JPS62257473A - Artificial leather - Google Patents

Abstract

PURPOSE:An artificial leather that is composed of the base sheet and a resin layer which is formed on one surface of the base sheet and modified with a specific modifier, thus showing excellent stain, water and abrasion resistances, because of no bleeding trouble caused by additives in the layer. CONSTITUTION:The base sheet for the artificial leather such as a nonwoven fabric is coated, on at least one surface, with a resin layer which is prepared by modifying a resin reactive with isocyanate groups such as polyvinyl chloride or polyvinylidene chloride with a modifier bearing at least one of free isocyanate group, which is prepared by addition reaction between a fluorine compound bearing organic groups such as amino or carboxyl groups reactive with isocyanate group and an organic polyisocyanate such as toluene-2,4-diisocyanate to give the objective artificial leather with excellent surface properties such as resistances to stain and water.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to simulated leather, and more particularly to simulated leather having excellent surface properties.

(Prior Art) Conventionally, fake leather is widely used, which is a synthetic resin layer provided on the surface of a base sheet of woven or nonwoven fabric. The surface of the resin layer of these pseudo-leathers is required to have excellent stain resistance, hardness, abrasion resistance, adhesion resistance, etc., and depending on the use, a low surface friction coefficient is required.

In order to meet such demands, methods have been used to add additives such as silicone oil, 2x, fatty acids, etc., which impart lubricity and water properties to the resin layer.

(Problem to be solved by the invention) According to the method described above, the objective is achieved to a certain extent, but in such a method, the additive added to the resin layer is deposited on the surface of the resin layer over time. Since bleed-out causes various problems such as severe contamination and blocking, the amount of additives added is limited to a few percent at most, and therefore, the desired performance cannot be fully exhibited.

As a result of intensive research in order to solve the above-mentioned drawbacks of the conventional technology and meet the above-mentioned demands, the present inventor modified the resin using a specific modifier to form a resin layer of fake leather. completed the present invention by finding that the above-mentioned drawbacks of the prior art could be solved and that a simulated leather with excellent surface properties could be provided.

(Means for Solving the Problems) That is, the present invention provides 2! A material sheet and a resin layer provided on at least one surface of the base material sheet, the resin layer being a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate, and at least one This is a pseudo-leather characterized by being made of a resin modified with a modifier having free isocyanate groups.

To explain the present invention in more detail, the resin modifier used in the present invention and which primarily characterizes the present invention is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate. , the reaction product has at least one free isocyanate group in one molecule.

The fluorine compound having a reactive organic functional group used to obtain such a modifier may be any compound capable of reacting with an isocyanate group, such as an amino group, a carboxyl group, a water mu, or a thioalcohol group. However, particularly preferred examples are fluorine compounds represented by the following formula.

(1) H(CF2CF2)ncH20H (n=1~?
)(2) CF3(CF2CF2)ncH2G)120
H(n-1-10)(3) CF3(CF2CF2)n
cOOH (n=1-10) (4) CF3 (CF2CF
2) Fluorine compounds having a reactive organic functional group such as ncH2cH2sH (n = 1 to 10) are examples of preferred fluorine compounds in the present invention, and the present invention is not limited to these examples. The above-mentioned exemplified compounds and other fluorine compounds are currently reprinted and readily available on the market, and any of them can be used in the present invention.

Used in the present invention to secondly characterize the present invention.

The organic polyisocyanate is a compound having at least two isocyanate groups in an aliphatic or aromatic compound, and 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 preferred 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(phenylisocyanate), Shuryen diisocyanate.

1.5-Naphthalene diisocyanate, benzidine diisocyanate.

0-Nitrobenzidine diisocyanate.

4.4-Dibenzyl diisocyanate, 1.4-tetramethylene diisocyanate.

1.6-tetramethylene diisocyanate.

1.10-decamethylene diisocyanate.

1.4-Cyclohexylene diisocyanate.

Xylylene diisocyanate, 4,4-methylenebis(cyclohexylisocyanate).

1.5-Tetrahydronaphthalene diisocyanate.

Furthermore, adducts 1 of these organic polyisocyanates and other compounds, such as those of the following structural formula,
Not limited to these.

