WO2016052906A1 - Suede type artificial leather with antifouling property, and preparation method therefor - Google Patents

Abstract

The present invention relates to suede type artificial leather with an antifouling property, and relates to suede type artificial leather with an antifouling property, in which a polymer elastomer is infiltrated into a nonwoven fabric formed by three-dimensional interlacing of an ultrafine fiber and raising is carried out, wherein the polymer elastomer is a fluorine-containing modified polyurethane, and the fluorine-containing modified polyurethane is prepared so as to have a weight average molecular weight (Mw) of 500,000-800,000 by preparing a urethane prepolymer having a weight average molecular weight (Mw) of 400,000-700,000 by reacting a diol with a diisocyanate, and reacting the prepared prepolymer with a fluorinated carbon compound in which hydroxyl functional groups are provided at both ends thereof. According to the present invention, the suede type artificial leather with an antifouling property, in which a separate fluorine-based surfactant for an antifouling property does not need to be used and artificial leather surface aging caused by using a fluorine-based surfactant does not occur, can be provided by using a fluorine-containing polyurethane elastomer provided with an antifouling function when preparing the artificial leather.

Description

Suede-type artificial leather with antifouling properties and a method of manufacturing the same

The present invention relates to a suede-type artificial leather having antifouling properties, and more particularly, to an artificial leather impregnated with a modified polyurethane having an antifouling function, and to a simple manufacturing method without additional addition of an antifouling function. .

Artificial leather is made of polymer elastomer impregnated with a nonwoven fabric formed by interweaving microfibers three-dimensionally, and has a soft texture and unique appearance similar to natural leather, such as shoes, clothing, gloves, sundries, furniture, and automobile interior materials. It is widely used in various fields.

Such artificial leather has different characteristics to be provided according to its use. For example, the characteristics required for artificial leather for clothes include high durability, high sensitivity, excellent dyeability and high fastness that can be dyed in various colors and concentrations.

Among these required characteristics, it is required to impart antifouling functions including water repellent and oil repellent functions such that generation of contamination is suppressed even when used for a long time in order to improve durability.

When manufacturing artificial leather to impart antifouling function, fluorine- or silicon-based surfactants are mixed with polyurethane, a polymer elastomer, and impregnated into a nonwoven fabric to incubate fluorine or silicon chains on the surface of artificial leather to suppress contamination from the outside. There is a way.

However, fluorine-based or silicon-based surfactants are generally inert additives and do not form chemical bonds when mixed with polyurethane, resulting in free behavior in the urethane molecular structure, which leads to the transition of artificial leather to the surface of artificial leather. There is a problem causing change over time.

A modified polyurethane in which fluorine is bonded without adding a fluorine-based compound and a method of manufacturing a leather-like sheet-like article using the modified polyurethane are described in Korean Patent No. 0969839.

According to the said patent, 3-12 fluorine-containing side chains of the molecular weight 200-1,000 are couple | bonded with the urethane bond containing compound of molecular weight 500-5,000, and fluorine content is 20-60 weight% in conversion to a fluorine atom, and 1 molecule The use of the fluorine-containing side chain-modified urethane compound containing 6 to 36 sugar urethane bonds and the urethane compound has been described to be excellent in water repellency and water resistance in the cut section of the leather-like sheet-like product.

However, the modified polyurethane according to the above patent is used as an additive added together with polyurethane, which is an elastic body, as a treatment liquid of a leather-like sheet form, and shows an effect as a water repellent.

Therefore, development is being progressed to exhibit antifouling properties by the impregnated elastic body without using antifouling additives in artificial leather.

In order to solve the above problems, an object of the present invention is to provide an artificial leather impregnated with a new modified polyurethane which will have an antifouling function without the addition of an antifouling function.

