KR20190059557A - Water-repellent Coating Composition for Synthetic Leather and Water-repellent Synthetic Leather Using the Same - Google Patents

Abstract

The present invention relates to a water repellent coating composition for synthetic leather and a water repellent synthetic leather using the same. More particularly, the present invention relates to a water repellent coating composition for synthetic leather which is excellent in film forming ability when coated on synthetic leather, has no deterioration in peel strength, Water-repellent coating composition and a water-repellent synthetic leather product using the same.

Description

Technical Field [0001] The present invention relates to a water-repellent coating composition for synthetic leather and a water-repellent synthetic leather product using the same,

The present invention relates to a water-repellent coating composition for synthetic leather and a water-repellent synthetic leather product using the same. More particularly, the present invention relates to a water-repellent coating composition for synthetic leather, which is excellent in film forming ability when coated on synthetic leather, wicking properties and a water repellent synthetic leather product using the water repellent coating composition.

Background Art [0002] Leather-like sheets such as synthetic leather have excellent tactile feel comparable to natural leather and are therefore used in various fields such as medical care (apparel), furniture, automobile interior materials, shoes, bags and the like.

As the leather-like sheet, in general, an intermediate layer such as a porous layer is laminated on the surface of a support such as a fibrous substrate and the like, and in many cases, a skin layer made of urethane resin or the like is laminated on the surface thereof. Is required. Specifically, the intermediate layer is required to have a soft touch and the like, and the skin layer is often required to have durability such as water resistance in addition to the above flexibility. Particularly, in the skin layer, Even when rainwater or the like is adhered, a high level of water resistance that does not cause discoloration or the like on the surface of the leather-like sheet is required.

Japanese Patent Laid-Open Nos. 1985-239573, 1985-252780 and Korean Patent No. 0969839 disclose a method for producing a leather-like sheet such as artificial leather to improve water resistance and water repellency, A method of adding a fluorine-containing urethane compound as a water-repellent agent to a polymeric elastomer solution and coagulating is disclosed.

The fluorine-containing urethane compound disclosed in these publications is an addition reaction product of a urethane prepolymer having an isocyanate group at the terminal and a perfluoroalkyl group-containing compound having an active hydrogen group. However, the perfluoroalkyl group-containing compound is preferably a perfluoroalkyl group having 6 to 12 carbon atoms in which -SO ₂ NH ₂ or -SO ₂ -N (R) -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n OH Wherein R is an alkyl group having 1 to 3 carbon atoms and n is 0 or a positive integer of 1 to 20). Recently, however, these sulfonamide group-containing perfluoroalkyl compounds have been widely used There is a problem that a burden material may be generated, and it is being regulated, and such monomers are not economical because they are expensive.

For this reason, the development of a material capable of imparting excellent water resistance and the like without using a fluorinated compound is required by the industry, but it is possible to exhibit a water repellency performance comparable to that of a conventional fluorinated compound-containing composition, A material capable of imparting excellent water resistance to the skin layer of the present invention has not been found.

Japanese Laid-Open Patent No. 1985-239573 (published on November 28, 1985) Japanese Patent Laid-Open No. 1985-252780 (published on Dec. 13, 1985) Korean Patent No. 0969839 (published on March 15, 2005)

The main object of the present invention is to provide a non-fluorine-based water repellent coating composition having excellent film-forming ability, high peel strength, sufficient durability and wicking property when coated on synthetic leather, .

The present invention also provides a method for producing a water-repellent synthetic leather product produced using the water-repellent coating composition and a water-repellent synthetic leather product produced by the method.

In order to achieve the above object, an embodiment of the present invention is a water repellent coating composition of synthetic leather comprising at least components (A), (B) and (C), wherein the component (A) (A1) selected from (meth) acrylic acid esters having a molecular weight of 16 to 22 and mixtures thereof; And a halogen-containing alkene monomer (a2) selected from a mixture of alkenes having 2 to 10 carbon atoms and at least one halogen atom bonded to a vinyl group, and mixtures thereof; and the component (B) is a copolymerized non- Is a nonionic surfactant having a hydrophile-lipophile balance (HLB) of 7 to 19, wherein the component (C) is water and the component (A) (A2) in an amount of 10 wt% to 60 wt%, based on the total weight of the water-repellent coating composition.

In a preferred embodiment of the present invention, the component (A) comprises 55 wt% to 75 wt% of component (a1) and 25 wt% to 45 wt% of component (a2), based on the total weight of the non- .

In one preferred embodiment of the invention, the water repellent coating composition of synthetic leather comprises 5 wt% to 30 wt% of component (A), 1 wt% to 20 wt% of component (B) and 55 wt% to 80 wt% based on the total weight of the composition.

