KR20150131639A - Eco-friendly fluoro-polyurethane resin composition and surface-waterproof agent using the fluoro-polyurethane resin - Google Patents

Abstract

The present invention relates to an environmentally friendly fluorinated polyurethane resin composition and a surface water repellent agent using the same.
The present invention uses a fluoroalcohol having a polyfluoroalkyl group having 6 or less carbon atoms (Rf group) to reduce the environmental load without containing perfluorooctanoic acid (PFOA), which is an environmental regulatory substance at home and abroad, and to produce a copolymerized polycarbonate polyol And a water-repellent and hydrolysis-resistant property due to the lowering of the carbon number is solved by optimizing the composition of the fluorine-containing polyurethane resin composition containing the fluorine-containing polyurethane resin, Is water repellent to various base materials including synthetic leather, water repellency and hydrolysis resistance can be realized.

Description

TECHNICAL FIELD [0001] The present invention relates to an environmentally friendly fluoropolyurethane resin composition and a surface water repellent agent using the same. BACKGROUND ART [0002]

The present invention relates to an environmentally friendly fluorinated polyurethane resin composition and a surface water repellent agent using the same, and more particularly, to a fluorinated polyurethane resin composition comprising a fluorinated alcohol having a polyfluoroalkyl group having 6 or less carbon atoms (hereinafter referred to as " Rf group & The present invention provides an environmentally friendly fluorinated polyurethane resin composition which is low in environmental load and contains a copolymerized polycarbonate polyol to optimize its composition to solve the water repellency and hydrolysis resistance property problems due to the lowering of the carbon number. The present invention relates to an environmentally friendly fluorinated polyurethane resin composition and a surface water repellent agent using the same, wherein a surface water repellent agent in the form of a solution containing a polyurethane resin is subjected to water repellency treatment on various substrates including synthetic leather to realize excellent water repellency and hydrolysis resistance.

As a method for imparting water repellency to the surfaces of products such as fibers and synthetic leather, it is possible to prepare a composition comprising a polyacrylic copolymer or a polyurethane copolymer based on a monomer having an Rf group having 8 or more carbon atoms, Coating and drying are known.

As a report on improving water repellency, Korean Patent Publication No. 2005-26383 discloses a fluorinated polyurethane resin having improved water repellency when a urethane resin is synthesized using a fluorine chain introduced into the side chain, and Korean Patent No. 0343549 And a fluorinated water-dispersible polyurethane which realizes low surface energy and water dispersion stability.

Korean Patent Laid-Open No. 2001-0017938 also discloses a method of reacting an isocyanate compound selected from diisocyanate and polymeric isocyanate with a specific fluorine-containing monofunctional compound and a fluorine-free polyfunctional compound selected from polyhydric alcohol and polycarboxylic acid The water-repellent ability is improved by using a monofunctional fluororesin which imparts water repellency, oil repellency, high water-resistance, surface lubricity and surface luster to maintain the properties after washing. Have reported excellent polyurethane resin compositions.

However, the conventional polyurethane resin compositions thus synthesized can exhibit high water repellency due to the use of fluoroalcohol having an Rf group of not less than 8 carbon atoms, but the environment and living body due to PERFLUOROOCTANOIC ACID (hereinafter referred to as " PFOA & The problem of high environmental load is pointed out.

Recent studies [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf) Concerns about the environmental load due to PFOA, a kind of roalkyl compound, have been found, and the long chain fluoroalkyl group (telomer) is a foam stabilizer; Care products and cleaning products; It is used in many products including carpet, textile, paper, leather-based water-repellent oil-coating and antifouling coating.

Such telomeres have been reported to be capable of producing PFOA by degradation or metabolism [Federal Register (FR Vol. 68, No. 73 / April 16, 2003 [FRL-2303-8], http: // www. epa.gov/opptintr/pfoa/pfoafr.pdf) [EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003, EPAINTENSIFIES SCIENTIFIC INVESTIGATlON OF A CHEMICAL PROCESSING AID] (http://www.epa.gov/opptintr/pfoa/ pfoaprs.pdf) or [EPA OPPT FACT SHEET April 14, 2003] (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf)]. On April 14, 2003, the US Environmental Protection Agency (EPA) announced that it would strengthen scientific research on PFOA.

According to such a situation, a polyacrylic water repellent agent formed of a monomer component having an Rf group having 6 or less carbon atoms has been developed. However, the water repellency is lowered as compared with a polyacrylic water repellent agent formed of a monomer component having an Rf group having a carbon number of 8 or more, I can not.

These results are attributed to the surface orientation due to the difference in the number of carbon atoms in the Rf group, and show the same results in polyurethane water repellent as well as polyacrylic water repellent.