(Left below) C0NH ((:H2)8NCO In the presence or absence of an organic solvent and a catalyst, the functional group and the isocyanate group have a functional group ratio such that one or more isocyanate groups are in excess, preferably 1 to 2 isocyanate groups in one molecule, and approximately θ to It can be easily obtained by reacting at a temperature of 150°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. (1) For example, preferred organic solvents include methyl ethyl ketone, Methyl-n-
Propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl vinegar, 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,
Benzene, toluene, xylene, chloroform, four groups 4
Examples include tJ''R, chlorobenzene, perchlorethylene, trichlorethylene, and the like.

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

According to various analyzes 1, such as infrared absorption spectrum, elemental analysis, molecular weight measurement, etc., the modifier used in the present invention as described above shows that the isocyanate group of the organic polyisocyanate and the reactive organic functional group of the fluorine compound are added together. For example, when the reactive organic functional group is an amino group, -
It was revealed that the two were bonded together through an NHCONH-bond, and that the compound had at least one free isocyanate group in one molecule.

According to the inventor's detailed research, the modifier used in the present invention has free isocyanate, and therefore has, for example, a hydroxyl group, a primary to secondary amine group, an amide group, a carboxyl group, etc. It is reactive with various resins and is bonded to the main chains of these resins as side chains rather than the main chains of these resins.

When a resin layer of fake leather is formed from these resins without reducing the various properties that the resin has naturally, it improves the stain resistance, adhesive resistance, etc. of the resin layer, and
It has been found that various surface properties such as significantly lowering the coefficient of friction can be improved.

Furthermore, this unexpected effect is due to the fact that the modifier used in the present invention has free isocyanate groups.
This is because the isocyanate groups also act as a type of modifier that reacts with each other or with the resin before, during, or during the formation of the resin layer of the fake leather.

In the present invention, the resin modified with the above-mentioned modifier is a variety of conventionally known resins, and any of these can be used. For example, vinyl chloride resin, vinylidene chloride resin, vinyl chloride/acetic acid resin, etc. Vinyl/vinyl alcohol copolymer resin, alkyd resin, epoxy resin,
Acrylonitrile-butadiene resins, polyurethane resins, polyurea resins, nitrocellulose resins, polybutyral resins, polyester resins, fluorine resins, melamine resins, urea resins, acrylic resins, polyamide resins, etc. Of these, particularly preferred are resins having, in their structure, the above-mentioned reactive groups capable of reacting with isocyanate groups. These resins can be used alone or as a mixture, and can be used as a solution or dispersion in an organic solvent.

The reaction between the resin and the modifier can be carried out by reacting at a temperature of about 0 to 150°C, preferably 20 to 80°C, for about 10 minutes to 3 hours in the presence or absence of an organic solvent and a catalyst. It can be done easily.

The reaction between the modifier and the resin may be carried out at any time, such as during or after the preparation of the paint for forming the resin layer of fake leather, or during or after the formation of the resin layer. If the modifier does not have a group that reacts with the group, the modifiers may react with each other.

If water or a polyfunctional residue compound such as a polyamine is added, the modifier has a high molecular weight and produces the same effect as when a reactive resin is used.

To form the resin layer of the simulated leather of the present invention, it is preferable to dissolve or disperse the resin modified with the above-mentioned modifier in the above-mentioned medium and use it in a form such as a paint. For example, in the case of a paint form, the concentration of the resin is preferably about 10 to 50% by weight, and the modifier can be used at a ratio of about 1 to 100 parts by weight per 100 parts by weight of these resins. .

The base sheet for the fake leather of Kokuhatsu IJ1 may be various woven fabrics, non-woven fabrics, etc. that have been used as base sheets for conventionally known fake leather, or these base sheets may be impregnated with resin or have a porous layer on their surface. In the present invention, a resin layer made of the above-mentioned 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, a paint containing the modifier and resin as essential components is formed, and this is applied to the surface of the base sheet.

A method of forming a resin layer by impregnating cloth or drying it, a method of applying these paints on 65 paper and dry-exploding it to form a film, and bonding the film to a base sheet, a method of calendering from modified resin. etc. to form a film,
A method of forming a resin layer, and furthermore, a method of forming a resin layer with a resin before modification by the method described above, and then impregnating the resin layer with a solution of the modifier to modify the resin layer with the modifier is useful. It is. These resin layers may have any thickness, but generally have a thickness of about 0.1 to 1004 m.

In the present invention, any conventionally known additives such as colorants, plasticizers, antistatic agents, surfactants, anti-aging agents, crosslinking agents, etc. can be added to the resin layer. Of course.

