JPH0633573B2 - Artificial leather - Google Patents

Description

TECHNICAL FIELD The present invention relates to pseudo leather, and more particularly to pseudo leather having excellent surface properties.

(Prior Art) Conventionally, pseudo leather in which a synthetic resin layer is provided on the surface of a base material sheet such as a woven fabric or a non-woven fabric has been widely used. The surface of the resin layer of these pseudo leathers is required to have excellent stain resistance, water resistance, abrasion resistance, adhesion resistance and the like, and a low surface friction coefficient is required for some applications.

To meet such demands, a method of adding additives such as silicone oil, wax, fatty acid, etc., which imparts lubricity and water repellent property to the resin layer has been carried out.

(Problems to be Solved by the Invention) According to the method as described above, the object is achieved to some extent. However, in such a method, the additive added to the resin layer is not deposited on the surface of the resin layer over time. Since bleeding out causes various problems such as severe contamination and blocking,
The additive is limited to the amount added at most about several percent, and therefore, the desired performance cannot be sufficiently exhibited.

As a result of earnest research to solve the above-mentioned drawbacks of the prior art and to meet the above-mentioned demands, the present inventor modified a resin with a specific modifier to form a resin layer of pseudo leather. Completed the present invention by discovering that the above-mentioned drawbacks of the prior art can be solved and a pseudo leather having excellent surface properties can be provided.

(Means for Solving Problems) That is, the present invention comprises a substrate sheet and a resin provided on at least one surface of the substrate sheet, and the resin layer comprises
In a pseudo leather, which is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate, which is made of a resin modified with a modifier having substantially no free isocyanate group. is there.

The present invention will be described in more detail. The modifier of the film-forming resin used in the present invention, which is the first feature of the present invention, is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate. And the reaction product has substantially no free isocyanate group.

The fluorine compound having a reactive organic functional group used for obtaining such a modifier is any one having a group capable of reacting with an isocyanate group such as an amino group, a carboxyl group, a hydroxyl group and a thioalcohol group. However, a particularly preferable example is a fluorine compound represented by the following formula.

(1) H (CF ₂ CF ₂ ) _n CH ₂ OH (n = 1 to 7) (2) CF ₃ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OH (n = 1 to 10) (3) CF ₃ (CF ₂ CF ₂ ) _n COOH (n = 1 to 10) (4) CF ₃ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ SH (n = 1 to 10) (5) H (CF ₂ CF ₂ ) ₁ (CH ₂ ) _m (OCH ₂ CH ₂ (OH) CH ₂ ) _n OH (1 = 1 to 1
0, m = 1 to 10, n = 1 to 3) (6) F (CF ₂ CF ₂ ) ₁ (CH ₂ ) _m (OCH ₂ CH ₂ (OH) CH ₂ ) _n OH (1 = 1 to 1)
0, m = 1 to 10, n = 1 to 3) The fluorine compound having a reactive organic functional group as described above is
Examples of preferred fluorine compounds in the present invention,
The present invention is not limited to these exemplifications, and the above-exemplified compounds and other fluorine compounds are presently commercially available and can be easily obtained from the market, and any of them can be used in the present invention. It is a thing. The organic polyisocyanate used in the present invention and secondly characterizing the present invention is a compound having at least two isocyanate groups in an aliphatic or aromatic compound,
It has been widely used as a raw material for synthesizing polyurethane resins.

Any of these known organic polyisocyanates are useful in the present invention. Particularly preferable organic polyisocyanates are as follows.

Toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene Diisocyanate, 2,4-diisocyanate-diphenyl ether, mesitylene diisocyanate, 4,4-methylenebis (phenyl isocyanate), durylylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4-diisocyanate dibenzyl , 1,4-tetramethylene diisocyanate, 1,6-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-silane Chlorohexylene diisocyanate, xylylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, etc. Further, adducts of these organic polyisocyanates with other compounds, for example, There are things like
It is not limited to these.

(However, ) The modifier used in the present invention is a fluorine compound having a reactive organic functional group as described above and an organic polyisocyanate as described above, the reactive organic functional group and the isocyanate group, after the isocyanate group is reacted. So as not to remain, preferably in a functional group ratio of 1: 1 in the presence or absence of an organic solvent and a catalyst, at a temperature of about 0 to 150 ° C., preferably 20 to 80 ° C. for about 10 minutes to 3 hours. It can be easily obtained by reacting.