From various research results thus far, it is shown that, in practical treatment of a surface treating agent, particularly a water repellent agent, a dynamic contact angle, particularly a receding contact angle, is important as its surface property, not a static contact angle.

That is, although the advancing contact angle of water does not depend on the number of side chain carbon atoms in the Rf group, it can be confirmed that the receding contact angle of water becomes significantly smaller at 7 or less as compared with 8 or more of the side chain carbon atoms in the Rf group.

As a result of X-ray analysis, it has been confirmed that, in the case of a monomer having an Rf group having 7 or more carbon atoms in the side chain, crystallization of the side chain occurs, practical water repellency has a correlation with the crystallinity of the side chain, Is known to be an important factor in the development of practical performance [Maekawa and Takashiga, Fine Chemical, Vol. 23, No. 6, P12 (1994)]. Therefore, it has been considered that the polymer having a short Rf group with a carbon number of the side chain of 7 or less (especially 6 or less) in the side chain has low crystallinity of the side chain and thus can not satisfy the practical performance, particularly the water repellency.

The properties of the polyurethane resin are greatly affected by the structure of the polyol. The properties of the polyol, which plays a role of a soft segment in the urethane polymer chain, affect the tensile strength, elasticity and elongation. These oligomers are also as important as isocyanates in determining the surface properties of urethane polymers and affect adhesion to surfaces, water repellency and stain resistance. Therefore, the structure of the polyol plays an important role in determining the physical properties and surface characteristics of the urethane resin.

The raw materials of the main soft segment portion of the polyurethane resin produced on the conventional industrial scale include a polyether type represented by polytetramethylene glycol, a polyester type represented by adipate ester, a polylactone type represented by polycaprolactone, Quot; Polyurethane Basis and Application ", pp. 96-106, supervised by Matsunaga Katsuji, CMC Publishing Co., Ltd., published November 2006].

Among them, the ether type is excellent in hydrolysis resistance, flexibility and stretchability, but has poor heat resistance and light resistance. On the other hand, the polyester polyol type has improved heat resistance and weather resistance, .

On the other hand, the polylactone type has superior hydrolysis resistance as compared with the polyester polyol type, but hydrolysis can not be completely suppressed because there is an ester group in the same way. It has also been proposed to use these polyester polyol type, ether type and polylactone type in combination, but even in this case, it is not possible to completely compensate for each defect.

On the other hand, the polycarbonate-type polyol is mainly a polycarbonate diol obtained by reacting 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc., Is superior in water resistance, weather resistance, hydrolysis resistance and chemical resistance as compared with polyurethanes obtained from other polyester polyols and polyether polyols, and also has excellent mechanical strength such as tensile strength, and as a raw material for polyurethane, Artificial leather, (water-based) paints, and adhesives.

However, currently available polycarbonate diols are polycarbonate diols synthesized from 1,6-hexanediol, and they are crystalline and therefore have no fluidity in the form of wax at room temperature, which is another problem that is difficult to handle.

Also, the polyurethane resin prepared by using a polycarbonate diol synthesized from 1,6-hexanediol as a polyurethane raw material has a high cohesion of a soft segment, inferiority in flexibility, elongation, bending property and elasticity recovery at low temperature, The solution viscosity of the polyurethane solution is also high, so that it is difficult to operate in molding or coating and is used for limited use. Particularly, in the case of artificial leather produced from this, it is pointed out that the texture is lower than that of natural leather due to the hard texture.

Accordingly, the present inventors have made efforts to solve the environmental load and harmfulness problem due to PFOA while maintaining the physical properties of the water repellent polyurethane resin. As a result, it has been found that by using a fluorine alcohol containing Rf group having 6 or less carbon atoms, A surface-water repellent agent in the form of a solution containing a fluorinated polyurethane resin obtained from the environmentally friendly fluorinated polyurethane resin composition is obtained by dissolving a copolymerizable polycarbonate polyol in a decomposition- To confirm excellent water repellency and hydrolysis resistance, thereby completing the present invention.

An object of the present invention is to provide an environmentally friendly fluorinated polyurethane resin composition excellent in water repellency and hydrolysis resistance.

Another object of the present invention is to provide a surface water repellent agent containing the fluorinated polyurethane resin.

The present invention relates to (A) an aliphatic or aromatic diisocyanate component,

(B) a polyhydric polyol containing a copolymerized polycarbonate polyol component and

(C) a monohydric alcohol component containing an Rf group having 1 to 6 carbon atoms. The present invention also provides an environmentally friendly fluorinated polyurethane resin composition.

In the environmentally friendly fluoropolymer resin composition of the present invention, the monohydric alcohol as the component (C) is a fluorinated alcohol (a) having an Rf group having 1 to 6 carbon atoms and a fluorine-free aliphatic More specifically, the fluorine-containing fluorine alcohol (a) having 1 to 6 carbon atoms and the fluorine atom-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms are contained in an amount of from 99: 1 to 50: 50 by weight.

