KR20170053756A - Non-solvent polyurethane and method for manufacturing synthetic leather of car seat using thereof - Google Patents

Abstract

The present invention relates to a solventless polyurethane resin and a process for producing synthetic leather for automobile seat using the same. More particularly, the present invention relates to a process for producing synthetic leather for automobile seat using a solventless polyurethane resin, And a method for producing synthetic leather for automobile seat using the polyurethane resin.
A method of manufacturing a synthetic leather for automobile seat according to the present invention includes: a first step of preparing a subject of a polymer compound containing active hydrogen; A second step of preparing a curing agent of a diisocyanate compound capable of reacting with active hydrogen; A third step of preparing a solvent-free polyurethane resin by mixing and stirring the mixture of a subject and a curing agent; A fourth step in which the polyurethane resin is coated on a releasing paper or a substrate to perform first warm-drying; And a fifth step of secondarily heating and drying the releasing paper or base material with the fabric.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polyurethane resin,

The present invention relates to a solventless polyurethane resin and a process for producing synthetic leather for automobile seat using the same. More particularly, the present invention relates to a process for producing synthetic leather for automobile seat using a solventless polyurethane resin, And a method for producing synthetic leather for automobile seat using the polyurethane resin.

Generally, synthetic leather is one of synthetic leather. A surface layer corresponding to a grain layer of leather is formed of a polyurethane foam on a support such as a woven fabric or a knitted fabric, and polyamide has sometimes been used once. Recently, due to the development of technology, appearance and performance are not lowered compared to natural leather, and it is used in bags, automobile seats, furniture and the like.

Meanwhile, the conventional polyurethane resin for synthetic leather coating is dissolved in an organic solvent such as dimethylformamide (DMF), methylethylketone (MEK), and toluene (Toluene) Synthetic leather is produced.

Synthetic leather made of such a conventional polyurethane resin is essentially used as an organic solvent in the process. However, such an organic solvent is volatilized into the atmosphere by heating during processing, causing environmental pollution problems in the world, There is a problem that the organic solvent remains and is harmful to the human body.

In addition, in the case of the conventional solution type polyurethane adhesive, a cross-linking agent is added to give a reticular structure, resulting in poor flexibility and deteriorating the feel of natural leather.

Korean Registered Patent No. 10-1171634 (July 27, 2012)

Disclosure of the Invention The present invention has been conceived to solve the problems described above. It is an object of the present invention to provide a solvent-free polyurethane resin which is environmentally friendly, And a manufacturing method thereof.

It is another object of the present invention to provide a durable polyurethane resin capable of providing a tactile sensation of natural leather more effectively, and a method of producing synthetic leather for automobile seat using the polyurethane resin.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems to be solved by the present invention, which are not mentioned here, As will be appreciated by those skilled in the art.

A method of manufacturing a synthetic leather for automobile seat according to the present invention includes: a first step of preparing a subject of a polymer compound containing active hydrogen; A second step of preparing a curing agent of a diisocyanate compound capable of reacting with active hydrogen; A third step of preparing a solvent-free polyurethane resin by mixing and stirring the mixture of a subject and a curing agent; A fourth step in which the polyurethane resin is coated on a releasing paper or a substrate to perform first warm-drying; And a fifth step of secondarily heating and drying the releasing paper or base material with the fabric.

Further, the subject matter of the method for producing a synthetic leather for automotive seat of the present invention includes at least one of polyester polyol, polyether polyol, polycarbonate polyol or polycaprolactane polyol each containing active hydrogen And a chain extender containing at least one or more of a polyol and an olefinic hydrocarbon or glycol alcohol.

Also, 10 to 30 parts by weight of the chain extender is mixed with 100 parts by weight of the polyol of the present invention.

Further, the curing agent according to the method for producing a synthetic leather for automotive seat of the present invention comprises at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol or a polycaprolactane polyol each containing active hydrogen And reacting the polyisocyanate with a diisocyanate containing at least one or more of polyol and toluene diisocyanate, methylene diphenyl diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate to produce a diisocyanate prepolymer.