In order to solve the above problems, the present invention, in the artificial leather in which the polymer elastic body is impregnated and raised in a non-woven fabric formed by interweaving ultrafine fibers in three dimensions, the polymer elastic body is a fluorine-containing modified polyurethane, A fluorine-containing modified polyurethane is a polymerization product by reaction of the urethane prepolymer in which the isocyanate group is located in the terminal obtained by making diol and diisocyanate react, and the fluorinated carbon compound provided with the hydroxy functional group at both terminals, and has a weight average molecular weight (Mw). It provides a suede-type artificial leather having antifouling properties characterized in that 50) ~ 800,000.

In addition, the present invention is a method of manufacturing artificial leather in which the nonwoven fabric formed by interweaving microfibers three-dimensionally immersed in the impregnation solution containing a polymer elastomer, the polymer elastic body is impregnated and brushed, the polymer elastic body is fluorine-containing Modified polyurethane, wherein the fluorine-containing modified polyurethane reacts with diol and diisocyanate to prepare a urethane prepolymer having a weight average molecular weight (Mw) of 400,000 ~ 700,000, and the prepared prepolymer and hydroxy functional groups at both ends It provides a method for producing suede artificial leather having antifouling properties characterized in that the weight average molecular weight (Mw) is made of a polymer of 500,000 ~ 800,000 by reacting the fluorinated carbon compound.

Artificial leather impregnated with a fluorine-containing modified polyurethane elastic body imparted with antifouling function according to the present invention exhibits excellent water repellency in addition to antifouling properties, and artificial leather prepared by adding a fluorine-based surfactant separately changes surface surface upon implementation of the surfactant. Compared to the large occurrence of the artificial leather of the present invention can make the surface aging change small.

In addition, since the fluorine-based surfactant does not need to be added separately, the manufacturing method can be simplified.

1 is a polymerization scheme of a fluorine-containing modified polyurethane according to an embodiment of the present invention,

2 is a picture of the water repellency evaluation test apparatus of artificial leather,

3 is a rating criteria of the water repellency evaluation.

The present invention relates to an artificial leather, wherein the polymer elastic body is a fluorine-containing modified polyurethane in an artificial leather in which a polymer elastic body is impregnated and raised to a nonwoven fabric formed by interweaving microfibers three-dimensionally.

The fluorine-containing modified polyurethane is a urethane prepolymer having a weight average molecular weight (Mw) of 400,000 to 700,000 having an isocyanate group at the terminal obtained by addition reaction of a diol and a diisocyanate, and a fluorinated carbon to which hydroxy functional groups are provided at both terminals. As a polymerization product by addition reaction of a compound, it is a fluorine-containing modified polyurethane whose Mw is 500,000-800,000.

Diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol may be used alone or in combination. Can be used.

The diisocyanate is 1,4-tetramethylene diisocyanate, 1,6 hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- to 1,4-diisocyanate, 1-isocyanate 3-isocyanatemethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate), bis- (4-isocyanate cyclohexyl) methane (hydrogenated MDI), 2- to 4-isocyanate cyclohexyl-2-isocyanate cyclo Hexylmethane, 1,3- to 1,4-tetramethylxylene diisocyanate, 2,4- to 2,6-diisocyanate toluene, 2,2-2,4- to 4,4'-diphenylmethane diisocyanate , 1,5-naphthalene diisocyanate, xylene diisocyanate, diphenyl-4,4-diisocyanate, and the like.

In this invention, when making a diol and diisocyanate react, it is necessary for the ratio to make it react the ratio which all NCO groups become excess rather than all OH groups. Thus, by adjusting and adjusting the ratio of diol and diisocyanate, the urethane prepolymer obtained can have an isocyanate group terminal in a side chain.

At this time, the molar ratio of diol and diisocyanate is preferably in the range of 1: 1.2 to 1: 1.4, since it is possible to produce a fluorine-containing modified polyurethane having a weight average molecular weight range of the present invention.