At this time, the fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms is preferably any one selected from the following (1) to (6).

(In the above, Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms.)

Further, the fluorine-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms is preferably selected from the group consisting of octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, Alcohol, and the like.

In the fluorinated polyurethane resin composition, the polyhydric polyol component as the component (B) may further contain, alone or in combination with the copolymerized polycarbonate polyol component, a polyether polyol or a polyester polyol .

At this time, the copolymerized polycarbonate polyol component is a polycarbonate diol obtained by copolymerizing 1,6-hexanediol and 1,5-pentanediol, a polycarbonate diol copolymerized with 1,6-hexanediol and 1,4-butanediol, , A polycarbonate diol in which 3-propanediol and 1,5-pentanediol are copolymerized, and a polycarbonate diol in which 1,3-propanediol and 1,4-butanediol are copolymerized.

Further, the present invention provides a surface water repellent agent containing a fluorinated polyurethane resin represented by the following general formula (1).

Formula 1

(1)

R _{1 is a} monovalent alcohol group containing an alkyl group-containing fluorine alcohol (a) having 1 to 6 carbon atoms and a fluorine atom-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms,

R ₂ : an aliphatic or aromatic diisocyanate residue,

R ₃ is a polyhydric alcohol group containing a copolymerized polycarbonate polyol.)

More preferably, the surface water repellent of the present invention is in the form of a solution containing 20 to 80% by weight of a fluorinated polyurethane resin.

The above surface water repellent agent is subjected to water-repellent treatment by wet processing or dry processing on the surface of the substrate. As a preferable substrate, synthetic leather having excellent water repellency and hydrolysis resistance can be provided by applying the surface water repellent agent have.

As another substrate, the surface water repellent may be applied to any one selected from stone, glass, paper, wood, brick, cement and plastic to realize excellent water repellency and hydrolysis resistance.

INDUSTRIAL APPLICABILITY The environmentally friendly fluorinated polyurethane resin composition of the present invention uses fluoroalcohol having an Rf group having 6 or less carbon atoms and does not contain perfluorooctanoic acid (PFOA) which is an environmental regulatory substance at home and abroad, The problem of harmfulness can be solved and the composition containing the copolymerized polycarbonate polyol can be optimized to solve the problem of deterioration of the water repellency and hydrolysis property due to the decrease of the carbon number.

Thus, by providing a surface water repellent agent in the form of a solution containing a fluorinated polyurethane resin obtained from the environmentally friendly fluoropolymer resin composition of the present invention, water repellency and water repellency comparable to those in the case of using a fluoropolymer resin obtained by conventional PFOA- Degradability is realized.

Further, by providing the surface water repellent of the present invention to water-repellent treatment on various substrates including synthetic leather, various substrates including synthetic leather realized excellent water repellency and hydrolysis resistance are provided.

1 is a photograph showing the water repellency of external contaminants (water and cola) after water repellent treatment of the surface water repellent of the present invention on synthetic leather,
FIG. 2 is a photograph showing the water repellency of external pollutants (water and cola) after water repellent treatment of conventional PFOA-containing surface water repellent to synthetic leather,
Fig. 3 is a photograph showing the water repellency of external pollutants (water and cola) on synthetic leather on which the surface water repellent agent is not treated.

Hereinafter, the present invention will be described in detail.

The present invention relates to (A) an aliphatic or aromatic diisocyanate component,

(B) a polyhydric polyol containing a copolymerized polycarbonate polyol component and

(C) a monohydric alcohol component containing an Rf group having 1 to 6 carbon atoms. The present invention also provides an environmentally friendly fluorinated polyurethane resin composition.

The environmentally friendly fluoropolymer resin composition as described above can solve the environmental load and harmfulness problem caused by PFOA by using a fluorine-containing alcohol having an Rf group as the component (C), and the copolymerizable polycarbonate polyol component Whereby the water repellency due to the lowering of the carbon number and the lowering of the hydrolysis resistance are solved.

More specifically, in the environmentally friendly fluorinated polyurethane resin composition of the present invention, the monohydric alcohol as the component (C) is a fluorinated alcohol (a) having an Rf group having 1 to 6 carbon atoms and an alkyl group having 8 to 22 carbon atoms (A) having an Rf group of 1 to 6 carbon atoms and the fluorine-free aliphatic alcohol (b) having an alkyl group having a carbon number of 8 to 22 in a ratio of from 99: 1 to 50: 50, more preferably from 99: 1 to 80:20.

The fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms is preferably a monohydric alcohol containing a linear or branched perfluoroalkyl group (Rf group) having 6 or less carbon atoms, and the number of carbon atoms of the Rf group is preferably 1 to 6 And more preferably 4 to 6 carbon atoms.