Further, the viscosity of each of the subject matter and the curing agent of the present invention is 1000 to 10,000 cps.

Also, 100 to 110 parts by weight of a subject is mixed with 100 parts by weight of the curing agent of the present invention.

In addition, the first warming-up time of the present invention is the time for the chemical reaction to proceed from 30 to 60% from the first warming-up start time, and the fifth step is performed after the fourth cooling step .

The solventless polyurethane resin according to the present invention is a polymeric compound containing active hydrogen; And a curing agent of a diisocyanate compound capable of reacting with active hydrogen.

Further, the subject matter of the solventless polyurethane resin according to the present invention is a polyurethane resin comprising at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol or a polycaprolactane polyol each containing an active hydrogen, A polyether polyol, a polycarbonate polyol, or a polycarbonate polyol, each of which is composed of an active hydrogen, with a chain extender containing at least one of an olefinic hydrocarbon and a glycol alcohol, A polyisocyanate, a polyol, and a diisocyanate containing at least one or more of toluene diisocyanate, methylene diphenyl diisocyanate, isophorone diisocyanate, or hexamethylene diisocyanate is reacted with a diisocyanate prepolymer Division doedoe, characterized in that the subject 100 to 110 parts by weight mixed with respect to 100 parts by weight of a curing agent.

According to the solution of the above-mentioned problems, the method of producing the polyurethane resin of the present invention and the synthetic leather for automobile seat using the same, without using the organic solvent harmful to the human body, manufactures the solvent-free polyurethane resin and the synthetic leather for environment- There is no environmental pollution and there is no fear that the organic solvent will remain in the synthetic leather, and the productivity can be improved by simplifying the working process, shortening the working time, and reducing the equipment cost by using the existing dry processing equipment as it is.

In addition, the method for producing a synthetic leather for automobile seat using the dyed polyurethane resin of the present invention and the synthetic leather for automobile seat using the dyed polyurethane resin according to the present invention has a linear structure and is more effective in achieving tactile feeling of natural leather.

1 is a flow chart for explaining a method of manufacturing a synthetic leather for a car seat according to an embodiment of the present invention.

The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the accompanying drawings.

1 is a flow chart for explaining a method of manufacturing a synthetic leather for a car seat according to an embodiment of the present invention.

As shown in Fig. 1, a method for manufacturing synthetic leather for automobile seat according to an embodiment of the present invention is performed according to the following steps.

First, in a first step (S110), a subject of a polymer compound containing active hydrogen is prepared.

Specifically, the subject matter is a polyether polyol (PolyEsterPolyol) having an active hydrogen of 500 to 4000 in molecular weight, a polyetherpolyol having an active hydrogen of 500 to 4000 in molecular weight, an active hydrogen having a molecular weight of 500 to 4000 A polycarbonate polyol or a polyol obtained by mixing two or more polyols of one of polycaprolactone polyols containing an active hydrogen having a molecular weight of 500 to 4000 and an olefinic hydrocarbon or a glycol (Glycole) alcohol And a chain extender containing at least one of the above chain extender.

At this time, it is possible to mix 10 to 30 parts by weight of the chain extender with respect to 100 parts by weight of the polyol. This is because, in case of the chain extender, elasticity and flexibility are determined according to the input amount, and the hardness is adjusted to various kinds and the product can be used for various purposes. When the ratio of the chain extender is less than 10 parts by weight, heat resistance, , It is not suitable for a resin for a car seat requiring high physical properties because of its low water resistance, and when it exceeds 30 parts by weight, the feeling becomes hard and the use range is limited.

Next, in a second step (S120), a curing agent of a diisocyanate compound capable of reacting with active hydrogen is prepared.