The organic solvent that may be used in the production of such a modifier may be any organic solvent that is inert to the respective reaction raw materials and products, and for example, preferable organic solvents include methyl ethyl ketone and methyl. -N-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, methyl cellosolve , Butyl cellosolve, cellosolve acetate, dimethylformamide, dimethylsulfoxide, pentane, hexane, cyclohexane, heptane, octane, mineral spirits, petroleum ether, gasoline, benzene, toluene Xylene, chloroform, carbon tetrachloride, chlorobenzene, perchlorethylene, trichlorethylene, and the like.

The modifier obtained as described above and used in the present invention may be separated from the organic solvent when it is produced using an organic solvent, or may be used as a solution of the organic solvent as it is. The modifier used in the present invention separated from the organic solvent is generally a white or brown liquid or solid, and is easily soluble in various organic solvents.

The modifier used in the present invention as described above, various analyzes, for example, infrared absorption spectrum, elemental analysis, molecular weight measurement, etc., the isocyanate group of the organic polyisocyanate and the reactive organic functional group of the fluorine compound are added. After reaction, for example, when the reactive organic functional group is an amino group, it has been revealed that the compound is a compound in which both are bonded by a urethane bond and which does not substantially have a free isocyanate group.

In the present invention, what is used as the film-forming resin is any conventionally known various film-forming resins, and any of these conventionally known resins can be used, for example, vinyl chloride resin, vinylidene chloride resin, chloride. Vinyl / vinyl acetate / vinyl alcohol copolymer resin, alkyd resin, epoxy resin, acrylonitrile-butadiene resin, polyurethane resin, polyurea resin, nitrocellulose resin, polybutyral resin, polyester resin, fluorine resin Resins, melamine resins, urea resins, acrylic resins, polyamide resins, etc.,
Particularly preferred is a polyurethane resin having a urea bond or a urethane bond in its structure. Any of these resins may be used alone or as a mixture, and may be a solution or dispersion in an organic solvent.

In forming the resin layer of the pseudo leather of the present invention, it is preferable to dissolve or disperse the resin modified with the above-mentioned modifier in the above medium and use it in the form of a paint. Of course, the usage form is not limited to the paint type. For example, in the case of a paint form, the resin concentration is preferably about 10 to 50% by weight, and the modifier is about 1 to 100 per 100 parts by weight of these resins.
It can be used in a proportion of parts by weight.

As the base sheet of the pseudo leather of the present invention, various woven fabrics, non-woven fabrics and the like which are conventionally used as the base sheet of the pseudo leather, or these base sheets are impregnated with a resin or a porous layer is formed on the surface thereof. Any of those formed can be used, and in the present invention, a resin layer comprising the above-described modifier and resin is formed on at least one surface of such a known base sheet.

The resin layer may be formed by any method, for example, by forming a coating material containing the above modifier and resin as essential components, coating or impregnating this on the surface of the substrate sheet, and drying to form the resin layer. To form a film by coating these coatings on release paper and drying to form a film, and then laminating the film to a base material sheet, forming a film from a modified resin by a calendering method, etc. to form a resin layer. how to,
Furthermore, a method in which a resin layer is formed from the resin before modification by the method as described above, and then a solution of the modifying agent is impregnated to modify the resin layer with the modifying agent is useful. These resin layers may be of any thickness, but are generally about 0.1
To about 100 μm in thickness.

In the present invention, conventionally known additives such as colorants, plasticizers, antistatic agents, surface active agents, antiaging agents, and crosslinking agents can be added to the resin layer. It is natural.

(Operation / Effect) In the pseudo leather of the present invention as described above, the resin layer is modified with a specific modifier, so that the formation of the resin layer is not limited to a specific resin and can be formed by various resins. According to the type of the modified resin, various properties originally possessed by the modified resin, such as strength, flexibility, electrical, chemical, and physical properties are maintained, and It is possible to remarkably improve the surface characteristics of the resin layer to be formed, for example, stain resistance, water resistance, abrasion resistance, adhesion resistance, heat resistance, etc., and also to significantly reduce the friction coefficient of the resin layer.