A preferred example of the fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms is any one selected from the following (1) to (6).

(In the above, Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms.)

The fluorine-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms is preferably a monohydric saturated alcohol or an unsaturated alcohol containing an alkyl group having 8 to 22 carbon atoms, and preferred examples thereof include octyl alcohol, decyl alcohol, Lauryl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, arachidyl alcohol and biphenyl alcohol.

In addition, the physical properties of the fluorinated polyurethane resin are affected not only by the isocyanate but also by the structure of the polyol. The polyhydric polyol component of the component (B), which plays a role of a soft segment in the polyurethane chain, The carbonate polyol component may further contain, alone or in combination, a polyether polyol or a polyester polyol.

More specifically, the polyether group-containing polyol as the component (B) may be a divalent or trivalent polyol such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol having a number average molecular weight in the range of 200 to 4000, Preferably, the divalent and trivalent polyols of polypropylene glycol and divalent polyols of polytetramethylene glycol are used.

The polyester polyol as the component (B) is an aromatic ester polyol having a number average molecular weight in the range of 200 to 2000, and an aliphatic ester polyol.

The polycarbonate group polyol as the component (B) is a polycarbonate group-containing divalent polyol having a number average molecular weight in the range of 500 to 2000.

Generally, in a polycarbonate polyol obtained by reacting 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or the like with phosgene, the present invention relates to 1,6- And 1,5-pentanediol, a polycarbonate diol obtained by copolymerizing 1,6-hexanediol with 1,4-butanediol, a polycarbonate diol obtained by copolymerizing 1,3-propanediol and 1,5- And a polycarbonate diol obtained by copolymerizing 1,3-propanediol with 1,4-butanediol, is used as the polycarbonate polyol.

More preferably, a polycarbonate diol in which 1,6-hexanediol is copolymerized with 1,5-pentanediol, or a polycarbonate diol in which 1,6-hexanediol and 1,4-butanediol are copolymerized is used.

In the environmentally friendly fluorinated polyurethane resin composition of the present invention, the component (A), which is the main component of the polyurethane, is a mixture of one or two aliphatic or aromatic diisocyanates, and the component (A) Is an isocyanate group (i.e., an NCO group).

Preferred examples include methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (Polymeric-MDI), toluene-2,4-diisocyanate (2,4-TDI), toluene- Isocyanate (2,6-TDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4-dimethylenedicyclohexyldiisocyanate (H12MDI), tetramethyl- (M-TMXDI), xylene diisocyanate (XDI), naphthylene-1,5-diisocyanate (NDI), and paraphenylene diisocyanate (PPDI).

Further, the present invention provides a surface water repellent agent containing a fluorinated polyurethane resin represented by the following general formula (1).

Formula 1

(1)

R _{1 is a} monovalent alcohol group containing an alkyl group-containing fluorine alcohol (a) having 1 to 6 carbon atoms and a fluorine atom-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms,

R ₂ : an aliphatic or aromatic diisocyanate residue,

R ₃ is a polyhydric alcohol group containing a copolymerized polycarbonate polyol.)

That is, the fluorinated polyurethane resin represented by the formula (1) of the present invention is obtained by reacting a polyether polyol, a polyester polyol and a copolymerized polycarbonate polyol having a number average molecular weight ranging from 200 to 4000 with respect to the component (A) of an aliphatic or aromatic diisocyanate (C) component of a monohydric alcohol containing a fluorine-containing alcohol (a) having an Rf group having 1 to 6 carbon atoms and introduced into the urethane main chain to have the structure of the formula (1) do.

A typical solution type polyurethane resin can be produced by reacting a diisocyanate with a polyol in an organic solvent, and the fluorine-based polyurethane resin of the present invention can also be produced by a conventional solution-type polyurethane resin synthesis method have.

More specifically, the solution type polyurethane resin is subjected to a step of progressing the urethane reaction under an uncatalyzed and catalyst under an organic solvent. That is, the reaction product is dissolved in an organic solvent, and after nitrogen substitution, an exothermic reaction is carried out in a temperature range of 30 to 90 ° C to prepare a prepolymer. Then, depending on the degree of reaction in each step, until the final isocyanate group (-NCO) The reaction proceeds to prepare the final fluorinated polyurethane resin.

In the case of the catalytic reaction, preferred examples of the reaction catalyst include a tertiary amine catalyst, a metal catalyst such as tin (Sn), silver (Ag), zinc (Zn), and a cyclic amidine . At this time, the catalyst is used in an amount of 0.001 to 1 part by weight, preferably 0.001 to 0.1 part by weight based on 100 parts by weight of the total amount of the reactants.

