JPH06146175A - Leathery sheet good in fouling resistance - Google Patents

Abstract

PURPOSE:To obtain a leathery sheet excellent in fouling resistance by impregnating an entangled nonwoven fabric with a polyurethane resin prepared by reacting specific components at a specified blending ratio and excellent in mechanical characteristics, durability, processing suitability, etc. CONSTITUTION:This leathery sheet is obtained by reacting (A) an intermediate diol, having terminal OH groups and prepared by reacting (A1) a fluorine- containing diol obtained by radically polymerizing a perfluoroalkyl ester of (meth)acrylic acid in the presence of a compound containing hydroxyl groups and one thiol group with (A2) a polymer diol, selected from polyesters, polycarbonates and lactones, etc., and having 500-3000 number-average molecular weight and (A3) an organic diisocyanate in a quantitative relationship so as to provide 0.5-0.99 equiv. ratio of NCO/OH and (B) a low-molecular diol and (C) diphenylmethane-4,4'-diisocyanate, impregnating an entangled nonwoven fabric composed of ultrafine fiber bundles having preferably <=0.1d size with the resultant polyurethane resin and coagulating the polyurethane resin. This sheet is soft and excellent in fouling resistance and durability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a leather-like sheet having excellent stain resistance. More specifically, it is excellent in various physical properties such as mechanical properties and durability obtained by blending and reacting the specific components that make up the polyurethane resin in a specific formulation in a specific order, and has excellent stain resistance. Good leather-like sheet.

[0002]

2. Description of the Related Art Polyurethane has excellent mechanical performance, and a solution of polyurethane is impregnated and / or applied to a fibrous substrate,
BACKGROUND ART A leather-like sheet material obtained by forming naps on the surface of a fiber structure obtained by wet coagulation or dry coagulation or by providing a surface finishing layer mainly composed of polyurethane is used in various fields. However, as can be seen from the fact that conventional polyurethane resins are used as adhesives, they have good adhesion to various substances, that is, they are very poor in stain resistance, probably because they are well compatible with dirt components, and are practically used. Had become a problem. As an attempt to improve these drawbacks, attempts have been made to surface-treat with a fluorine-based compound, but during use, washing, dry cleaning, etc.,
Further improvement is desired, such as falling off and deterioration of pollution prevention effect.

JP-A-4-178416 and JP-A-4-178417 have a radically polymerizable unsaturated bond in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. A method for producing a polyurethane resin by reacting a macromonomer (A) obtained by radical polymerization of a monomer, a polyol (B) and a polyisocyanate (C), and a polyurethane resin composition comprising the resin are disclosed. In these publications, 3-mercapto-1,2-propanediol is used as a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group, and a perfluoroalkyl group is used as a monomer having a radically polymerizable unsaturated bond. Examples of the monomers are shown, the obtained polyurethane is shown to be excellent in water repellency and oil repellency, and its superiority is claimed. However, the polyurethane resins obtained by the methods of those publications are not particularly limited in their reaction sequence, or because each component in the resin does not have a controlled array structure, during polymerization, It was not possible to industrially implement it because it was difficult to obtain a polyurethane resin having a sufficient viscosity and a sufficient balance of physical properties such as heat resistance, cold resistance and strength of the obtained polyurethane resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to use a perfluoroalkyl group-introduced polyurethane having excellent physical properties such as mechanical properties and durability and excellent workability, and a leather-like sheet having good stain resistance. Is to provide industrially stable.

[0005]

The present invention is obtained by radical polymerization of a perfluoroalkyl ester of acrylic acid and / or methacrylic acid in the presence of a compound containing two hydroxyl groups and one thiol group. A fluorine-containing diol (A), a polymer diol (B) having a number average molecular weight of 500 to 3000 selected from the group consisting of polyester, polycarbonate, polylactone and polyether, and an organic diisocyanate (C1).
Intermediate diol (D) of terminal OH obtained by reacting in a quantitative relationship such that the equivalent ratio of O / OH is 0.5 to 0.99.
And low molecular diol (E), diphenylmethane-4,4
A leather-like sheet having good stain resistance, which is characterized by comprising polyurethane and a fiber structure obtained by reacting with'-diisocyanate (C2).