Further, the modifier used in the present invention, the modifier is a polar group such as urethane bond or urea bond in the resin layer, for example, because of the hydrogen bond or the like between modifiers, or because it is integrated with the resin, The problem that the additive bleeds over the surface of the resin layer with time to cause various problems like the additive of the prior art has been solved, so that a large amount of the modifier can be included in the resin layer. As a result, the surface properties of the resin layer can be further improved.

Next, the present invention will be described more specifically with reference to Examples, Use Examples and Comparative Examples. In the text, parts and% are based on weight.

Reference Example 1 (Production Example of Modifier) Addition product of hexamethylene diisocyanate and water (Duranate 24A-100, Asahi Kasei, NCO% 23.5)
While well stirring 52 parts at 60 ° C., 80 parts of a fluorinated alcohol having the following structure was gradually added dropwise to the mixture to cause a reaction, and 129 parts of a colorless and transparent liquid modifier (M1) was obtained.

H (CF ₂ CF ₂ ) ₅ OH According to the infrared absorption spectrum of this modifier, 2270 /
Absorption by cm free isocyanate groups was not observed,
An absorption band due to —CF ₂ — groups was shown at 1190 / cm.

Therefore, the main structure of the above modifier is estimated to be the following formula.

Reference Example 2 (Production Example of Modifier) Addition product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TD1) (Coronate L, manufactured by Nippon Polyurenta, NCO% 12.5, solid content 75%) 1
While thoroughly stirring 20 parts at 50 ° C., 171 parts of a fluorinated alcohol having the following structure is gradually added dropwise thereto to cause a reaction.

After the completion of the CF ₃ (CF ₂ CF ₂ ) ₃ OH reaction, 251 parts of a transparent liquid modifier (M2) was obtained.

According to the infrared absorption spectrum of this modifier, 2270 /
Absorption by cm free isocyanate groups was not observed,
An absorption band due to —CF ₂ — groups was shown at 1190 / cm.

Therefore, the main structure of the above modifier is estimated to be the following formula.

Reference Example 3 (Production Example of Modifier) 186 parts of an adduct of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate (Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd., NCO% 11.5, solid content 75%) was well treated at room temperature. While stirring, 258 parts of a fluorinated alcohol having the following structure was gradually added dropwise to this and reacted.

CF ₃ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ SH After completion of the reaction, 384 parts of a transparent liquid modifier (M3) was obtained.

According to the infrared absorption spectrum of this modifier, 2270 /
Absorption by cm free isocyanate groups was not observed,
An absorption band due to —CF ₂ — groups was shown at 1190 / cm.

Therefore, the main structure of the above modifier is estimated to be the following formula.

X = SCH ₂ CH ₂ (CF ₂ CF ₂ ) ₃ CF ₃ Reference Example 4 (Modification of resin) 150 parts of polybutylene adipate having a hydroxyl group at the terminal and a molecular weight of 2,000, 1,3-butylene glycol 20
And 52 parts of tolylene diisocyanate are subjected to an addition reaction in 412 parts of methyl ethyl ketone to give a viscosity of 200 poise /
A polyurethane resin solution (solid content: 35%) at 20 ° C. was obtained. To 100 parts of this polyurethane resin solution, a modifier (M
1) 5 parts was added to obtain a modified resin solution (UR1-1).

Reference Example 5 (Modification of Resin) Instead of the modifier (M1) in Reference Example 4, a modifier (M
A modified resin solution (UR1-2) was obtained in the same manner as in Reference Example 4 except that 2) was used.

Reference Example 6 (Modification of Resin) Instead of the modifier (M1) in Reference Example 4, a modifier (M
A modified resin solution (UR1-3) was obtained in the same manner as in Reference Example 4 except that 3) was used.

Example 1 A polyurethane adhesive solution (Resamine VD-602 was applied onto a woven fabric.
5, manufactured by Dainichiseika Kogyo Co., Ltd. was applied and dried so that the coating amount when dried was 10 / m ² to obtain a base sheet for pseudo leather.

