JPH0637748B2 - 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, artificial leather having a synthetic resin layer provided on the surface of a base material sheet such as woven cloth or non-woven cloth is 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.

In order to meet such demands, a method of adding additives such as silicone oil, wax, fatty acid, etc., which gives lubricity and water-repellency 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 base material sheet and a resin layer provided on at least one surface of the base material sheet, the resin layer having a reactive organic functional group. A pseudo-leather, which is a reaction product of a compound and an organic polyisocyanate, comprising a resin modified with a modifier having at least one free isocyanate group.

The present invention will be described in more detail. The resin modifier used in the present invention and which is the first feature of the present invention is a reaction product of a silicone compound having a reactive organic functional group and an organic polyisocyanate. The reaction product has at least one free isocyanate group in one molecule.

Preferred examples of the silicone compound having a reactive organic functional group used to obtain such a modifier include the following compounds.

(1) Amino-modified silicone oil (M = 1-10, n = 2-10, R = CH3 or OCH3) (M = 1-10, n = 2-10, R = CH3 or OCH3) (M = 0 to 200) (N = 2 to 10) (Division point = 2 to 3, R = lower alkyl group, 1 = 2 to 200,
m = 2-200, n = 2-200) (N = 1 to 200, R = lower alkyl group) (2) Epoxy-modified silicone oil (N = 1 to 200) (M = 1-10, n = 2-10) (N = 1 to 200) (Branch point = 2 to 3, R = lower alkyl group, 1 = 2 to 200,
m = 2-200, n = 2-200) (N = 1 to 10) (M = 1-10, n = 2-10) (3) Alcohol-modified silicone oil (N = 1 to 200) (M = 1-10, n = 2-10) (N = 0 to 200) (1 = 1 to 10, m = 10 to 200, n = 1 to 5) (N = 1 to 200, R = lower alkyl) (4) Mercapto-modified silicone oil (M = 1-10, n = 2-10) (N = 2 to 10) (Division point = 2 to 3, R = lower alkyl group, 1 = 2 to 200,
m = 2-200, n = 2-200) (N = 1 to 200, R = lower alkyl group) (5) Carboxyl-modified silicone oil (M = 1-10, n = 2-10) (N = 1 to 200) (Division point = 2 to 3, R = lower alkyl group, 1 = 2 to 200,
m = 2-200, n = 2-200) (N = 1 to 200, R = lower alkyl group) The silicone compound having a reactive organic functional group as described above is an example of a preferred silicone compound in the present invention, and the present invention is limited to these examples. Rather, the above-exemplified compounds and other silicone compounds are presently commercially available and readily available on the market, and any of them can be used in the present invention.

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, and has been conventionally used as a raw material for synthesizing a polyurethane resin. Widely used.

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 (phenylene 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- Cyclohexylene diisocyanate, xylylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, and adducts of these organic polyisocyanates with other compounds, for example, those having the following structural formula Can be mentioned,
It is not limited to these.

The modifier used in the present invention comprises a silicone compound having a reactive organic functional group as described above and an organic polyisocyanate as described above, wherein the reactive organic functional group and the isocyanate group are isocyanate groups in one molecule. In the presence or absence of an organic solvent and a catalyst at a functional group ratio of 1 or more, preferably 1 to 2 in excess, about 0 to 150.
It can be easily obtained by reacting at a temperature of C, preferably 20 to 80 C for about 10 minutes to 3 hours.

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, preferred 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, dimethyl sulfoxide,
Pentane, hexane, cyclohexane, heptane, octane, mineral spirits, petroleum ether, gasoline,
Examples thereof include benzene, toluene, xylene, chloroform, carbon tetrachloride, chlorobenzene, perchlorethylene and trichloroethylene.

The modifier used in the present invention obtained as described above 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. The modifier used in the present invention separated from the organic solvent is generally a white to brown liquid or solid, and is easily soluble in various organic solvents.