In a preferred embodiment of the present invention, the component (a1) may have a cetyl (meth) acrylate ester having 16 carbon atoms in an amount of 70 wt% or more based on the total weight of the ester monomer (a1).

In a preferred embodiment of the present invention, the component (a2) may be characterized by being vinyl chloride or vinylidine chloride.

In a preferred embodiment of the present invention, the component (B) may be a surfactant containing a polyoxyalkylene group.

Another embodiment of the present invention is directed to a method of making a waterproof coating composition comprising: (i) mixing a water repellent coating composition of the synthetic leather and a crosslinking agent; And (ii) coating the mixture on the surface of the artificial leather.

In another preferred embodiment of the present invention, the crosslinking agent may be characterized in that it comprises a compound having a block isocyanate group.

Another embodiment of the present invention provides a water repellent synthetic leather product made by the above-described method.

The water repellent coating composition according to the present invention uses a polymer obtained by polymerizing vinyl chloride or vinylidene chloride with an ester monomer having a specific range of the content of ester having a specific value of the number of carbon atoms in the ester moiety, By adding a nonionic surfactant with controlled HLB value, it is possible to produce a synthetic leather product which is excellent in film forming ability when coated on synthetic leather, has no problem in peel strength, exhibits sufficient endurance repellency and wicking property .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In the present invention, '(meth) acrylic acid ester' means an acrylic acid ester or a methacrylic acid ester or a mixture thereof. That is, '(meth) acrylic acid ester' should be understood to mean a single component of an acrylic acid ester compound or a single component of a methacrylic acid ester compound or a mixed component of the acrylic acid ester compound and a methacrylic acid ester compound, Acrylic acid amide 'should be interpreted in the same sense.

The present invention relates to a water repellent coating composition of synthetic leather comprising at least components (A), (B) and (C), wherein said component (A) is a (meth) acrylic acid ester having 16 to 22 carbon atoms in the ester moiety, Ester monomer (a1) selected from mixtures; And a halogen-containing alkene monomer (a2) selected from a mixture of alkenes having 2 to 10 carbon atoms and at least one halogen atom bonded to a vinyl group, and mixtures thereof; and the component (B) is a copolymerized non- Is a nonionic surfactant having a hydrophile-lipophile balance (HLB) of 7 to 19, wherein the component (C) is water and the component (A) (A2) in an amount of 10 wt% to 60 wt%, based on the total weight of the composition.

That is, the water repellent coating composition of the present invention comprises a (meth) acrylic acid ester monomer (component (a1)) having a specific range of carbon number of the ester moiety [component (a1)] and an alkene having 2 to 10 carbon atoms (component (B)] in which the HLB value is adjusted to the non-fluorine-based polymer [component (A)] obtained by copolymerizing the component (a2) It is possible to provide a synthetic leather product exhibiting excellent film-forming ability, high peel strength, sufficient durability in water repellency and wicking property when it is coated on synthetic leather.

The component (A) in the present invention is a copolymerized non-fluorine-based polymer which is coated on a synthetic leather product and imparts durability to water repellency, wicking property and the like, and a (meth) acrylic acid ester having 16 to 22 carbon atoms in the ester moiety, And a halogen-containing alkene monomer (a2) selected from an alkene monomer having 2 to 10 carbon atoms in which at least one halogen atom is bonded to a vinyl group and a mixture thereof, as monomer units, Is a non-fluorine-based polymer.

The component (a1) is selected from (meth) acrylic acid ester monomers and mixtures thereof, and the alcohol-derived portion of the ester is preferably a hydrocarbon group having from 16 to 22 carbon atoms, and the hydrocarbon group may be linear or branched, Saturated hydrocarbon or unsaturated hydrocarbon, and may be aliphatic cyclic or aromatic cyclic.

For example, the component (a1) may be selected from cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate, isostearyl acrylate, isostearyl methacrylate, oleyl acrylate, oleyl methacrylate, Behenyl, behenyl methacrylate, and mixtures thereof.

If the number of carbon atoms in the alcohol-derived portion of the (meth) acrylic acid ester monomer according to the present invention is less than 16, sufficient water repellency can not be exhibited when the water-repellent coating composition is adhered to a synthetic leather product or the like. Acrylic acid ester monomer having a carbon number of 16 to 22 in the remaining part except for the (meth) acrylic acid part can be used. In addition, It may preferably have a carbon number of 16 to 20, and most preferably have a carbon number of 16 to 18, and in particular, a cetyl (meth) acrylate having a carbon number of 16 may be used.