When the molar ratio is less than 1: 1.2, side reactions occur due to moisture in the air, active hydrogen, or the like, or isocyanates react to form a trimer to form a trimer, thereby increasing the inert NCO, thereby decreasing polymerization efficiency. When the molar ratio is greater than 1: 1.4, the shortage of the OH group becomes severe due to the excess NCO group, making it difficult to increase the degree of polymerization, which is not preferable.

In order to secure the mechanical properties required when the fluorine-containing modified polyurethane of the present invention is applied to artificial leather, it is necessary to easily increase the polymerization molecular weight to an appropriate level. For this purpose, a urethane prepolymer may be prepared first.

When the weight average molecular weight (Mw) of the urethane prepolymer is less than 400,000, the molecular weight of the finally obtained fluorine-containing modified polyurethane is lowered, thereby lowering mechanical properties such as tear strength, and chemical properties such as thermal stability and hydrolysis resistance. If it exceeds 700,000, gelation may occur in the production of the fluorine-containing modified polyurethane, and when the mixture is prepared with an elastomeric impregnating solution, the viscosity of the fluorine-containing modified polyurethane may be high, resulting in deterioration of workability. The resulting fluorine-containing modified polyurethane can be hardened, and the quality of sensibility can be degraded in artificial leather, which is undesirable.

The fluorinated carbon compound provided with hydroxy functional groups at both ends thereof is represented by the following Chemical Formula 1, wherein 8 to 14 fluorine groups are bonded to one side chain, and the fluorine content is 50 to 70 mol% at one structural end. And ether diols having hydroxy functional groups at both ends.

[Formula 1]

HO-CH ₂ -CF ₂ -O- (CF ₂ CF ₂ O) _m- (CF ₂ O) _n -CF ₂ -CH ₂ -OH

By reacting the ether diol of the formula (1) with the urethane polymer by binding fluorine present in the elementary state to the side chain of the urethane polymer as a diatomic molecule, it is possible to inhibit the binding to other atoms or molecules to impart water and oil repellency have. Because of this, the fluorine-containing modified polyurethane of the present invention can suppress the deposition of the external pollution source and can be easily removed the contamination rate of the coating surface.

Solvay's FLUOROLINK ^® is a commercialized product of fluorinated carbon compounds with hydroxy functional groups at both ends.

Polymerization of the fluorine-containing modified polyurethane of the present invention, the urethane prepolymer is a fluorinated carbon compound having a hydroxy functional group at both ends by the molar excess of isocyanate (mol) of the urethane prepolymer isocyanate is bonded to both ends The addition polymerization can be carried out while adding dropwise to until it reaches the appropriate molecular weight.

When the fluorinated carbon compound imparted with hydroxy functional groups at both ends is added at a time, partial bonding is performed, and thus dispersion of fluorine groups is insufficient, and thus it is difficult to express uniform antifouling performance as a whole. desirable.

The fluorine-containing modified polyurethane of the present invention is polymerized by the above method, characterized in that the weight average molecular weight (Mw) is 500,000 ~ 800,000, if the weight average molecular weight (Mw) is less than 500,000 mechanical strength such as tear strength in artificial leather It may cause the deterioration of chemical properties such as strength, thermal stability and hydrolysis resistance. If it exceeds 800,000, the viscosity of the fluorine-containing modified polyurethane is high when the elastomeric impregnating solution is formulated. The resulting fluorine-containing modified polyurethane may be hardened, and thus the quality of the sensitization in artificial leather may be degraded, which is not preferable.

Preferably, the fluorine-containing modified polyurethane of the present invention has a fluorine content of 5 to 20 mol%, but if it is 5 mol% or less, the expression of antifouling performance is insufficient, and if the content exceeds 20 mol%, the water repellent performance is too strongly expressed to prepare artificial leather. Substituted solidification of the fluorine-containing modified polyurethane may not be achieved in the process, which is not preferable.

An example of the synthesis scheme of the fluorine-containing modified polyurethane described above can be represented by the following scheme.

[Scheme]

At this time, R and R 'are each independently an alkyl group.