The fluorine-containing diol (A) can be obtained by a known method. For example, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate in the presence of 3-mercapto-1,2-propanediol. , 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-)
Methylbutyl) ethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-
Pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-)
Methyl butyl) ethyl acrylate, alkyl monomer using an initiator such as azobisisobutyronitrile, azobisisovaleronitrile, vanzoyl peroxide,
Can be polymerized. In addition, it does not matter that butyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, and other perfluoroalkyl-free methacrylates, acrylates, and other copolymerizable vinyl monomers are used in combination within a range that does not impair the object of the present invention. There is no.

The molecular weight of the fluorine-containing diol (A) is not particularly limited and is 400 to 500 depending on the monomer used.
0 is preferably 500 to 3000 among others.
If it exceeds 5,000 and is too large, a polymer having no hydroxyl group is likely to be produced during production, and it may be difficult to be effectively used for polyurethane, which may be a difficulty in industrial production.
The compounding amount is not particularly limited, but it is usually 0.1 to 20% by weight, and particularly 1 to 10% by weight, depending on the molecular structure, required water repellency, oil repellency and the like. preferable.

The polymer diol (B) used in the present invention is selected from the group consisting of polyester, polycarbonate, polylactone and polyether. The number average molecular weight is 500 to 3000, and more preferably 7
The range of 00 to 2500 is selected. If it is less than 500, the flexibility of the leather-like sheet material tends to be lost, or the texture tends to decrease. If it exceeds 3000, the urethane group concentration inevitably decreases, and the texture, flexibility,
Not only is it difficult to obtain a leather-like sheet material with well-balanced cold resistance, heat resistance, and durability, but there are difficulties in industrial production of the polymer diol.

The polyester diol used in the present invention can be obtained, for example, by reacting a dibasic acid with a diol. Examples of dibasic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, and aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. It is possible to use one type of basic acid or a combination thereof. Among them, aliphatic dibasic acids, especially adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid and the like, having a methylene chain length of 4 to 8 are more preferably used. As the diol, ethylene glycol optionally substituted with a lower alcohol, propylene glycol, butanediol, neopentyl glycol,
Aliphatic diols such as methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, cyclohexanediol, alicyclic diols such as hydrogenated xylylene glycol, xylylene glycol, etc. One kind or a mixture of two or more kinds of aromatic diols is used. Among them, aliphatic diols, especially butanediol, methylpentanediol, hexanediol, heptanediol, methyloctanediol, nonanediol, etc. One or a mixture of two or more of 4 to 9 aliphatic diols is preferably used.

The polycarbonate diol can be obtained, for example, by reacting a carbonate compound with a diol. As the carbonate compound, dimethyl carbonate, diphenyl carbonate, ethylene carbonate and the like can be used. As the diol, ethylene glycol optionally substituted with lower alcohol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol,
One or a mixture of two or more of aliphatic diols such as decanediol and dodecanediol, alicyclic diols such as cyclohexanediol and hydrogenated xylylene glycol, aromatic diols such as xylylene glycol, and the like is used. Among them, aliphatic diols, particularly butane diol, methyl pentane diol, hexane diol, heptane diol, methyl octane diol, nonane diol and the like, are suitable one or a mixture of two or more aliphatic diols having a carbon chain length of 4 to 9. Used for.

Examples of the polylactone diol include poly-ε-caprolactone diol and poly-trimethyl-ε.
-Caprolactone diol, poly-β-methyl-δ-valerolactone diol and the like can be mentioned. Examples of the polyether diol include polytetramethylene glycol, polypropylene glycol, polyethylene glycol and the like.

The organic diisocyanate (C1) is, for example, diphenylmethane-4,4'-diisocyanate,
Aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, meta or paraphenylene diisocyanate, 1,5 naphthylene diisocyanate,
Non-aromatic diisocyanates such as isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and hydrogenated MDI are used. Of these, isophorone diisocyanate and 2,4- or 2,6-tolylene diisocyanate are preferable because the sheet-like material obtained by coagulating with a nonsolvent has good surface properties and texture.