Specifically, the curing agent is selected from the group consisting of a polyester polyol containing an active hydrogen having a molecular weight of 500 to 4000, a polyether polyol containing an active hydrogen having a molecular weight of 500 to 4000, an active hydrogen having a molecular weight of 500 to 4000 A polycarbonate polyol or a polyol obtained by mixing two or more of the polyols of polyCaprolactonePolyol having an active hydrogen having a molecular weight of 500 to 4000 and a polyol such as toluene diisocyanate (TDI), methylene diphenyl A diisocyanate prepolymer is produced by reacting a diisocyanate containing at least one of MDI (methylene diphenyl diisocyanate), isophorone diisocyanate (IPDI), or hexamethylene diisocyanate (HDI) do.

Here, the diisocyanate prepolymer is a diisocyanate prepolymer having a terminal free NCO content of 10 to 29% by reacting a diisocyanate with a polymer having an active hydrogen.

Next, in a third step (S130), the base and the curing agent are mixed and stirred to prepare a solventless polyurethane resin.

In one embodiment of the present invention, it is preferable to mix 100 to 110 parts by weight with respect to 100 parts by weight of the curing agent. That is, since the above-prepared base and curing agent are mixed and stirred at a precise chemical equivalent molar ratio, if the raw materials are not mixed at a precise chemical equivalent molar ratio, unreacted raw materials are left and the quality of the product is lowered. . A more detailed description thereof will be described later with reference to experimental examples.

In addition, the viscosity of each of the base and the curing agent according to one embodiment of the present invention is 1000 to 10000 cps. When the viscosity is less than 1,000 cps, the surface tension during coating is lowered due to mixing, so that the solventless polyurethane resin aggregates. When the viscosity exceeds 10,000 cps, unevenness occurs during coating due to high viscosity. It is needless to say that, when the difference between the viscosity of the curing agent and the subject increases, it is difficult to uniformly formulate the curing agent so as to have a similar viscosity.

The solvent-free polyurethane resin according to one embodiment of the present invention thus produced is environmentally friendly and has a relatively simple reaction process and relatively low viscosity as compared with the conventional solution type polyurethane resin, There is an advantage that the ease of adjustment and the workability due to viscosity can be improved.

Next, in a fourth step (S140), a non-solvent-type polyurethane resin is coated on a release paper or a substrate and subjected to first warm-drying. At this time, the heating condition is 30 to 150 ° C, and the chemical reaction is partially advanced over time under the first heating condition.

Next, in a fifth step (S150), the releasing paper or base material is kneaded with the fabric and then subjected to second warm-drying to complete the synthetic leather for automobile seat. At this time, the heating condition is 30 to 80 ° C, and the remaining chemical reaction is completed under the second heating condition.

Here, the first primary warming-up time according to an embodiment of the present invention is a time period during which the chemical reaction proceeds from 30 to 60% from the initial warming-up start time, and the fourth step is followed by the fifth step . This is due to the fact that the state of the synthetic leather varies depending on the progress of the chemical reaction in the fourth step. It is noted that the chemical reaction is proportional to the temperature and time, and the chemical reaction after the start of the first warm- %.

In other words, it can be confirmed that when the bonding is performed at a point where a chemical reaction of less than 30% is started, it can not penetrate into the fabric and can not be bonded. In case of exceeding 60%, the chemical reaction progresses much, but the adhesion to the fabric is poor, but the adhesion is poor. In particular, in the I-test, the fabric and the resin can be separated.

As described above, the non-solvent-based polyurethane resin according to one embodiment of the present invention and the method for manufacturing the synthetic leather for automobile seat using the same can be used for manufacturing a solvent-free polyurethane resin and synthetic leather for environment- Thus, there is no environmental pollution and there is no fear that the organic solvent remains in the synthetic leather, and the productivity can be improved by simplifying the working process, shortening the working time, and reducing the equipment cost by using the existing dry processing equipment as it is.

The polyurethane resin of the present invention and the method of manufacturing synthetic leather for automobile seat using the polyurethane resin according to an embodiment of the present invention are advantageous in that the natural texture of natural leather can be more effectively achieved by the linear structure.

Hereinafter, the optimum ratio condition of the above-mentioned subject and the curing agent, and the optimal distribution condition of the chemical reaction progress ratio between the fourth and fifth steps will be described below through experiments.

