester-based polyurethanes include those using polymethylvalerolactone polyol as a polyol component. The diisocyanate compounds and chain extenders used in these polycarbonate-based, polytetramethylene ether-based, polypropylene ether-based, polyester-ether-based, and polymethylvalerolactone ester-based polyurethanes are the same as those used in the polycarbonate-based polyurethanes mentioned above. things are used. Various additives such as antioxidants, light stabilizers, ultraviolet absorbers, and hydrolysis inhibitors can be added to these polyurethanes as necessary.

Examples of crosslinking agents used in urethane adhesives include adducts of trimethylolpropane (TMP) and TDI, and TMP.
and HMDI adduct bodies, TMP and IPDI adduct bodies, and HMDI I trimer body. The amount of the crosslinking agent added is 5 to 20 parts by weight per 100 parts by weight of polyurethane (polyurethane solid content). If the amount of crosslinking agent is too small, the adhesive strength will be insufficient, and if it is too large, it will become too hard. Further, it is preferable to add an amine catalyst to the urethane adhesive as a crosslinking promoter, if necessary. The adhesive layer 3 can also be colored if necessary. Moreover, the thickness of the adhesive layer 3 is preferably 10 to 100 μm.

The phosphorus-containing bromine urethane compound contained in the adhesive layer 3 has a phosphorus content of 1 to 10% and a from content of 10%.
~40% of the compound is preferred, and the amount added is preferably 10 to 40 parts by weight per 100 parts by weight (solid content) of the adhesive.

Examples of the phosphorus-containing bromo-urethane compound used in the present invention include phosphorus-containing bromo-urethane compounds having a urethane bond in the molecule, such as Frame Guard PU-300 (product name) manufactured by Dainippon Ink Company. It will be done.

The polyurethane resin layer 4 has a 100% modulus of 30 to 2.
00 kg/aj is preferably made of polyurethane resin, and its thickness is preferably 3 to 100 μm. When this polyurethane resin layer 4 is thin, it does not necessarily need to contain flame retardant, but when it is thick (usually 7
When the adhesive layer is about M or higher), it is preferable to contain the same phosphorus-containing bromine urethane compound as contained in the adhesive layer 3. When adding a phosphorus-containing bromine urethane compound to this polyurethane resin N4, it is preferably added in an amount of 10 to 40 parts by weight per 100 parts by weight of the polyurethane resin layer. The polyurethane resin constituting the polyurethane resin layer 4 is preferably polycarbonate polyurethane. The polyurethane resin layer 3 is formed by coating a release paper with a polyurethane solution for forming a polyurethane resin layer, drying it to form a polyurethane film, and then applying an adhesive (phosphorus-containing bromine) as exemplified in the adhesive layer 3 on top of this film. It can be formed by a transfer method in which after applying a urethane compound (containing a urethane compound), the adhesive is bonded to the fiber base material 2, the adhesive is reacted and cured, and then the release paper is peeled off. After forming a polyurethane film on a release paper and then applying an adhesive to the surface of this polyurethane film, the method of laminating it with a fiber base material is a wet lamination method, a dry lamination method, or a semi-wet lamination method using a combination of these methods, a semi-dry method. Lamination method etc. are adopted. The polyurethane resin layer 4 may be made of transparent polyurethane or colored polyurethane.

In the present invention, the polyurethane resin layer is not limited to one layer, but may have a two-layer structure including a middle skin layer 5 and a skin layer 6, as shown in FIG. In this case, the intermediate skin ji5 is preferably made of polyurethane having a 100% modulus of 20 to 180) cg/cd, and preferably has a thickness of 10 to 100 microns. The polyurethane constituting the middle skin N5 is preferably polycarbonate polyurethane, polytetramethylene ether polyurethane, or polymethylvalerolactone polyurethane. The skin layer 6 is preferably made of polyurethane having a 100% modulus of 30 to 200 kg/cd, and preferably has a thickness of 5 to 50 microns. As the polyurethane constituting the outer skin layer 6, polycarbonate polyurethane is preferable.
i5, the epidermal layer 6 may be colored if necessary. Furthermore, the intermediate skin layer 5 is not limited to a non-foamed one, but may be a foamed one.

It is preferable that the medium skin layer 5 contains the same phosphorus-containing bromine urethane compound as described above, and the amount added is preferably 10 to 40 parts by weight per 100 parts by weight of polyurethane (solid content). Further, the same amount of phosphorus-containing bromine urethane compound can be contained in the skin layer 6, but when the thickness of the skin layer 6 is thin, the phosphorus-containing bromine urethane compound is not necessarily contained. Tomoyoshi.