The intermediate diol (D) having a substantially OH terminal constitutes a substantially soft segment of the resulting polyurethane, and comprises the component (A), the polymer diol (B), and the organic diisocyanate (C1). And NC
It is obtained by reacting in a quantitative relationship such that the equivalent ratio of O / OH is 0.5 to 0.99. NCO / OH equivalent ratio is 0.5
If the amount is less than the above, the amount of the urethane bond incorporated into the intermediate diol having an OH terminal is substantially small, although it varies depending on the blending amount of the component (A), the molecular weight of the polymer diol (B), and the type of the organic diisocyanate (C1). It is difficult to balance the surface slimyness, texture, flexibility, cold resistance, and heat resistance of the leather-like sheet, probably because it is too small or the molecular weight becomes too small, and the effect of the present invention cannot be sufficiently obtained. . When the NCO / OH equivalent ratio exceeds 0.99,
Although it depends on the blending amount of the component (A), the molecular weight of the polymer diol (B), and the type of the organic diisocyanate (C1), the amount of the urethane bond incorporated into the intermediate diol having an OH at the end is too large. Probably because the molecular weight of the intermediate diol (D) becomes too large, it is difficult to balance the surface property, feel, flexibility, cold resistance and heat resistance of the leather-like sheet material.

As the low molecular weight diol (E), ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, which may be substituted with a lower alcohol, Aliphatic diols such as decane diol and dodecane diol, cyclohexane diol, alicyclic diols such as hydrogenated xylylene glycol, aromatic diols such as xylylene glycol, and one or a mixture of two or more such as diethylene glycol. Of these, aliphatic diols, especially ethylene glycol and butanediol, are preferably used from the viewpoint of the balance of the texture, flexibility, cold resistance and heat resistance of the leather-like sheet material.

The amount of the low molecular diol (E) used is not particularly limited, but it depends on the molecular structure, the amount of the component (A), the molecular weight of the polymer diol (B), the type of organic diisocyanate, and the NCO / OH equivalent ratio. Usually, the equivalent ratio of (E) / (B) to the polymer diol (B) is 0.5 to 7.0, and in particular 1.0 to 5.5, a leather-like sheet. It is often suitable in terms of texture, flexibility, cold resistance and heat resistance.

The amount of diphenylmethane-4,4'-diisocyanate (C2) used is not particularly limited, but the viscosity of the polyurethane solution, the molecular weight of the fluorine-containing diol (A), the polymer diol (B), and the fluorine-containing diol (A). , The NCO / OH equivalent ratio of the polymer diol (B) and the organic diisocyanate (C1), the reaction solvent, the fluorine-containing diol (A), the polymer diol (B), the water content contained in the low molecular weight diol (D), etc. But,
Usually, the equivalent ratio (NCO / OH) of NCO and fluorine-containing diol (A) from (C1) and (C2) and hydroxyl group from polymer diol (B) and low molecular diol (D) is 0.
It is preferably 95 to 1.2, especially 0.97 to 1.1.

Further, a catalyst is not always necessary when carrying out the polymerization method used in the present invention, but catalysts used in the usual production of polyurethane, for example, metal compounds such as titanium tetraisopropoxide, dibutyltin dilaurate and tin octate. , Tetramethylbutanediamine,
Tertiary amines such as 1,4-diaza (2,2,2) bicyclooctane can be used.

As the solvent for the polyurethane obtained by the method used in the present invention, for example, a commonly used solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate, methyl ethyl ketone, tetrahydrofuran and the like can be used. Polyurethane obtained by the method used in the present invention, various additives used in conventional polyurethane in use,
For example, phosphorus compounds, flame retardants such as halogen-containing compounds,
Antioxidants, ultraviolet absorbers, pigments, dyes, plasticizers, surfactants and the like can be added.