<Comparative Example>

In the comparative example, the physical properties of the organic solvent type resin for automobile sheet used in the past are compared.

<Experimental Example 1>

The optimum mixing ratio of the base and the curing agent is 105 parts by weight based on 100 parts by weight of the curing agent and the physical properties are tested.

Thereafter, in the case of Experimental Examples 2 to 5, the mixing ratio is adjusted to conduct the test. The physical properties test was performed by the test items and test methods shown in Table 1 below.

The composition is mixed and agitated at a precise chemical equivalent molar ratio to apply a certain amount of the resin on the release paper or substrate. At this time, the temperature in the heating chamber is raised to 60 to 150 캜 so as to quickly react the composition applied to the release paper or the substrate, so that the reaction is rapidly performed. At this time, it is coated by a roll or knife method, and a chemical reaction is progressed by 50 to 60% in the process of polymer progression. The roll is pressed under a roll pressure at 30 to 80 ° C for 12 to 48 hours and then peeled off to produce an environmentally friendly synthetic leather.

<Experimental Example 2>

In Experimental Example 2, 95 parts by weight of a base was mixed with 100 parts by weight of the curing agent using the composition of Experimental Example 1, and the same procedure as in Experimental Example 1 was conducted to prepare a synthetic leather.

<Experimental Example 3>

In Experimental Example 3, 100 parts by weight of a base was mixed with 100 parts by weight of a curing agent using the composition of Experimental Example 1, and synthetic leather was prepared in the same manner as Experimental Example 1. [

<Experimental Example 4>

In Experimental Example 4, 110 parts by weight of a base was mixed with 100 parts by weight of the curing agent using the composition of Experimental Example 1, and the same procedure as in Experimental Example 1 was carried out to prepare a synthetic leather.

<Experimental Example 5>

In Experimental Example 5, 115 parts by weight of a base was mixed with 100 parts by weight of a curing agent using the composition of Experimental Example 1, and synthetic leather was produced through the same procedure as in Experimental Example 1. [

The physical properties of the solvent-resistant polyurethane resin and synthetic leather for automobile seat thus manufactured were measured by the same method as in Table 1, and the results are shown in Tables 2 to 6 below.

At this time, the solvent-free polyurethane resin was mixed and agitated at a precise chemical equivalent molar ratio and aged for 12 hours after the application of the release paper, and synthetic leather was formed by bonding the fabric to the fabric in a state where the chemical reaction of the composition proceeded by 50 to 60% The results of the tests of the two physical properties are shown in Tables 2 to 6.

The following Table 2 shows the physical properties of the product when the resin alone is coated in Experimental Examples 1 to 5.

The following Table 3 shows the physical properties of the product after heat-aging (120 ° C * 7 days) after the resin alone coating in Experimental Examples 1 to 5.

The following Table 4 shows the physical properties of the synthetic leather products in Experimental Examples 1 to 5.

The following Table 5 shows the physical properties of the synthetic leather products in Experimental Examples 1 to 5 (120 ° C * 7 days).

The following Table 6 shows the results of physical properties test (120 ° C * 95% * 2 days) of the synthetic leather products in Experimental Examples 1 to 5.

<Experimental Example 6>

In Experimental Example 6, synthetic leather was prepared by bonding the fabric of Experimental Example 1 with the chemical reaction proceeding 10 to 20%.

<Experimental Example 7>

In Experimental Example 7, synthetic leather was prepared by bonding the fabric of Experimental Example 1 with the chemical reaction proceeding 30 to 40%.

<Experimental Example 8>

In Experimental Example 8, synthetic leather was prepared by bonding the fabric of Experimental Example 1 with 70 to 80% chemical reaction.

The non-solvent polyurethane synthetic leather for automobile seat thus manufactured was measured in the same manner as in Table 1, and the results are shown in Tables 7 to 9.

Table 7 shows the physical properties of the synthetic leather products in Experimental Examples 6 to 8.

Table 8 shows the physical properties of the synthetic leather products in Experimental Example 7 and Experimental Example 8 at 120 ° C for 7 days.