In general, artificial leather is immersed in the impregnating solution containing a polymer elastic body such as polyurethane to immerse the non-woven fabric formed by three-dimensional intertwined fibers, impregnated and solidified the polymer elasticity, imparts an elastic body to the non-woven fabric, then grinding and brushed It can be prepared by dyeing.

In the present invention, the fluorine-containing modified polyurethane of the present invention can be used as the polymer elastic body of the impregnation liquid, impregnated by diluting the fluorine-containing modified polyurethane in dimethylformamide of 100 to 200% by weight of the fluorine-containing modified polyurethane. Can be used as a liquid.

Below, this invention is demonstrated concretely by an Example and a comparative example. However, the following Examples and Comparative Examples are only for illustrating the present invention, and the present invention is not limited to the following Examples, and other examples substituted and equivalent within the scope without departing from the technical spirit of the present invention. It will be apparent to those skilled in the art to which the present invention pertains.

[Production Example 1]

0.45 mol (Mw: 1500 to 2500) of polytetramethylene glycol, 0.47 mol of ethylene glycol and 0.08 mol of 1,4-butanediol were polymerized by addition reaction with 1.2 mol of 4,4'-diphenylmethane diisocyanate, and thus polymerized. NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 700,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.

The prepared prepolymer was added with 0.2 mol of fluorinated carbon compound (trade name FLUOROLINK D10-H, Solvay Co., Mw: 1,400) having a hydroxyl group at both ends, and after addition polymerization, dimethylform was added so that the total solid of the polymerized polymer was 30% by weight. A fluorine-containing modified polyurethane compound having a weight average molecular weight (Mw) of 800,000 in which the final reaction was terminated by dissolving in amide was prepared.

[Production Example 2]

0.45 mol (Mw: 1500 to 2500) of polytetramethylene glycol, 0.47 mol of ethylene glycol and 0.08 mol of 1,4-butanediol were polymerized by addition reaction with 1.3 mol of 4,4'-diphenylmethane diisocyanate, and thus polymerized. NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 600,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.

The prepared prepolymer was added with 0.3 mol of fluorinated carbon compound (trade name FLUOROLINK D10-H, Solvay, Mw: 1,400) having a hydroxyl group at both ends, and after addition polymerization, dimethylform was added so that the total solid of the polymerized polymer was 30% by weight. A fluorine-containing modified polyurethane compound having a weight average molecular weight (Mw) of 700,000 in which the final reaction was terminated by dissolving in amide was prepared.

[Production Example 3]

0.45 mol (Mw: 1500 to 2500) of polytetramethylene glycol, 0.47 mol of ethylene glycol and 0.08 mol of 1,4-butanediol were polymerized by addition reaction with 1.4 mol of 4,4'-diphenylmethane diisocyanate, and thus polymerized. NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 400,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.

After prepolymerization of the prepared prepolymer with 0.4 mol of hydroxy group side-linked fluorinated carbon compound at both ends, it was diluted and dissolved in dimethylformamide so that the total solid content of the polymerized polymer was 30% by weight. A fluorine-containing modified polyurethane compound having a Mw) of 500,000 was prepared.

[Production Example 4]

0.45 mol (Mw: 1500 to 2500) of polytetramethylene glycol, 0.47 mol of ethylene glycol and 0.08 mol of 1,4-butanediol were polymerized by addition reaction with 1.0 mol of 4,4'-diphenylmethane diisocyanate. A reaction-terminated polyurethane compound having a weight average molecular weight (Mw) of 700,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 70% by weight.

Production Example 5

0.45 mol (Mw: 1500 to 2500) of polytetramethylene glycol, 0.47 mol of ethylene glycol and 0.08 mol of 1,4-butanediol were polymerized by addition reaction with 1.7 mol of 4,4'-diphenylmethane diisocyanate, and thus polymerized. NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 350,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.