The fiber base material is not particularly limited and is selected from synthetic fibers such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon and other spinnable polyamide having an aromatic group. At least one kind of polyamide, polyester such as polyethylene terephthalate, polybutylene terephthalate, vinylon, polyacrylonitrile, etc., artificial fibers such as rayon, cupra, acetate, etc., or natural fibers such as silk, cotton, wool, hemp, etc. Any of cloth, woven cloth, non-woven cloth, three-dimensionally entangled ultrafine fiber bundle having an average single fineness of 0.1 denier or less can be used. Above all, average fineness of three-dimensionally entangled 0.1
A non-woven fabric composed of an ultrafine fiber bundle having a denier or less, and further 0.005 to 0.1 denier can be preferably used.

A non-woven fabric composed of such an ultrafine fiber bundle is
It can be derived from an ultrafine fiber-generating fiber composed of two or more kinds of polymer components containing a known polyamide resin, polyester resin or the like as an ultrafine fiber component. Other polymers constituting the ultrafine fiber-generating fiber are not particularly limited, are different in solubility or decomposability with respect to the solvent or decomposing agent with the ultrafine fiber component, a resin having little affinity with the ultrafine fiber component,
And any resin having a melt viscosity smaller than that under spinning conditions may be used, and examples thereof include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene- α-olefin copolymer, polystyrene, styrene-isoprene copolymer, hydrogenated product of styrene-isoprene copolymer, stellene-butadiene copolymer, stellene-
It is selected from hydrogenated butadiene copolymers and the like. Such ultrafine fiber-generating fibers are prepared by mixing respective component resins in a predetermined mixing ratio, dissolving them in the same dissolving system, forming a mixed system and spinning, or dissolving in another dissolving system and spinning. Occupy in the fibers by a method of repeating the joining-splitting in the head portion several times to form a mixed system and spinning, and a method of dissolving in a separate dissolving system and spinning by defining the fiber shape in the spinneret of the spinning machine. An ultrafine fiber-generating fiber having a resin component of 40 to 80% by weight and a fine fiber component in the fiber of 5 or more, preferably 50 to 800 is obtained. If necessary, the ultrafine fiber-generating fiber may have a fineness of 2 to 15 denier and an average fineness (calculated value) of the ultrafine fiber component of 0.2 denier or less, preferably 0.0 through a normal fiber treatment process such as stretching and heat setting.
The fiber has a denier of 05 to 0.1.

The ultrafine fiber-generating fibers are defibrated with a card to form a random web or a cross wrap web through a web bar, and the resulting fiber web is laminated to have a desired weight and thickness. Then, the fiber web is subjected to a fiber entanglement treatment using a needle punch, a water jet, an air jet or the like by a conventionally known method to obtain a fiber entangled nonwoven fabric.

Next, the fiber-entangled nonwoven fabric is a composition liquid obtained by adding a coagulation regulator, a mold release agent, a plasticizer, a stabilizer, an antioxidant, a light-proofing agent, a coloring agent, etc. to the polyurethane solution. And impregnating and / or coating the fibrous substrate,
Wet coagulation or dry coagulation. In the case of ultrafine fiber generation type fiber, impregnation of the polyurethane entangled liquid into the fiber entangled nonwoven fabric,
Prior to coating or after impregnation and coating, treatment is performed with a solvent of another resin constituting the fiber and a non-solvent of the fiber to obtain an ultrafine fiber structure. The amount of the polyurethane resin in the sheet material is not particularly limited, but the weight fraction is preferably 10 to 60%, and more preferably 15 to 45%. If the amount of urethane used is small, the texture is rather flat, and 1
When it is less than 0%, it becomes remarkable. If the amount of urethane is large, it will become hard and the texture will not bulge easily. 6
The tendency becomes remarkable when it is used in excess of 0%.

If necessary, the sheet-like material is further provided with a porous or non-porous coating layer obtained from the above-mentioned polyurethane on the surface to obtain a silver-finished leather-like sheet, or
At least one surface of the fiber-raised suede-like leather-like sheet can be treated by raising. Further, if necessary, it is possible to perform slice division into an arbitrary thickness in the thickness direction at an arbitrary stage.