The organic solvent is inert to the monomers and dissolves them. Examples of the solvent include acetone, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, 1,4- Methyl isobutyl ketone, ethyl acetate, butyl acetate, dimethylformamide, and the like. The organic solvent is used in an amount of 10 to 300 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the total amount of the reactants.

The fluorinated polyurethane resin of the present invention is preferably in the form of a solution under an organic solvent. More preferably, in the fluorinated polyurethane resin of the present invention, the concentration of the fluorinated polyurethane resin is in the form of a solution containing 20 to 80% by weight. If the concentration of the fluorine-based polyurethane resin is less than 20% by weight, the fluorine-based polyurethane resin concentration becomes low and it is difficult to exhibit the required performance. As a result, the amount of the fluorine-based polyurethane resin is increased and the economic loss is increased due to the decrease in productivity and transportation cost. If it exceeds 80% by weight, it is difficult to control the polyurethane reaction due to an increase in the viscosity of the fluorinated polyurethane resin solution, which makes it difficult to produce a polyurethane resin composition of suitable quality.

(A) an aliphatic or aromatic diisocyanate component, (B) a polyhydric polyol containing a copolymerized polycarbonate polyol component, and (C) a monohydric alcohol component containing an Rf group having 1 to 6 carbon atoms Is the same as that described above in the environmentally friendly fluorinated polyurethane resin composition.

Particularly, the fluorinated polyurethane resin of the present invention can solve the environmental load and harmfulness problem caused by PFOA by using (C) a monohydric alcohol component containing an Rf group having 1 to 6 carbon atoms, (B) a polyvalent polyol containing a copolymerized polycarbonate polyol component, thereby realizing excellent water repellency and hydrolysis resistance.

More specifically, the component (C) is a mixture of a fluorine-containing alcohol (a) having an Rf group having 1 to 6 carbon atoms and a fluorine-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms in a ratio of from 99: 1 to 50:50 The fluorine-containing alcohol (a) having an Rf group having 1 to 6 carbon atoms in weight ratio is any one selected from the following (1) to (6), and a fluorine-free aliphatic alcohol having an alkyl group having a carbon number of 8 to 22 b) is any one selected from the group consisting of octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, arachidyl alcohol and biphenyl alcohol.

(In the above, Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms.)

Further, the polyvalent polyol component (B) may further contain, alone or in combination with the copolymerized polycarbonate polyol component, a polyether polyol or a polyester polyol.

Further, in the surface water repellent agent containing the fluorinated polyurethane resin represented by the general formula (1) of the present invention, water repellent treatment such as wet or dry can be applied to the substrate surface.

In the examples of the present invention, the synthetic leather is described as an example of a preferable surface of the base material. However, the synthetic leather is not limited to synthetic leather, but may be applied to a fiber as well as a synthetic leather, Any one selected can be applied as a description.

Specifically, at the time of producing synthetic leather, the surface water repellent agent containing the fluorinated polyurethane resin of the present invention can be subjected to water-repellent treatment by wet processing or dry processing.

Thus, wet processing can be carried out by impregnating or coating a substrate with a solution containing 20 to 80% by weight of a fluorine-based polyurethane resin of the present invention as a water repellent agent in a wetting polyurethane base resin, a diluting solvent, a toner, a penetrating agent and other functional additives Water repellent treatment can be performed.

In the dry processing, a synthetic leather is prepared by mixing a dry polyurethane base resin with a diluting solvent, a toner, a penetrating agent, and other functional additives, and then a water repellent agent containing the fluorinated polyurethane resin of the present invention is added to a diluting solvent Diluted, and subjected to a secondary processing treatment by a spray method to perform surface water repellent treatment. At this time, the fluorinated polyurethane resin is contained in an amount of 20 to 80% by weight.

FIG. 1 is a photograph showing the water repellency of an external contaminant (water and cola) after water repellent treatment of a surface water repellent of the present invention to synthetic leather. FIG. 2 is a photograph showing a conventional water repellent agent containing PFOA, Water and cola).

That is, water (72 mN / m) and cola (45 mN / m) having different surface tension are selected as external pollutants which can be easily contacted in everyday life and the surface water repellent of the present invention is subjected to water- As a result of observing the water repellency, it is possible to confirm the water repellency as in the case of treating the surface water repellent containing PFOA which is conventionally used to provide water repellency to the product surface of the conventional synthetic leather.

3 is a photograph showing the water repellency of external contaminants (water and cola) on the water repellent untreated synthetic leather without the surface water repellent. From the above results, it can be confirmed that the surface water repellent of the present invention has excellent water repellency without containing PFOA.