(Action-Effect) Since the resin layer of the fake leather of the present invention as described above is modified with a specific modifier, the formation of the resin layer is difficult.

It is not limited to a specific resin, and can be formed and used with a variety of resins, and depending on the type of modified resin, the various properties that the modified resin has, such as strength, flexibility, and electrical properties. The surface properties of the resin layer formed from the resin, such as stain resistance, water resistance, abrasion resistance, adhesion resistance, and heat resistance, are significantly improved while maintaining the physical, chemical, and physical properties. The friction coefficient of the resin layer can be significantly reduced.

In addition, the modifier used in the present invention reacts with each other or with the resin in the resin layer, becomes a polymer μ, and is integrated with the resin. As shown, the additive bleeds onto the surface of the resin layer over time,
The disadvantage of causing various problems has been solved, and therefore 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 explained in more detail by giving Examples, Usage Examples, and Comparative Examples. Note that 1 part or % in the text is based on weight.

Reference Example 1 (Production example of modifier) Adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Asahi Kasei, 800% 23.5)
While thoroughly stirring 52 parts at 60° C., 53 parts of a fluorinated alcohol having the structure shown below was gradually added dropwise thereto to cause a reaction, thereby obtaining 103 parts of a colorless and transparent liquid modifier (Ml).

H(CF2CF2)50H According to the infrared absorption spectrum of this modifier, 22707
The absorption due to free isocyanate groups at cm remained, and an absorption band due to -CF2- groups was shown at 1190/am. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 2.65%, whereas the actual value was 2.51%.

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

Reference Example 2 (Manufacturing Example of Modifier) Adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, Japan Polyurethane Acid, N00% 12°5, solid content 75%) 1
While thoroughly stirring 20 parts at 50° C., 114 parts of a fluorinated alcohol having the structure shown below is gradually added dropwise to react.

CF3 (CF2CF2) 30H After the reaction was completed, 198 parts of the modifier (M2) in the form of a transparent liquid was obtained.

According to the infrared absorption spectrum of this modifier, 2270
The absorption band due to free isocyanate groups at /cm remained, and an absorption band due to -CF2- groups was shown at 1190/cm. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 2.83%, whereas the actual value was 2.68%.

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

(Leaving space below) Reference Example 3 (Manufacturing example of modifier) 186 parts of adduct of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate (Takenate D11ON, manufactured by Takeda Pharmaceutical, NC 0% 11.5, solid content 75%) While thoroughly stirring the mixture at room temperature, 172 parts of a fluorinated alcohol having the structure shown below was gradually added dropwise thereto to cause a reaction.

After the CF3(CF2(:F2)3C:H2CH2SH reaction was completed, 320 parts of a transparent liquid modifier (M3) was obtained.

According to the infrared absorption spectrum of this modifier, 2270
The absorption band due to free isocyanate groups at 1190/cm remained, and an absorption band due to -CF2- groups was observed at 1190/cm. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 2.69%, whereas the actual value was 2.51%.

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

CX=SCH2CH2 (CF2CF2>3CF3) Reference Example 4 (Modification of resin) 150 parts of polybutylene adipate with a molecular weight of 2,000 having a hydroxyl group at the end, ■, 3-butylene glycol 20
52 parts of tolylene diisocyanate were subjected to an addition reaction in 412 parts of methyl ethyl ketone, and the viscosity was 200 voids/2.
A polyurethane resin solution (solid content 35%) at 0°C was obtained.

Modifier (Ml) was added to 100 parts of this polyurethane resin solution.
5 parts and reacted at 80°C for 3 hours to obtain a modified resin solution (URl-1) in which the modifier and polyurethane resin were combined.
I got it.

In the resin obtained above, no isocyanate groups were observed by infrared absorption spectrum. This is presumed to be due to graft bonding of the modifier to the resin.

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

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

Example 1 A polyurethane adhesive solution (Lethermin VDJ) was applied onto a woven fabric.
O25 (manufactured by Dainichiseika Kagyo Kogyo), the coating amount when drying is 1O/r.
It was coated and dried to give IT', and a base sheet for fake leather was obtained.