[0024]

The thus obtained leather sheet material of the present invention is useful for various purposes such as clothing, shoes, bags, furniture, vehicle interior materials and sundries. In the manufacturing process of the leather-like sheet material, the polyurethane resin gave stain-resistant and good-feeling leather-like sheet material without losing its desirable mechanical properties and processability. Its action mechanism is not clear. The fluorine-containing diol (A), the polymer diol (B) of 500 to 3000 and the organic diisocyanate (C1) as N
A substantially OH intermediate diol (D) obtained by reacting in a quantitative relationship such that the equivalent ratio of CO / OH is 0.5 to 0.99; and a low molecular diol (E), And a soft segment and a hard segment constituting the polyurethane resin are kept in a desirable microphase-separated state, and a leather layer is impregnated with the polyurethane resin as a coat layer because a fluorine atom component is introduced near the surface. It is considered that the sheet-like product for use has the above-mentioned preferable characteristics.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the examples, parts and% relate to weight unless otherwise specified.

Example 1 Fluoro-containing diol (A) 160 having an average molecular weight of 1600 obtained from a 1: 1 mixture of 2- (perfluorohexyl) ethyl methacrylate and butyl methacrylate and 3-mercapto-1,2-propanediol. Parts by weight, 300 parts by weight of polyhexylene carbonate having a number average molecular weight of 1000 as the polymer diol (B) and 600 parts by weight of polybutylene adipate having a number average molecular weight of 1000, and 2,4-tolylene diisocyanate and 2,2 as the organic diisocyanate (C1). 165 parts by weight of a mixture of 6-tolylene diisocyanate (80:20) (NCO / OH = 0.
95), and 5370 parts by weight of DMF are charged into the reactor,
The reaction was performed under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate. After confirming that the isocyanate group had disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 66,000.

DMF of the intermediate diol (D) obtained above
106 parts by weight of ethylene glycol and 459 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added to the solution as a low molecular diol (E) and reacted to obtain a polyurethane solution having a weight average molecular weight of 390,000. To 100 parts by weight of the obtained polyurethane solution, 92 parts by weight of DMF,
Crisbon Assister SD7 (trademark: Dainippon Ink and Chemicals, Inc.) 1.5 parts by weight, Crisbon Assister SD14
(Trademark: Dainippon Ink Co., Ltd.) Add 1.5 parts by weight,
The impregnating liquid was used.

On the other hand, a web is formed by using staple fibers of ultrafine fiber-generating fibers (6-nylon is an ultrafine fiber component) obtained by melt spinning 50 parts by weight of 6-nylon and 50 parts by weight of highly fluid polyethylene. A woven non-woven fabric made by needle punching. This entangled nonwoven fabric was impregnated with the above impregnating liquid and then put into a 25% aqueous solution of DMF to coagulate. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. This sheet material was divided into two, and the divided surface was buffed with sandpaper to have a thickness of 0.56 mm. Further, the surface at the time of coagulation was treated with an emery buffing machine to form a nap surface. The sheet having the napped surface was cut and attached to an armchair of an office chair as a stain resistance test and tested for 4 months from June to September. The stain state was observed, but it was found to be almost stain-free. However, the advantages of the present invention are obvious.

Comparative Example 1 The same raw material composition as in Example 1 was put into a reactor all at once and reacted at a predetermined temperature for a predetermined time under a nitrogen stream to obtain a polyurethane solution having a weight average molecular weight of 370,000. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1. The entangled nonwoven fabric of Example 1 was impregnated with the above impregnating liquid and then put into a 25% aqueous solution of DMF to coagulate. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The obtained sheet-like material was hard and had an extremely poor feel to the touch, and was hardly called a leather-like sheet. As described above, when the polyurethane obtained without passing through the intermediate (D) obtained by reacting the fluorine-containing diol (A), the polymer diol (B), and the organic diisocyanate (C1) is used, a sheet having a good texture is obtained. Is not obtained, and the superiority of the technique of going through the intermediate (D) of the present invention is clear in comparison with Example 1.