From the above results, the surface water repellent agent containing the fluorine-based polyurethane resin of the present invention can be obtained by using fluorine-based polyurethane resin containing fluoro alcohol having Rf group having 6 or less carbon atoms which does not contain PFOA and fluorine- It is possible to provide a synthetic leather having water repellency equal to that of an alcohol-containing surface water repellent agent.

In addition, not only the water repellency but also the water resistance and hydrolysis resistance are comparable to those of the conventional surface water repellent agent [Table 7].

Hereinafter, the present invention will be described in more detail with reference to Examples.

The present invention is intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these embodiments.

≪ Example 1 > Production of fluorinated polyurethane resin

100 g of isophorone diisocyanate (IPDI, manufactured by Bayer), 90 g of polyether type polyol PP-2000 (OH: 54 to 58 mg KOH / g, manufactured by KPX Chemical), copolymerized polycarbonate type polyol T- 120 g KOH / g, manufactured by Asahi Kasei), 0.05 g of dibutyltin dilaurate (DBTDL) and 350 g of dimethylformamide (DMF) were reacted to prepare a prepolymer. Then, CF ₃ -CF ₂ - (CF ₂ -CF ₂ ) ₂ -CH ₂ -CH ₂ -OH (perfluoroalkyl group-containing monohydric alcohol, PFOA-free C ₆ Type fluorine alcohol), 9 g of lauryl alcohol and 150 g of dimethylformamide (DMF) were added and reacted to prepare a fluorinated polyurethane resin.

Example 2: Production of fluorinated polyurethane resin

100 g of polymeric methylene diphenyl diisocyanate (Polymeric-MDI, M20S, manufactured by BASF), 37 g of polyether type polyol PP-1000 (OH value: 108 to 116 mg KOH / g, manufactured by KPX Chemical), copolymerized polycarbonate type polyol G- 117g of 3,450J (OH: 130 to 150mg KOH / g, manufactured by Asahi Kasei), 75g of dimethylformamide (DMF) and 175g of methyl ethyl ketone (MEK) were reacted to prepare a prepolymer. Then, CF ₃ -CF ₂ - (CF ₂ -CF ₂ ) ₂ -CH ₂ -CH ₂ -OH (perfluoroalkyl group-containing monohydric alcohol, PFOA-free C ₆ Type fluorinated alcohol), 20 g of stearyl alcohol, 80 g of dimethylformamide (DMF) and 40 g of methyl ethyl ketone (MEK) were added and reacted to prepare a fluorinated polyurethane resin.

Example 3: Production of fluorinated polyurethane resin

30 g of polymeric methylene diphenyl diisocyanate (Polymeric-MDI, M20S, manufactured by BASF), 70 g of toluene diisocyanate (TDI, manufactured by KPX Fine Chemical), polyether type polyol PP-400 (OH content: 265 to 295 mg KOH / g, (OH value: 51 to 61 mg KOH / g, manufactured by KPX Chemical), 4.3 g of a polyether type polyol GP-250 (OH value: 650 to 700 mgKOH / g, manufactured by KPX Chemical), 20.4 g of a copolymerized polycarbonate type polyol T- , Manufactured by Asahi Kasei), 140 g of dimethylformamide (DMF) and 320 g of methyl ethyl ketone (MEK) were reacted to prepare a prepolymer. Thereafter, CF ₃ -CF ₂ -CF ₂ -CF ₂ -SO ₂ -N (CH ₃ ) CH ₂ -CH ₂ -OH (perfluoroalkyl group-containing monohydric alcohol, PFOA-free C ₄ Type fluorinated alcohol), 4.8 g of lauryl alcohol, 120 g of dimethylformamide (DMF) and 50 g of methyl ethyl ketone (MEK) were added and reacted to prepare a fluorinated polyurethane resin.

≪ Examples 4 to 5 > Production of fluorinated polyurethane resin

A fluorinated polyurethane resin composition was prepared in the same manner as in Example 2, except that the isocyanate shown in Table 1 was used.

Examples 6 to 8 Production of fluorinated polyurethane resin

A fluorinated polyurethane resin composition was prepared in the same manner as in Example 2, except that the isocyanate and the polyol shown in Table 1 were used.

Comparative Example 1 Production of fluorinated polyurethane resin

40 g of a polyether type polyol PP-1000 (OH: 108 to 116 mg KOH / g, manufactured by KPX Chemical), 40 g of a copolymer type polycarbonate type polyol G-3450J (OH ratio: 130 , 150 g KOH / g, manufactured by Asahi Kasei), 65 g of dimethylformamide (DMF) and 150 g of methyl ethyl ketone (MEK) were reacted to prepare a prepolymer. Thereafter, 160 g of CF ₃ -CF ₂ - (CF ₂ -CF ₂ ) ₃ -CH ₂ -CH ₂ -OH (monohydric alcohol containing perfluoroalkyl group, fluoro alcohol of C ₈ type containing PFOA), 7 g of lauryl alcohol, 110 g of formamide (DMF) and 60 g of methyl ethyl ketone (MEK) were added and reacted to prepare a fluorinated polyurethane resin.