The component (a1) may contain 40 wt% to 90 wt%, preferably 50 wt% to 80 wt%, and more preferably 55 wt% to 75 wt%, based on the total weight of the non-fluorinated polymer have. If the content of the component (a1) is less than 40 wt% based on the total weight of the non-fluorinated polymer, the water repellency or wicking property of the synthetic leather product coated with the water repellent coating composition may not be sufficient, The water repellency and wicking property may be lowered due to lack of base adhesion of the synthesized non-fluoropolymer.

The content of the component (a1) may be 70 wt% or more, and preferably 85 wt%, based on the content of the ester monomer (a1), the cetyl (meth) acrylate having 16 carbon atoms. At this time, when the content of the cetyl (meth) acrylic acid ester having 16 carbon atoms in the ester monomer in the component (a1) is high, the film forming ability is excellent and the film can have a good wicking property.

On the other hand, the component (a2) is selected from alkene monomers having 2 to 10 carbon atoms in which at least one halogen atom is bonded to a vinyl group, and mixtures thereof, and the halogen-containing alkene monomer may be alkene represented by the following formula (A).

(A)

In the above formula A, the substituents X, Y and Z may be the same or different and are each independently selected from the group consisting of hydrogen, deuterium or halogen selected from F, Cl, Br and I, and at least one of the substituents X, Y and Z Is a halogen selected from F, Cl, Br and I, and R is a substituent selected from hydrogen, deuterium, and straight-chain or branched alkyl groups having 1 to 8 carbon atoms.

The alkene having 2 to 10 carbon atoms represented by the above formula (A) may be an alkene having 2 to 5 carbon atoms in which at least one halogen atom is bonded, preferably a vinyl chloride or vinylidene chloride as a commercially available monomer. Chloride can be used.

At this time, the component (a2) may contain 10 wt% to 60 wt%, preferably 20 wt% to 50 wt%, more preferably 25 wt% to 45 wt%, based on the total weight of the non- have. If the content of the component (a2) is less than 10 wt% based on the total weight of the non-fluorinated polymer, the water repellency or wicking property of the synthetic leather product coated with the water repellent coating composition may not be sufficient, The water repellency and the wicking property may be lowered due to the lack of the base adhesion of the synthesized non-fluoropolymer.

The non-fluorinated polymer obtained by copolymerizing the component (a1) and the component (a2) may have a water repellency and a stain If the content of the water-repellent coating composition is more than 30 wt%, the resulting non-fluorine water-repellent agent may have difficulty in commercialization due to poor appearance and emulsion stability, , 5 wt% to 30 wt%, preferably 10 wt% to 30 wt%.

On the other hand, the component (B) is for improving the dispersion stability of the water-repellent coating composition, and includes polyoxyalkylene straight chain alkyl ether, polyoxyalkylene branched decyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkyl phenyl It may be preferable to use a nonionic surfactant containing a polyoxyalkylene group such as an ether, a polyoxyalkylene alkylarylphenyl ether, or a polyoxyalkylene fatty acid ester, and the amphoteric surfactant may be water ), The hydrophile lipophile balance (HLB) may be 7.0 to 19.0, preferably 7.9 to 18.3 in terms of the emulsifying and dispersing power and the dispersion stability of the composition after polymerization.

If the HLB value of the component (B) is less than 7.0, the hydrophilic property is insufficient and the O / W type emulsion is not stable, so that the emulsion polymerization is not performed well and the stability of the product emulsion after polymerization deteriorates, May be generated. If it exceeds 19.0, the water repellency does not greatly affect the water repellency. However, there may be a problem that the wicking property is deteriorated due to the hydrophilic surfactant remaining on the substrate to be treated.

The HLB value is a value indicating the degree of affinity to water and oil as a proposed concept in accordance with a demand for finding a dispersant suitable for the purpose of use because there are many kinds of surfactants. The HLB value ranges from 0 to 20, The lipophilic property is better, and the closer to 20, the better the hydrophilic property.

The component (B) may comprise 1 wt% to 20 wt%, preferably 1 wt% to 10 wt%, based on the total weight of the water repellent coating composition. If the content of the component (B) is less than 1 wt% based on the total weight of the water-repellent coating composition, the dispersion stability of the water-repellent coating composition may deteriorate, resulting in poor appearance and performance during polymerization. If it exceeds 20 wt%, the wicking property or durability of the water repellent coating composition may be deteriorated due to an excess amount of the surfactant.