On the other hand, each of the modified resin solutions UR1-1 to UR1-3 is coated on a release paper and dried to obtain three kinds of about 15 μm.
A film having a thickness of 5 mm was formed, and the film was attached to the above-mentioned substrate sheet to obtain 5 kinds of artificial leather of the present invention. As Comparative Example 1, a resin solution before modification was used in place of the modified resin, and as Comparative Example 2, a polyurethane resin solution for pseudo leather (solid content 30%, Resamine ME-88N, Dainichi Seika Kogyo Co., Ltd.). As a comparative example 3, artificial leather was similarly prepared by adding 5 parts of silicone oil (SH-200, manufactured by Toray Silicone) to Resamine ME-88N.

Friction coefficient (A), water repellent property (B) of the pseudo leather obtained above,
Blocking resistance (C) and surface state (D) are as follows.
It was as shown in the table.

The coefficient of friction (μK) is the coefficient of friction with iron, the water repellent property is the H 2 O contact angle, and the blocking resistance is 13
Peeling after aging at 0 ° C. for 1 hour, ◯ indicates no peeling, and x indicates peeling. The surface condition is a change after 3 days of production, ◯ indicates no change, and X indicates bleeding of the additive.

As described above, according to the present invention, the coefficient of friction of the resin layer can be remarkably reduced and good water repellency, blocking resistance and surface condition can be maintained.

Reference Example 7 (Modification of Resin) 150 parts of polybutylene adipate having a hydroxyl group at the terminal and a molecular weight of 2,000, 20 parts of 1,4-butanediol,
4,4'-methylenebis (phenylisocyanate) 7
5 parts were subjected to an addition reaction in 286 parts of dimethylformamide and 286 parts of methyl ethyl ketone to obtain a polyurethane resin solution (solid content 35%) having a viscosity of 560 poise / 20 ° C. To 100 parts of this polyurethane resin solution, a modifier (M
1) 5 parts was added to obtain a modified resin solution (UR2-1).

Reference Example 8 (Modification of Resin) Instead of the modifier (M1) in Reference Example 7, a modifier (M
A modified resin solution (UR2-2) was obtained in the same manner as in Reference Example 7 except that 2) was used.

Reference Example 9 (Modification of Resin) Instead of the modifier (M1) in Reference Example 7, a modifier (M
A modified resin solution (UR2-3) was obtained in the same manner as in Reference Example 7 except that 3) was used.

Example 2 100 parts of the modified resin solution (UR1-1 to UR1-5, solid content 30%) Coronate L (NCO% 12.5, solid content 75% made by Nippon Polyurethane) 2 parts Methyl ethyl ketone 120 parts The above composition is nylon. It was applied on taffeta at a rate of 70 to 80 g / m ² and immediately dried in a dryer to obtain three kinds of pseudo leather of the present invention. In addition, as a comparative example, the following composition was used, and the pseudo leather of the comparative example was prepared in the same manner as above.

Thermoplastic urethane elastomer solution (solid content 30%, Resamine ME-88N, made by Dainichiseika Kogyo) 100 parts Coronate L (NCO% 12.5, solid content 75% made by Nippon Polyurethane) 2 parts Silicone oil (SH-200, Toray Silicone)
1 part Methyl ethyl ketone 120 parts The water resistance and water repellent property of the above-obtained pseudo leather were compared before and after the dry cleaning test, and the results are shown in Table 2 below.

The A and B are water pressure resistance (mm) and water repellency before the dry cleaning test, and the above C and D are water pressure resistance (mm) and water repellency after the dry cleaning test is performed three times.

Perchlorethylene 30 for dry cleaning test
Test pieces and 10 steel balls (diameter 6.4 mm) were placed in 0 cc, and 125 times / min. On the shaker for 15 minutes.

The water repellent property was evaluated by dropping water drops on the test piece and completely repelling water with a water repellent degree of 100, and completely impregnating water with 0.

As described above, according to the present invention, a pseudo leather having durable water pressure resistance and water repellency is provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoko Goto 4-4-33 Nishi-Aoki, Kawaguchi City, Saitama Prefecture

Claims (1)

[Claims] 1. A substrate sheet and a resin layer provided on at least one surface of the substrate sheet, wherein the resin layer is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate. A pseudo leather, which is made of a resin modified with a modifier having substantially no free isocyanate group.