The modifying agent used in the present invention as described above, according to various analyses, for example, infrared absorption spectrum, elemental analysis, molecular weight measurement and the like, the isocyanate group of the organic polyisocyanate and the reactive organic functional group of the silicone compound are added. When reacted, for example, when the reactive organic functional group is an amino group, it is a compound in which both are bonded by an —NHCONH— bond and which has at least 11 free isocyanate groups in one molecule. It became clear.

According to a detailed study by the present inventor, since the modifier used in the present invention has a free isocyanate, it has, for example, a hydroxyl group, a primary / secondary amino group, an amide group, a carboxyl group and the like. These resins are reactive to various resins and are bonded to the main chain of the resin as a side chain, not to the main chain of these resins, so that the various properties that the resin originally possesses are not deteriorated. From the above, it was found that when the resin layer of pseudo leather is formed, it improves the stain resistance, the adhesion resistance and the like of those resin layers, and also improves various surface properties such as the friction coefficient being remarkably lowered.

Further, such an unexpected effect is that the modifier used in the present invention has a free isocyanate group,
This is because the isocyanate groups also act as one type of modifier that reacts with each other or with the resin before, during or after the formation of the resin layer of the pseudo leather.

In the present invention, as the resin modified with the above-mentioned modifier, various conventionally known resins can be used, and any of them can be used, for example, vinyl chloride resin, vinylidene chloride resin, vinyl chloride / vinyl acetate. / Vinyl alcohol copolymer resin, alkyd resin, epoxy resin, acrylonitrile-butadiene resin, polyurethane resin, polyurea resin, nitrocellulose resin, polybutyral resin, polyester resin, silicone resin, melamine resin Resin, urea resin, acrylic resin,
Polyamide resins and the like are mentioned, and particularly preferable ones are
It is a resin having a reactive group as described above which can react with an isocyanate group 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 addition, the reaction between the resin and the modifier is carried out by reacting 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 done easily.

The reaction between the modifier and the resin may be carried out at any time, for example, at the time of preparation of the coating material for forming the resin layer of pseudo leather, after the preparation, at the time of forming the resin layer, after the formation. Further, when the resin does not have a group that reacts with an isocyanate group, the modifiers react with each other, or if a polyfunctional compound such as water or polyamine is added, the modifier becomes a high molecular weight reactive resin. The same effect as when used is obtained.

In the formation of 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 medium as described above 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 can be used in a ratio of about 1 to 100 parts by weight per 100 parts by weight of these resins.

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 a release paper and drying to form a film, and laminating the film to a base material sheet, forming a film from a modified resin by a calendar method, etc. to form a resin layer. Further, a method of forming a resin layer from the resin before modification by the method as described above, and then impregnating with a solution of the modifying agent to modify the resin layer with the modifying agent is useful. These resin layers may have any thickness, but generally have a thickness of about 0.1 to 100 μm.

Incidentally, in the present invention, any conventionally known additive such as a colorant, a plasticizer, an antistatic agent, a surfactant, an antiaging agent and a crosslinking agent can be added to the above 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, since the modifier used in the present invention has a high molecular weight and is integrated with the resin by reacting the modifiers with each other or with the resin in the resin layer, it is similar to the additive of the prior art. , The additive bleeds over the surface of the resin layer over time,
The drawback of causing various problems has been solved, so that a large amount of a 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 or% are based on weight.

Reference Example 1 (Production Example of Modifier) Addition product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, made by Nippon Polyurethane, NCO% 12.5, solid content 75%) 1
While thoroughly stirring 75 parts at 50 ° C., 880 parts of terminal aminopropylpolydimethylsiloxane (molecular weight 2,200) having the following structure is gradually added dropwise thereto for reaction.

(N is a value at which the molecular weight becomes 2,200) After the reaction was completed, the ethyl acetate was evaporated to obtain 976 parts of a denaturant (M1) in the form of a transparent liquid.

According to the infrared absorption spectrum of this modifier, 2270 /
The absorption by the free isocyanate groups of cm remains,
An absorption band due to the Si—O—C group was shown at 1090 / cm. Further, when the free isocyanate group in this modifier is quantified, the theoretical value is 0.83%, whereas
The actual value was 0.78%.