After prepolymerization of the prepared prepolymer with 0.7 mol of hydroxy group side-linked fluorinated carbon compound at both ends, the prepolymer was diluted and dissolved in dimethylformamide so that the total solid content of the polymerized polymer was 30% by weight (Mw). A fluorine-containing modified polyurethane compound having 450,000) was prepared.

[Manufacture example 6]

0.45 mol (Mw: 1500 to 2500) of polytetramethylene glycol, 0.47 mol of ethylene glycol and 0.08 mol of 1,4-butanediol were polymerized by addition reaction with 1.0 mol of 4,4'-diphenylmethane diisocyanate. A reaction-terminated polyurethane compound having a weight average molecular weight (Mw) of 700,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 70% by weight.

Example 1

An impregnation solution was prepared by diluting the fluorine-containing modified polyurethane compound of Preparation Example 1 in 150% of dimethylformamide relative to the weight of the compound.

A polyester fiber (0.3 denier, 51 mm long fiber) was immersed in the impregnation solution, and the solid nonwoven fabric was immersed in the impregnation solution, and coagulated in an aqueous solution in which 20 wt% of dimethylformamide was diluted to impregnate the fluorine-containing modified polyurethane compound elastomer. An elastic-impregnated nonwoven fabric was prepared in which a fine porous layer was formed in the fiber structure.

Thereafter, the surface of the elastomer-impregnated nonwoven fabric was ground to cultivate fiber raising on the surface to prepare a suede artificial leather.

Example 2

In Example 1, suede artificial leather was manufactured in the same manner as in Example 1, except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 2.

Example 3

In Example 1, suede artificial leather was manufactured in the same manner as in Example 1 except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 3.

Comparative Example 1

In Example 1, suede artificial leather was manufactured in the same manner as in Example 1 except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 4.

Comparative Example 2

In Example 1, suede artificial leather was manufactured in the same manner as in Example 1 except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 5.

Comparative Example 3

In Example 1, the impregnation solution was prepared by diluting the reaction-terminated polyurethane compound of Preparation Example 6 to a mixture of 150% dimethylformamide and 0.5% fluorine-based surfactant (trade name FC-4430, 3M company) by weight. Except that, suede-type artificial leather was manufactured in the same manner as in Example 1.

In this case, the weight average molecular weight (Mw) of the polymers prepared in Examples and Comparative Examples is a mobile phase using tetrahydrofuran (flow rate 1 mL / min) using gel permeation chromatography (GPC) (RI-8000, Tosoh). The TSKgel super HM-L, TSKgel super HM-M, and TSKgel super HM-N (tosoh, Inc.) were passed through a column connected in series, and the temperature of the column oven was measured at 40 ° C.

Table 1 shows the polymerization raw material composition ratio and the weight average molecular weight of the polymerized polymer for the above Preparation Example.

division	Preparation Example 1	Preparation Example 2	Preparation Example 3	Preparation Example 4	Preparation Example 5	Preparation Example 6
Dior	1 mol	1 mol	1 mol	1 mol	1 mol	1 mol
Diisocyanate	1.2 mol	1.3 mol	1.4 mol	1 mol	1.7 mol	1 mol
Prepolymer	700,000	600,000	400,000	700,000	350,000	700,000
FLUOROLINK D10-H	0.2 mol	0.3 mol	0.4 mol	-	0.7 mol	-
Fluorine-containing modified polyurethane	800,000	700,000	500,000	-	450,000	-
Surfactant (FC-4430)	-	-	-	-	-	0.5%
The value of the surfactant is the content in the elastomeric impregnation liquid.

The artificial leather prepared in Examples and Comparative Examples was evaluated according to the following pollution resistance evaluation method, and the results are shown in Table 2 below.

Pollution resistance evaluation method

The artificial leather measurement sample is cut into a size of 5 x 15 cm, placed in a friction fastness tester (model DL-2007), and a contaminated cloth (Test fabric, namely IEC carbon black / mineral oil, EMPA) is placed on the surface of the contaminated sample. In addition, 10 reciprocating frictions are performed and the contamination level is compared by visual comparison of the contaminated sample.