Table 9 shows the results of physical properties test (120 ° C * 95% * 2 days) of the synthetic leather products in Experimental Examples 7 and 8.

The results of Experimental Examples 1 to 5 show that Examples 1, 3, and 4 exhibit satisfactory results in terms of all properties such as adhesion, heat resistance, water resistance and light resistance when compared with Comparative Examples, 2 and Experimental Example 5, it was confirmed that the physical properties were deteriorated. That is, unreacted raw materials are left behind and the quality of the product is considered to be lowered. It was confirmed that even from 100 parts by weight to 110 parts by weight of the base material, 100 parts by weight of the curing agent could be used for a car seat.

In addition, the results of Experimental Examples 6 to 8 show that in the case of Experimental Example 6, when the bonding is performed at the point where the chemical reaction starts, the fabric can not penetrate into the fabric and can not be bonded. In Experimental Example 8, the chemical reaction progressed so much that the adhesive layer was bonded to the fabric but the adhesive strength was decreased.

Experimental Example 1 and Experimental Example 7 showing the most favorable results show that the most suitable fabric is preferably after 50 to 60% progress of the chemical reaction and 30 to 60% .

As described above, it is to be understood that the technical structure of the present invention can be embodied in other specific forms without departing from the spirit and essential characteristics of the present invention.

Therefore, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than the foregoing description, All changes or modifications that come within the scope of the present invention should be construed as being included within the scope of the present invention.

Claims (9)

A first step of preparing a subject of a polymer compound containing active hydrogen;
A second step of preparing a curing agent of a diisocyanate compound capable of reacting with the active hydrogen;
A third step of mixing and stirring the above-mentioned subject and said curing agent to prepare a solventless polyurethane resin;
A fourth step of coating the release agent or the substrate with the solvent-free polyurethane resin to perform first warm-drying; And
A fifth step of secondarily heating and drying the release paper or the base material with the fabric;
Wherein the synthetic leather is a synthetic leather. The method according to claim 1,
The above-
A polyol comprising at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol or a polycaprolactane polyol, each of which contains active hydrogen,
Olefinic hydrocarbons, and glycol alcohols. The method for producing a synthetic leather for automobile seat according to claim 1, 3. The method of claim 2,
Wherein 10 to 30 parts by weight of the chain extender is mixed with 100 parts by weight of the polyol. 3. The method of claim 2,
The curing agent,
A polyol comprising at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol or a polycaprolactane polyol, each of which contains active hydrogen,
Wherein the diisocyanate prepolymer is produced by reacting a diisocyanate containing at least one of toluene diisocyanate, methylenediphenyl diisocyanate, isophorone diisocyanate, or hexamethylene diisocyanate to produce a diisocyanate prepolymer. Way. The method according to claim 1,
Wherein a viscosity of each of the subject and the curing agent is 1000 to 10000 cps. The method according to claim 1,
Wherein 100 to 110 parts by weight of the subject is mixed with 100 parts by weight of the curing agent. The method according to claim 1,
Wherein the first warming-up time is a time for the chemical reaction to progress from 30 to 60% from the first warming-up start time, and the fifth step is performed after the fourth cooling step A method for producing synthetic leather. The subject of macromolecular compounds containing active hydrogen; And
A curing agent of a diisocyanate compound capable of reacting with the active hydrogen;
&Lt; / RTI &gt; 9. The method of claim 8,
The subject matter includes a polyol comprising at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol or a polycaprolactane polyol, each of which contains an active hydrogen, at least one of an olefinic hydrocarbon or a glycol alcohol Or more of a chain extender,
The curing agent may be at least one selected from the group consisting of a polyol containing at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol or a polycaprolactane polyol, each containing an active hydrogen, and at least one selected from the group consisting of toluene diisocyanate, methylenediphenyl diisocyanate, Wherein the diisocyanate prepolymer is produced by reacting a diisocyanate containing at least one of furandiisocyanate and hexamethylene diisocyanate,
Wherein 100 to 110 parts by weight of the subject is mixed with 100 parts by weight of the curing agent.

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