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

Reference Example 2 (Production Example of Modifier) 24 parts of phenyl isocyanate was added to 196 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight 980) having the following structure, and the mixture was stirred well at 60 ° C. and reacted to give a transparent liquid reaction product ( A) 213 parts were obtained.

(N is a value at which the molecular weight becomes 980) Next, an adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Asahi Kasei, NCO% 2)
3.5) While stirring 52 parts at 60 ° C. well, 22 parts of the above reaction product (A) was gradually added dropwise to the mixture to cause a reaction, and 263 parts of a colorless and transparent liquid modifier (M2) was obtained. It was

According to the infrared absorption spectrum of this modifier, 2270 /
The absorption by the free isocyanate groups of cm remains,
An absorption band due to the Si—O—C group was shown at 1090 / cm. Further, when the free isocyanate group in this modifier is quantified, the theoretical value is 1.54%, whereas
The measured value was 1.37%.

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

Reference Example 3 (Production Example of Modifier) To 230 parts of terminal aminopropylpolydimethylsiloxane (molecular weight 1,150) having the following structure, 15 parts of n-butyraldehyde was added, and the mixture was stirred well at 80 ° C. and reacted to produce The reaction was carried out for 3 hours while removing the formed water under reduced pressure outside the system to obtain 238 parts of a transparent liquid reaction product (B).

(N is a value at which the molecular weight becomes 1,150) Next, an adduct of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate (Takenate D110).
N, manufactured by Takeda Yakuhin, NCO% 11.5, solid content 75%) 1
While thoroughly stirring 86 parts at room temperature, 490 parts of the above reaction product (B) was gradually added dropwise thereto and reacted at 60 ° C.

After the completion of the reaction, the ethyl acetate was evaporated to obtain 610 parts of a denaturant (M3) as a transparent liquid.

According to the infrared absorption spectrum of this modifier, 2270 /
The absorption by the free isocyanate groups of cm remains,
An absorption band due to the Si—O—C group was shown at 1090 / cm. Further, when the free isocyanate group in this modifier is quantified, the theoretical value is 1.34%, whereas
The measured value was 1.25%.

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

Reference Example 4 (Production Example of Modifier) While thoroughly stirring 35 parts of 2,6-tolylene diisocyanate and 110 parts of ethyl acetate at 60 ° C., a terminal mercaptopropylpolydimethylsiloxane having the following structure (molecular weight 1, 580) 316 parts are gradually dropped to react.

(L, m, and n are values at which the molecular weight is 1,580) After the reaction was completed, ethyl acetate was evaporated to obtain 340 parts of a transparent liquid-like denaturant (M4).

According to the infrared absorption spectrum of this modifier, 2270 /
The absorption by the free isocyanate groups of cm remains,
An absorption band due to the Si—O—C group was shown at 1090 / cm. Also, when the free isocyanate group in this modifier is quantified, the theoretical value is 2.39%, whereas
The actual value was 2.12%.

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

(L, m, and n are values at which the molecular weight is 1,580) Reference Example 5 (Production Example of Modifier) 52 parts of hexamethylene diisocyanate and ethyl acetate 1
While thoroughly stirring 60 parts at 60 ° C., 450 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight 2,250) having the following structure is gradually added dropwise thereto for reaction.

(N is the value at which the molecular weight is 1,580) After the reaction was completed, the ethyl acetate was evaporated to obtain 488 parts of a transparent liquid denaturant (M5).

According to the infrared absorption spectrum of this modifier, 2270 /
The absorption by the free isocyanate groups of cm remains,
An absorption band due to the Si—O—C group was shown at 1090 / cm. Also, when the free isocyanate group in this modifier is quantified, the theoretical value is 1.67%, whereas
The actual value was 1.52%.

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

Reference Example 6 (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 / 2.
A polyurethane resin solution (solid content: 35%) at 0 ° C. was obtained.
A modifier (M1) was added to 100 parts of this polyurethane resin solution.
A modified resin solution (UR1-1) in which 5 parts were added and reacted at 80 ° C. for 3 hours to bond a modifier and a polyurethane resin
Got

The resin obtained above had no isocyanate group by infrared spectrum. It is presumed that the modifier was graft-bonded to the resin.