≪ Comparative Example 2 > Production of fluorinated polyurethane resin

37 g of polyether type polyol PP-1000 (OH: 108 to 116 mg KOH / g, manufactured by Asahi Kasei), 65 g of polyester type polyol JEP-1050 (OH: 106 to 118 mgKOH / g, produced by Jungwoo Fine Chemical Co., Ltd.), 70 g of dimethylformamide (DMF) and 170 g of methyl ethyl ketone (MEK) were reacted to prepare a prepolymer. Thereafter, 122 g of CF ₃ -CF ₂ - (CF ₂ -CF ₂ ) ₂ -CH ₂ -CH ₂ -OH (monohydric alcohol containing perfluoroalkyl group, fluoro alcohol of C ₆ type not containing PFOA), 7 g of lauryl alcohol, 90 g of dimethylformamide (DMF) and 35 g of methyl ethyl ketone (MEK) were added and reacted to prepare a fluorinated polyurethane resin.

≪ Comparative Examples 3 to 5 > Production of fluorinated polyurethane resin

A fluorinated polyurethane resin was prepared in the same manner as in Comparative Example 2, except that the polyol shown in Table 2 was used.

Example 9 Synthesis of Synthetic Leather

The PE nonwoven fabric was wet-impregnated with the prescription liquid shown in Table 3 below to prepare a synthetic leather specimen.

Thereafter, the synthetic leather specimen was subjected to a secondary coating treatment with the prescription liquid shown in Table 4 below to prepare a synthetic leather.

≪ Experimental Example 1 > Property evaluation

The water repellency, water resistance and hydrolysis resistance of each of the synthetic leathers subjected to the surface water repellent treatment were measured by the wet process method using the fluorinated polyurethane resin compositions prepared in Examples 1 to 8 and compared and evaluated.

1. Water repellency test

The water repellency was measured by the water repellency No. according to the AATCC-118 method. (See Table 5 below). The water repellency test was conducted under constant temperature and humidity conditions at a temperature of 23 ° C and a humidity of 50%. The test solution composed of the mixture of isopropyl alcohol (IPA) and water described in Table 5 was also stored at 23 ° C.

The test liquid was slowly dropped by 0.5 ml onto the synthetic leather specimen prepared by the impregnation process and allowed to stand for 60 seconds. When the droplet remained on the test specimen without being infiltrated or wetted, the test liquid was regarded as passing.

The water repellency was rated by evaluating the maximum isopropyl alcohol (IPA) content of the test liquid passed. At this time, the water repellency was evaluated in six levels of grade 1, 2, 3, 4, 5, and 6. The higher the number, the better the water repellency.

2. Water resistance test

The water resistance test was carried out under constant temperature and humidity conditions at a temperature of 23 ° C and a humidity of 50%. The test liquid (diluted with 0.5% dispersion dye) was also stored at 23 ° C.

The synthetic leather specimens prepared by the impregnation process were prepared in a size of 4 cm × 16 cm. The specimens prepared in the colored test liquid were immersed in a vertical 1 cm dipping state for 30 minutes, and then the height of the specimen was measured. The water resistance is judged to be better as the height at which the test solution penetrated is lower.

3. Hydrolysis test

The hydrolysis resistance test was carried out under constant temperature and humidity conditions of 23 ° C and 5% humidity, and the test solution (NaOH 10% alkali solution) was also stored at 23 ° C.

The synthetic leather specimens prepared by the impregnation process and the coating process were prepared in a size of 6 cm × 6 cm in size, immersed in an alkali test solution, allowed to stand for 24 hours, and then the specimens were taken out and washed (washed) Were measured.

The change in the state of the surface was judged by the following Table 6, and the hydrolysis resistance was indicated by No. (grade) after confirming the surface state by the following Table 6. The hydrolysis resistance was evaluated in five stages of grade 1, 2, 3, 4, and 5, and the lower the number (grade), the better the hydrolysis resistance.

4. Perfluorooctanoic acid (PFOA) Harmfulness

Each of the fluorinated polyurethane resin compositions prepared in Examples 1 to 8 was analyzed by LC / MS / MS quantitative analysis to determine the content and content of PFOA.

The results of evaluation of the physical properties of the synthetic leather using the respective fluorinated polyurethane resin compositions prepared in Examples 1 to 8 as surface water repellent agents are shown in Table 7 below and the fluorinated polyurethane resin prepared in Comparative Examples 1 to 5 The evaluation results of the physical properties of the synthetic leather using the composition are shown in Table 8.