On the other hand, each of the modified resin solutions UR1-1 to UR1-3 was coated on a thin paper and dried to give about 15 g of each of the three types.
A film having a thickness of 100 mL was formed, and this was laminated to the above base sheet to obtain 5 types of fake leather of the present invention. In addition, as Comparative Example 1, a resin solution before modification was used instead of the above-mentioned modified resin, and as Comparative Example 2, a polyurethane resin solution for fake leather (solid content 30%, Rezamin ME-88N, Dainichiseika Kogyo Co., Ltd.) was used. ), and as Comparative Example 3, Rethermin l'1E-
88N and 5 parts of silicone oil (SH-200, manufactured by Toshi Silicone Co., Ltd.) were added to make fake leather If.

S friction coefficient (A) and water resistance (B) of the fake leather obtained above
, blocking resistance (C) and surface condition (D) were as shown in Table 1 below.

-15''-1 to -1J~= A B CDURI-1
0,2195" O0 URI-20,1295" O0 URI-30,1195@OO Comparative example 1 0.62 ft5° × ○Comparative example 2 0.5685' X 0 Comparative example 3
0.23 95° O×Friction coefficient (final k)
is the coefficient of friction against iron, the Hough water resistance is the H20 contact angle, the blocking resistance is 2qs after 1-plane age puffing at 130°C, O indicates no peeling, and X indicates presence of 'A'. The surface condition shows changes after 3 days of production, where 0 indicates no change and × indicates bleeding of additives.

As described above, according to the present invention, the coefficient of friction of the resin layer can be significantly lowered, and a surface state with good Huff water resistance and blocking resistance can be maintained.

Reference Example 7 (Modification of resin) 150 parts of polybutylene adipate with a molecular weight of 2,000 having a hydroxyl group at the end, 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%) with a viscosity of 560 poise/20°C.

Modifier (Ml) was added to 100 parts of this polyurethane resin solution.
5 parts and reacted at 80°C for 3 hours to obtain a modified resin solution (UR2-1) in which the modifying agent and polyurethane resin were combined.
I got it.

In the resin obtained above, no isocyanate groups were observed by infrared absorption spectrum. This is presumed to be due to graft bonding of the modifier to the resin.

Reference Example 8 (Resin Modification) In place of the modifier (Ml) 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 Example 2) was used.

Reference Example 9 (Resin Modification) In place of the modifier (Ml) 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 Modified resin solution (URL-1-URI-5) (solid content 30%) 100 parts Coronay) L
(N (1:0% 12.5, solid content 75% manufactured by Nippon Polyurethane) 2 parts Methyl ethyl ketone 120 parts The above composition was applied on nylon taffeta at a rate of 70 to 80 g/mW and immediately dried in a dryer. Three types of simulated leather of the present invention were obtained.Furthermore, as a comparative example, the following composition was used, and other simulated leathers were prepared in the same manner as above.

Thermoplastic urethane elastomer solution (solid content 30%, Rezamin ME-88N, manufactured by Dainichiseika Chemical Industry Co., Ltd.) 100 parts Coronate L (N00% 12.5. Solid content 75% manufactured by Nippon Polyurethane) 2 parts, 71J Corfu Oil (SH- 200, East Silicone) 1 part Methyl ethyl ketone 120 parts The water pressure resistance and Hough water resistance of the fake leather obtained above were compared before and after the dry cleaning test, and the results were as shown in Table 2 below.

-Michi 22 Hikoe- Jukan I9 Good-ABCD U R2-113501001270100U R2-
214101001240100U R2-31440
1001280100 Comparative example 1380 100
850 40-50 The above A and B are the water pressure resistance (mm) and Hough water resistance before the dry cleaning test, and the above C and D are the water pressure resistance (mm) and the Hough water resistance after dry cleaning test 3. .

Dry cleaning test uses perchlorethylene 30
A test piece and 10 steel balls (diameter 6.4 mm) were placed in 0 cc, and the number of cycles was 125 times/min.

The shaker was used for 15 minutes.

Huff aqueous properties were evaluated by dropping water droplets on a test piece, and evaluating the test piece as 100 if it completely repelled water, and rated as O if the test piece completely soaked in water.

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

Claims (2)

[Claims] (1) Consisting of a base sheet and a resin layer provided on at least one surface of the base sheet, the resin layer being a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate; , a simulated leather comprising a resin modified with a modifier having at least one free isocyanate group. (2) The imitation leather of a resin according to claim (2), wherein the resin has a group capable of reacting with an isocyanate group.