In the synthetic leather of the present invention, it is also possible to use, as the fiber base material 2, the above-mentioned woven fabric, woven fabric, non-woven fabric, etc. impregnated with the same polyurethane as above. Further, as shown in FIG. 3, after forming a wet microporous layer 7 on the surface of the fiber base material 2, a medium skin layer 5 and an epidermis 16 are formed on the surface of the microporous layer 7 with an adhesive layer 3 similar to that described above. Alternatively, although not particularly shown, an adhesive layer 3 may be provided on the surface of the wet microporous 1i7.
It is also possible to provide only one polyurethane resin layer 4 with the polyurethane resin layer 4 interposed therebetween. This wet microporous layer 7 is formed by applying a water-miscible organic solvent solution of the same polyurethane resin as described above, and then immersing it in water to dissolve and remove the water-miscible organic solvent, thereby solidifying the polyurethane. can do. When providing a wet microporous layer 7, this wet microporous layer 7
It is also preferable to contain the same amount of the same phosphorus-containing bromourethane compound as above.

Hereinafter, the present invention will be explained in more detail by giving specific examples.

Example 1 100% modulus is 90 kg/c on release paper with diaphragm
-Polycarbonate polyurethane (manufactured by Dainichiseika):
A polyurethane solution containing 30 parts by weight of a phosphorus-containing bromine urethane compound (manufactured by Dainippon Ink ■: Frame Guard PU-300) per 100 parts by weight (polyurethane solid content) of Rethermin NE-8880) was added to a dry thickness of 10 μm. It was coated using a knife coater as described above and dried with hot air at 90° C. for 2 minutes to form a polyurethane film (skin N).

Then, on top of this film, a film with a 100% modulus of 55 kg was applied.
/cd polycarbonate polyurethane (Dainichiseika ■
A polyurethane solution containing 30 parts by weight of Frame Guard PU-300 per 100 parts by weight (manufactured by Rethermin NE-8850) was applied with a knife coater to a dry thickness of 25μ, and dried with hot air at 100°C for 2 minutes. A polyurethane film (medium skin layer) was formed. The surface of this polyurethane film (medium layer) has a 100% modulus of 2.
As a two-component adhesive of 5 kg/c- polycarbonate-based polyurethane (manufactured by Dainichiseika: Rezamin UD-8345), 30 parts by weight of Frame Guard PU-300 and a crosslinking agent (Japanese) were used per 100 parts by weight of polyurethane solid content. A mixture containing 15 parts by weight of polyurethane (Coronate L) and 067 parts by weight of a crosslinking accelerator (dimethylethanolamine) was applied using a knife coater to a dry thickness of 45μ, and the adhesive-coated side was was attached to the fiber base material with the raised side of the fiber base material facing, dried with hot air at 80 °C for 5 minutes, further aged at 60 °C for 48 hours to reaction cure the adhesive, and then peeled off the release paper. Synthetic leather was obtained. The above-mentioned fiber base material is a polyester/rayon blend fabric containing halogenated phosphate ester compound (Dainippon Ink ■
Manufactured by Frame Guard 5316-3) 15% by weight, phosphorus-containing nitrogen-containing compound (Dainippon Ink ■ Manufactured by Frame Guard VF)
74) Immerse it in a treatment solution containing 10% by weight, squeeze it so that the wet pickup rate is 80%, and heat it at 130°C for 5 minutes.
The material was dried with hot air for a minute to make it flame retardant.

The resulting synthetic leather closely resembles natural leather in both texture and appearance.
It was suitable as a material for furniture and vehicle seats.

Example 2 100% modulus is 100 kg on release paper with diaphragm
/c1i polycarbonate polyurethane (manufactured by Dainippon Ink ■: Crisbon 349B) 100 parts by weight (polyurethane solid content) contains 20 parts by weight of Frame Guard PU-300 as a phosphorus-containing bromourethane compound and 5 parts by weight of a colorant. Using a knife coater, apply the polyurethane solution to a dry thickness of 10 μm.
Dry with hot air for 2 minutes at °C to form a polyurethane film (skin layer).
was formed. Next, on this film, polytetramethylene ether polyurethane (manufactured by Dainichiseika) with a 100% modulus of 80 kg/cj (Rezamin ME-8115L) was applied.
P) Per 100 parts by weight, Frame Guard PU-300
30 parts by weight, light stabilizer (Sanol LS-744LD)
A polyurethane solution containing 0.5 parts by weight and 25 parts by weight of a coloring agent was applied using a knife coater to a dry thickness of 20μ, and dried with hot air at 100°C for 2 minutes to form a polyurethane film (medium layer). Formed. The surface of this polyurethane film (medium layer) has a 100% modulus of 20
kg/cJ polytetramethylene ether-based polyurethane two-component adhesive (manufactured by Dainippon Ink ■: Crisbon TA)
-265), per 100 parts by weight of polyurethane solid content, 20 parts by weight of Frame Guard PU-300, 20 parts by weight of crosslinking agent (manufactured by Dainippon Ink ■: Crisbon NX), and 1 part by weight of crosslinking accelerator (dimethylethanolamine). was added using a knife coater so that the dry thickness was 40μ, and after drying with hot air at 80°C for 3 minutes, the adhesive coated side was turned towards the raised side of the fiber base material. After bonding with a fiber base material and aging at 60"C for 48 hours to reaction-cure the adhesive, the release paper was peeled off to obtain synthetic leather.The fiber base material was polyester containing a phosphorus compound. A raised fabric made of flame-retardant polyester fibers obtained by copolymerization was used.