From the evaluation results of the physical properties shown in Tables 7 and 8, it can be seen that each of the fluorinated polyurethane resin compositions prepared in Examples 1 to 8 is an environmentally friendly composition containing no PFOA component, and in the case of synthetic leather using the same, , And excellent results were obtained in all properties evaluation of hydrolysis resistance.

As described above, the present invention provides an environmentally friendly fluorinated polyurethane resin composition having a composition containing a copolymerized polycarbonate polyol component, using a fluoro alcohol having an Rf group of 6 or less carbon atoms.

The environmentally friendly fluorinated polyurethane resin composition of the present invention uses fluoroalcohol having a polyfluoroalkyl group (Rf group) having not more than 6 carbon atoms and does not contain perfluorooctanoic acid (PFOA) And water repellency and hydrolysis resistance comparable to or superior to those in the case of using the fluorinated polyurethane resin obtained by incorporating PFOA in the prior art.

Furthermore, the present invention can be applied to water-repellent treatment on various substrates including synthetic leather by providing a surface wicking agent in the form of a solution containing a fluorinated polyurethane resin obtained from an environmentally friendly fluorinated polyurethane resin composition.

While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (15)

(A) for aliphatic or aromatic diisocyanate components,
(B) a polyhydric polyol containing a copolymerized polycarbonate polyol component and
(C) a monofunctional alcohol component containing a perfluoroalkyl group having 1 to 6 carbon atoms (Rf group). The process according to claim 1, wherein the monohydric alcohol is composed of a fluorine-containing alcohol (a) having an Rf group having 1 to 6 carbon atoms and a fluorine-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms. Type fluorinated polyurethane resin composition. The fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms and the fluorine-free aliphatic alcohol (b) having an alkyl group having a carbon number of 8 to 22 in a weight ratio of 99: 1 to 50:50 Wherein the fluorine-containing polyurethane resin is a fluorine-containing polyurethane resin. The environmentally friendly fluorinated polyurethane resin composition according to claim 2, wherein the fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms is any one selected from the following (1) to (6)

In the above, Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms. The fluorine-free aliphatic alcohol (b) as claimed in claim 2, wherein the fluorine-free aliphatic alcohol (b) having an alkyl group of 8 to 22 carbon atoms is at least one selected from the group consisting of octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, Wherein the fluorinated polyurethane resin is any one selected from the group consisting of dicyclohexyl alcohol, dicyclohexyl alcohol, diallyl alcohol, and biphenyl alcohol. The polyol as claimed in claim 1, A polyether polyol, a polyester polyol, a polyester polyol, a polyester polyol or a polyester polyol. The process according to claim 1, wherein the copolymerized polycarbonate polyol is a polycarbonate diol obtained by copolymerizing 1,6-hexanediol with 1,5-pentanediol, a polycarbonate obtained by copolymerizing 1,6-hexanediol and 1,4- Diol, a polycarbonate diol in which 1,3-propanediol and 1,5-pentanediol are copolymerized, and a polycarbonate diol in which 1,3-propanediol and 1,4-butanediol are copolymerized Wherein the fluorine-containing polyurethane resin is a fluorine-containing polyurethane resin. A surface water repellent agent containing a fluorinated polyurethane resin represented by the following formula (1):
Formula 1

In Formula 1,
R _{1 is a} monovalent alcohol group containing an alkyl group-containing fluorine alcohol (a) having 1 to 6 carbon atoms and a fluorine atom-free aliphatic alcohol (b) having an alkyl group having 8 to 22 carbon atoms,
R ₂ : an aliphatic or aromatic diisocyanate residue,
R ₃ is a polyvalent polyol containing a copolymerized polycarbonate polyol. The surface water repellent according to claim 8, wherein the fluoropolyurethane resin is in a solution phase containing 20 to 80 wt%. The fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms and the fluorine-free aliphatic alcohol (b) having an alkyl group having a carbon number of 8 to 22 in a weight ratio of 99: 1 to 50:50 Wherein the water repellent agent is a water repellent agent. The surface water repellent according to claim 10, wherein the fluorine-containing alcohol (a) having an Rf group of 1 to 6 carbon atoms is any one selected from the following (1) to (6)

In the above, Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms. The fluorine-free aliphatic alcohol (b) having an alkyl group with a carbon number of 8 to 22 as recited in claim 10, Wherein the water-repellent agent is any one selected from the group consisting of diallyl alcohol and biphenyl alcohol. The surface water repellent agent according to claim 8, wherein the surface water repellent agent is water repellent on the surface of the substrate by wet processing or dry processing. 14. The surface water repellent agent according to claim 13, wherein the substrate is synthetic leather or fiber. The surface water repellent agent according to claim 13, wherein the substrate is any one selected from the group consisting of stone, glass, paper, wood, brick, cement and plastic.

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