Comparative Example 2 A mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (weight ratio 80:20) was used in Example 1 as the organic diisocyanate (C1).
5 parts by weight (NCO / 0H = 0.20) and 5 parts DMF
An intermediate was obtained in the same manner except that the amount was changed to 540 parts by weight. After confirming that the isocyanate group had disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 12,000. 106 parts by weight of ethylene glycol and 646 parts by weight of diphenylmethane-4,4′-diisocyanate (C2) as a low-molecular diol (E) were added to the DMF solution of the intermediate diol (D) obtained above and reacted, A polyurethane solution having an average molecular weight of 380,000 was obtained. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1.

The entangled nonwoven fabric used in Example 1 was impregnated with the above-mentioned impregnating solution and then put into a 25% aqueous solution of DMF.
Coagulated. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The obtained sheet-like material was hard and had an extremely poor feel to the touch, and was hardly called a leather-like sheet. Thus, the fluorine-containing diol (A), the polymer diol (B), and the organic diisocyanate (C1) were added to the NC.
When a polyurethane obtained through the intermediate (D) obtained by reacting O / OH at 0.2 is used, a sheet having a good texture cannot be obtained, and the fluorine-containing diol (A) and polymer diol of the present invention are not obtained. (B), an intermediate (D) obtained by reacting the organic diisocyanate (C1) with NCO / OH of 0.5 or more
The superiority of the technology that goes through is clear in comparison with Example 1.

Example 2 1: 1 mixture of 2- (perfluoro-3-methylbutyl) ethyl methacrylate and methyl methacrylate and 3
-Fluoro-containing diol (A) 400 having an average molecular weight of 2000 obtained from mercapto-1,2-propanediol
Parts by weight, number average molecular weight 2 as polymer diol (B)
000 polyhexylene carbonate 600 parts by weight, number average molecular weight 2000 polybutylene adipate 500 parts by weight, and number average molecular weight 2000 polytetramethylene glycol 500 parts by weight, organic diisocyanate (C
1) 188 parts by weight of diphenylmethane-4,4'-diisocyanate (NCO / OH = 0.75), and D
MF10610 weight part was thrown into the reactor, and it was made to react at predetermined temperature for predetermined time under nitrogen stream, and the intermediate body was obtained. After confirming that the isocyanate group has disappeared, the intermediate is treated with GPC.
When the weight average molecular weight (converted to polystyrene) was measured using, it was 41,000.

DMF of the intermediate diol (D) obtained above
248 parts by weight of ethylene glycol and 1100 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added and reacted to the solution as a low molecular diol (E) to obtain a polyurethane solution having a weight average molecular weight of 410,000. 19 parts by weight of DMF to 100 parts by weight of the obtained polyurethane solution,
Crisbon Assister SD7 (trademark: Dainippon Ink and Chemicals, Inc.) 1.5 parts by weight, Crisbon Assister SD14
(Trademark: Dainippon Ink Co., Ltd.) Add 1.5 parts by weight,
The coating liquid was used. After impregnating the entangled nonwoven fabric of Example 1 with the impregnating liquid of Example 1, the coating liquid is applied to a thickness of 0.5 mm.
And coated in a 25% aqueous solution of DMF to coagulate. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 2.2 mm and having a good silver surface. When the obtained sheet material was subjected to a contamination test in the same manner as in Example 1, it was hardly contaminated, and the superiority of the present invention is clear.

Comparative Example 3 In Example 2, 256 parts by weight of diphenylmethane-4,4'-diisocyanate (NCO / OH = 1.0) was used.
An intermediate was obtained in the same manner except that the amount was changed to 2) and 10640 parts by weight of DMF. After confirming that the isocyanate group had disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 240,000. In the DMF solution of the intermediate diol (D) obtained above, 24 of ethylene glycol was added as the low molecular diol (E).
83 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) was added and reacted to obtain a polyurethane solution having a weight average molecular weight of 420,000.

A sheet with a silver surface was obtained in the same manner as in Example 2 except that the polyurethane solution obtained above was used. However, the foamed state of the silver surface was poor and hard and the texture was poor. Thus, the fluorine-containing diol (A), the polymer diol (B), and the organic diisocyanate (C1) were mixed with N
When the polyurethane obtained through the intermediate (D) obtained by reacting CO / OH at 1.02 is used, a sheet having a good texture cannot be obtained, and the fluorine-containing diol (A) of the present invention,
Polymer diol (B), organic diisocyanate (C
The superiority of the technique of going through the intermediate (D) obtained by reacting 1) with NCO / OH of 0.99 or less is clear in comparison with Example 2.