(Standard of pollution grade,

5: no contaminants visible at all, 4: slightly visible but almost invisible, 3: slightly contaminated and visible, 2: slightly contaminated, 1: severely contaminated )

Water repellency  Assessment Methods

The artificial leather measurement sample is fixed as shown in FIG. 2 (diameter 10 cm), and then tilted at an angle of 45 ° to be mounted. Thereafter, 100 ml of water is sprayed into the spray funnel located at the top, and after completion of spraying, the degree of distribution of water droplets formed on the surface of the sample is observed, and grades are given based on the criteria of FIG. 3.

	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3
Pollution Degree	3.5	3.5	3.5	2.0	2.5	3.5
Water repellency grade	3.5	4.0	4.5	2.5	3.0	2.5

The artificial leather of the Example which impregnated the fluorine-containing modified polyurethane of this invention as an elastic body in the state which does not add a fluorine-type surfactant separately from Table 2 is equivalent to the artificial leather (Comparative Example 3) which added the fluorine-type surfactant separately. It can be seen that it exhibits antifouling performance and at the same time has improved water repellency.

Artificial leather of the present invention is an artificial leather impregnated with a fluorine-containing modified polyurethane imparted with antifouling function, it is not necessary to use a fluorine-based surfactant for the antifouling property in the production of artificial leather to improve productivity, fluorine-based surfactant It improves the appearance quality of artificial leather by showing excellent antifouling performance that suppresses the change of surface of artificial leather over time.

Claims (6)

1. In an artificial leather in which a nonwoven fabric formed by entangled microfibers is impregnated with a polymer elastomer and a brush is formed,

   The polymer elastomer is a fluorine-containing modified polyurethane,

   The said fluorine-containing modified polyurethane is a polymerization product by reaction of the urethane prepolymer in which the isocyanate group is located in the terminal obtained by making diol and diisocyanate react, and the fluorinated carbon compound provided with the hydroxy functional group at both terminals, and has a weight average molecular weight ( Suede artificial leather having antifouling properties characterized in that Mw) is 500,000 ~ 800,000.
2. The method of claim 1,

   The urethane prepolymer has a weight average molecular weight (Mw) of suede artificial leather having antifouling properties, characterized in that 400,000 ~ 700,000.
3. The method of claim 1,

   The fluorinated carbon compound provided with hydroxy functional groups at both ends has 8 to 14 fluorine groups bonded to one side chain, 50 to 70 mol% of fluorine at one structural end, and hydroxy functional groups at both ends. Suede artificial leather having antifouling properties characterized in that the ether diol imparted.
4. In the manufacturing method of artificial leather formed by impregnating the polymer elastic body by immersing the nonwoven fabric formed by interweaving the ultrafine fibers in three dimensions in an impregnation solution containing a polymer elastomer,

   The polymer elastomer is a fluorine-containing modified polyurethane,

   The fluorine-containing modified polyurethane reacts with a diol and a diisocyanate to prepare a urethane prepolymer having a weight average molecular weight (Mw) of 400,000 to 700,000, and the fluorinated carbon compound to which hydroxy functional groups are provided at both ends of the prepared prepolymer. A method of producing a suede artificial leather having antifouling properties, characterized in that by reacting the weight average molecular weight (Mw) is made of a polymer of 500,000 ~ 800,000.
5. The method of claim 4, wherein

   The method for producing suede artificial leather having antifouling properties, wherein the molar ratio of diol and diisocyanate is reacted in the range of 1: 1.2 to 1: 1.4 when preparing the urethane prepolymer.
6. The method of claim 4, wherein

   The fluorinated carbon compound provided with hydroxy functional groups at both ends has 8 to 14 fluorine groups bonded to one side chain, 50 to 70 mol% of fluorine at one structural end, and hydroxy functional groups at both ends. Method for producing a suede artificial leather having antifouling properties characterized in that the ether diol imparted.

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