The resulting synthetic leather closely resembles natural leather in both texture and appearance.
It was suitable as a material for furniture and vehicle seats.

Comparative Example 1 Instead of the phosphorus-containing bromourethane compound, the same amount of halogen-containing condensed organic phosphoric acid ester (manufactured by Ohe Chemical Co., Ltd.: CR-5) was used.
Synthetic leather was obtained in the same manner as in Example 1 except that 05) was used.

Comparative Example 2 Synthetic leather was obtained in the same manner as in Example 2, except that the same amount of a halogenated phosphate ester compound (manufactured by Stofa Chemical Co., Ltd.: Phylor FR-2) was used instead of the phosphorous-containing bromourethane compound. Ta.

The combustion resistance, hydrolysis resistance, light resistance, and plume resistance of each synthetic leather obtained in Example 1.2 and Comparative Example 1.2 were tested under the conditions shown below. The results are shown in Table 1. In the blank test in Table 1, the synthetic leather was left at room temperature for 2 days, and then the resin layer was subjected to a load of 1 using a tapered abrasion tester.
It shows the state of wear on the surface when a wear test was conducted under the conditions of 2000 kg and 2000 wear cycles.

・Flame resistance test Tested according to JIS L1019B method.

The results are shown in carbonization distance (cm).

・Hydrolysis resistance test After leaving the synthetic leather sample piece at room temperature for 2 days, the relative humidity was 95%.
The resin layer of the sample piece was left for 10 weeks at a temperature of 70°C, and then the resin layer of the sample piece was subjected to an abrasion test using a tapered abrasion tester under the conditions of a load of 1 kg and a number of abrasion cycles of 2000 times, and the state of surface wear was observed.

・Light resistance test After leaving the synthetic leather test piece at room temperature for 2 days, it was irradiated with light for 300 hours using a fuudometer with a black panel temperature of 63°C, and then the resin layer of the test piece was tested using a tapered abrasion tester under a load of 1 kg. , abrasion test was carried out under the conditions of 2000 wear cycles,
The state of surface wear was observed.

In addition, the surface abrasion state after the hydrolysis resistance test, light resistance test, and blank test was determined as follows: ○...No damage on the surface.

Δ...Slight damage occurred on the surface.

×: Worn to the extent that the base material is exposed.

It was judged as.

・Bloom resistance test After the synthetic leather specimen was left at room temperature for 3 months, the surface condition was visually observed to determine the presence or absence of a flame retardant plume. ○...No flame retardant plume was observed.

x: Plume of flame retardant was observed.

It was judged as.

Table 1 As is clear from these results, the synthetic leather of the present invention has excellent flame retardancy, excellent hydrolysis resistance, and light resistance, and also exhibits very little flame retardant exudation. there were.

(Effects of the Invention) As explained above, the flame-retardant synthetic leather of the present invention uses a phosphorus-containing bromine urethane compound as a flame retardant, and incorporates this into at least the adhesive layer that adheres the fiber base material and the polyurethane resin layer. By adding this to the polyurethane resin, it has excellent flame resistance, and unlike conventional flame retardant synthetic leather, the polyurethane resin is less likely to become brittle or deteriorate due to the addition of flame retardants, making it highly resistant to hydrolysis and light. Excellent in sex etc.

In addition, the flame-retardant synthetic leather of the present invention does not easily generate a plume of flame retardant, and can maintain excellent flame retardancy for a long period of time. In particular, when a urethane adhesive is used as an adhesive, it is compatible with phosphorus-containing bromo-urethane compounds. It has particularly excellent bloom resistance.

[Brief explanation of drawings]

The drawings show one embodiment of the present invention, and FIG. 1 is a longitudinal cross-sectional view of one embodiment of the synthetic leather of the present invention, and FIGS. 2 and 3 are longitudinal cross-sections showing different embodiments of the synthetic leather of the present invention, respectively. It is a diagram. ■...Flame retardant synthetic leather 2...Fiber base material 3...
Adhesive N 4... Polyurethane resin layer End... Middle skin layer 6... Outer skin layer 7... Wet microporous layer 1: Tuna flammable synthetic leather 2: Fiber base material 3: Adhesive layer 4: Polyurethane resin Layer 5: Mesodermal layer 6: Epidermal layer 7: Warm microporous layer

Claims (2)

[Claims] (1) A flame-retardant fiber base material or a flame-retardant treated fiber base material and a polyurethane resin layer laminated on the surface of the fiber base material via an adhesive layer containing a phosphorus-containing bromourethane compound. A flame-retardant synthetic leather that is characterized by (2) The flame-retardant synthetic leather according to claim 1, wherein the adhesive layer is made of a polyurethane adhesive.