Example 3 Fluoro-containing diol (A) 320 having an average molecular weight of 1600, obtained from a 1: 1 mixture of 2- (perfluorohexyl) ethyl methacrylate and butyl methacrylate and 3-mercapto-1,2-propanediol. Parts by weight, 600 parts by weight of polyhexylene carbonate having a number average molecular weight of 2000 as the polymer diol (B) and 1000 parts by weight of polybutylene adipate having a number average molecular weight of 2000, and diphenylmethane as the organic diisocyanate (C1).
200 parts by weight of 4,4'-diisocyanate (NCO / O
H = 0.80) and 9440 parts by weight of DMF were charged into the reactor, and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate. After confirming that the isocyanate group had disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 49,000.

DMF of the intermediate diol (D) obtained above
186 parts by weight of ethylene glycol and 841 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) as a low molecular diol (E) were added and reacted with the solution to obtain a polyurethane solution having a weight average molecular weight of 380,000. Using the obtained polyurethane solution, an impregnating liquid was prepared in the same manner as in Example 1. The entangled non-woven fabric used in Example 1 was impregnated with the above impregnating liquid, and then put into a 25% aqueous solution of DMF for coagulation. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet. The obtained sheet-like material was a little hard, but it is practically sufficient,
When a stain resistance test was conducted as a sheet having naps in the same manner as in Example 1, a sheet having excellent stain resistance was obtained, and the superiority of the present invention is clear.

Comparative Example 5 A fluorine-containing diol (A) having an average molecular weight of 1600, obtained from a 1: 1 mixture of 2- (perfluorohexyl) ethyl methacrylate and butyl methacrylate and 3-mercapto-1,2-propanediol was used. Without using
750 parts by weight of polyhexylene carbonate having a number average molecular weight of 2000 as the polymer diol (B) and 1250 parts by weight of polybutylene adipate having a number average molecular weight of 2000,
200 parts by weight of diphenylmethane-4,4'-diisocyanate as an organic diisocyanate (C1) (NCO /
OH = 0.8) and 9684 parts by weight of DMF were charged into the reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate. After confirming that the isocyanate group had disappeared, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 53,000.

Ethylene glycol 186 was added as a low molecular diol (E) to a DMF solution of the intermediate diol obtained above.
By weight, 842 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) was added and reacted to obtain a polyurethane solution having a weight average molecular weight of 390,000. The obtained polyurethane solution was used as an impregnating liquid in the same manner as in Example 1 to obtain a sheet-like material having a raised surface. When the stain resistance test of the obtained sheet-like material was conducted under the same conditions as in Example 1, it became dark and had a bad appearance. In comparison with Example 3, the fluorine-containing diol (A) of the present invention was used. The effect is obvious.

[0040]

EFFECTS OF THE INVENTION The leather-like sheet of the present invention uses a polyurethane resin having various physical properties such as mechanical properties and durability, excellent workability, and excellent antifouling property. It is a leather-like sheet with excellent flexibility, cold resistance, heat resistance, durability and antifouling property, and is useful for various applications such as clothing, shoes, bags, furniture, vehicle interior materials, and sundries.

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Claims (1)

[Claims] 1. A fluorine-containing diol (A) obtained by radically polymerizing a perfluoroalkyl ester of acrylic acid and / or methacrylic acid in the presence of a compound containing two hydroxyl groups and one thiol group. The number average molecular weight selected from the group consisting of polyester, polycarbonate, polylactone and polyether is 500 to 300.
0 of the polymer diol (B) and the organic diisocyanate (C1) at an NCO / OH equivalent ratio of 0.5 to 0.
By reacting the terminal OH intermediate diol (D) obtained by reacting in a quantitative relationship such as 99, the low molecular diol (E) and diphenylmethane-4,4'-diisocyanate (C2) A leather-like sheet with good stain resistance, which is characterized by comprising the obtained polyurethane and a fiber structure.