Reference Example 7 (Modification of Resin) Instead of the modifier (M1) in Reference Example 6, a modifier (M
A modified resin solution (UR1-2) was obtained in the same manner as in Reference Example 6 except that 2) was used.

Reference Example 8 (Modification of Resin) Instead of the modifier (M1) in Reference Example 6, a modifier (M
A modified resin solution (UR1-3) was obtained in the same manner as in Reference Example 6 except that 3) was used.

Reference Example 9 (Modification of Resin) Instead of the modifier (M1) in Reference Example 6, a modifier (M
A modified resin solution (UR1-4) was obtained in the same manner as in Reference Example 6 except that 4) was used.

Reference Example 10 (Modification of Resin) Instead of the modifier (M1) in Reference Example 6, a modifier (M
A modified resin solution (UR1-5) was obtained in the same manner as in Reference Example 6 except that 5) was used.

Example 1 A polyurethane adhesive solution (Resamine VD-602 was applied onto a woven fabric.
5, manufactured by Dainippon Seika Kogyo Co., Ltd.) was applied and dried to give a dry coating amount of 10 / m ² to obtain a base sheet for pseudo leather.

On the other hand, each of the modified resin solutions UR1-1 to UR1-5 is coated on a release paper and dried to obtain five kinds of about 15 μm each.
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, Dainichiseika Kogyo). 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-repellency (B), blocking resistance (C) and surface state (D) of the pseudo leather obtained above.
Was as shown in Table 1 below.

The coefficient of friction (μk) is the coefficient of friction with iron, the water-repellency is the H2O contact angle, and the blocking resistance is 1
Peeling after aging at 30 ° 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 11 (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, 5 parts of the modifying agent (M1) was added, and the mixture was reacted at 80 ° C. for 3 hours to form a modified resin solution (UR having a modifying agent and a polyurethane resin bonded thereto (UR
2-1) was obtained.

No isocyanate group was found in the resin obtained above by infrared absorption spectrum. It is presumed that the modifier was graft-bonded to the resin.

Reference Example 12 (Modification of Resin) Instead of the modifier (M1) in Reference Example 11, a modifier (M
A modified resin solution (UR2-2) was obtained in the same manner as in Reference Example 11 except that 2) was used.

Reference Example 13 (Modification of Resin) Instead of the modifier (M1) in Reference Example 11, a modifier (M
A modified resin solution (UR2-3) was obtained in the same manner as in Reference Example 11 except that 3) was used.

Reference Example 14 (Modification of Resin) Instead of the modifier (M1) in Reference Example 11, a modifier (M
A modified resin solution (UR2-4) was obtained in the same manner as in Reference Example 11 except that 4) was used.

Reference Example 15 (Modification of Resin) Instead of the modifier (M1) in Reference Example 11, a modifier (M
A modified resin solution (UR2-5) was obtained in the same manner as in Reference Example 11 except that 5) was used.

Example 2 The modified resin solution (UR1-1 to UR1-5) (solid content 30%) 100 parts Coronate L (NCO% 12.5, solid content 75% made by Nippon Polyurethane) 2 parts Methyl ethyl ketone 120 parts The above composition It was applied onto nylon taffeta at a rate of 70 to 80 g / m ² and immediately dried in a dryer to obtain five 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, manufactured by Dainippon Seika 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 resistance of the artificial leather obtained above were compared before and after the dry cleaning test.
It was as shown in the table.

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

Perchlorethylene 30 for dry cleaning test
The test piece and 10 steel balls (diameter 6.4 mm) in 0 cc were put into the test piece, 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-repellency of 100, and when water was completely soaked with water.

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

Claims (2)

[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 silicone compound having a reactive organic functional group and an organic polyisocyanate. A pseudo-leather comprising a resin modified with a modifier having at least one free isocyanate group. 2. The pseudo leather of the resin according to claim (1), wherein the resin has a group capable of reacting with an isocyanate group.