Component (C) is a polymerization medium, typically water, which may be included in an amount of 55 wt% to 80 wt%, preferably 60 wt% to 80 wt%, based on the total weight of the water repellent coating composition. When the content of the component (C) is less than 55 wt% based on the total weight of the water-repellent coating composition, the O / W type emulsion polymerization is not possible because the proportion of the polymerization medium is low, The reaction rate is slow not only due to the low concentration of the coating composition but also has a different molecular weight distribution from that of the intended coating composition, resulting in the problem that the performance is not developed.

In addition, the water repellent coating composition of the present invention may further comprise at least one selected from organic solvents, initiators, chain transfer agents, emulsifying agents and additives as needed during the polymerization, Known additives may be included in the composition so as not to change the properties of the composition. Examples of the additive include an antimicrobial agent, a deodorant, a flame retardant, an antistatic agent, a softening agent, an emulsifying stabilizer and the like.

The organic solvent is not particularly limited as long as it is an organic solvent compatible with water, and examples thereof include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methine ethyl ketone, ethers such as diethyl ether Propylene glycol, dipropylene glycol, tripropylene glycol and the like, and the ratio of water to organic solvent is not particularly limited.

The initiator may be selected from known polymerization initiators such as azo type, peroxide type, and redox type. The content of the initiator may be determined in consideration of the molecular weight of the polymer to be polymerized, May range from 0.1 to 10 per 100 parts by weight of the non-fluorine-based polymer.

The chain transfer agent may be dodecylmercaptan, t-butyl alcohol or the like for the purpose of adjusting the molecular weight in the polymerization reaction, and the content thereof is preferably 5 parts by weight or less based on 100 parts by weight of the non-fluorinated polymer. If the content of the chain transfer agent is more than 5 parts by weight, the reduction of the molecular weight becomes serious, and it may be difficult to efficiently produce a non-fluorinated polymer having a weight average molecular weight of 100,000 g / mol or more. A polymerization inhibitor may be used for the purpose of adjusting the molecular weight. By adding the polymerization inhibitor, a non-fluorine-based polymer having a desired molecular weight can be easily obtained.

For the purpose of further improving the dispersion stability, the emulsifying aid may be a known emulsifying aid such as stearyldimethylamine hydrochloride, stearyltrimethylamine hydrochloride, etc. The content of the emulsifying aid may be, for example, It is preferably 10 parts by weight or less based on 100 parts by weight of the non-fluorine-containing polymer from the viewpoint of stabilizing the dispersion state of the composition.

The water-repellent coating composition according to the present invention may be prepared by preparing a mixed solution containing a non-fluorine-based polymer, a non-ionic surfactant, water, an initiator, an additive and the like and then dispersing the mixture in a known dispersing means such as a homomixer, , Ultrasonic dispersion or the like and dispersed and polymerized to prepare a water repellent coating composition of a synthetic leather according to the present invention.

When the polymerization temperature is lower than 50 ° C, the polymerization is insufficient. When the polymerization temperature is higher than 80 ° C, the radicals do not proceed as intended due to destruction of the radicals or emulsion breakage due to high temperature conditions It is difficult.

The water repellent coating composition of synthetic leather according to the present invention provides a non-fluorine-based water repellent coating composition having excellent film-forming ability, peel strength, and sufficient durability and wicking property when coated on synthetic leather .

The present invention also provides a method of making a waterproof coating composition comprising: (i) mixing a water repellent coating composition of the synthetic leather and a crosslinking agent; And (ii) coating the mixture on the surface of the artificial leather.

In more detail, as a first step, a cross-linking agent is mixed in the above-described water-repellent coating composition of synthetic leather [step (i)].

The crosslinking agent is used to improve the adhesion between the synthetic leather product and the water repellent coating composition by curing the water repellent coating composition applied to the synthetic leather product. The crosslinking agent may be used in an amount of 5 to 25 parts by weight based on 100 parts by weight of the water repellent coating composition . When the crosslinking agent is used in an amount of less than 5 parts by weight based on 100 parts by weight of the water-repellent coating composition, adhesion between the synthetic leather product and the water-repellent coating composition is poor, and water repellency and wicking property are deteriorated When the amount of the cross-linking agent is more than 25 parts by weight, hydrophilic properties of the unbonded portion of the cross-linking agent may deteriorate the water repellency and wicking property of the cross-linking agent, have.

The cross-linking agent may be selected from known cross-linking agents and may be selected from compounds having a block isocyanate group or an isocyanate group in view of the durability and adhesion of a synthetic leather product, preferably a MEK oxime block isocyanate group or pyrazole A block isocyanate group or a compound having an isocyanate group.

Meanwhile, in the method for producing a water-repellent synthetic leather product according to the present invention, at the time of mixing the water-repellent coating composition of the synthetic leather with the crosslinking agent, one or more selected from the group consisting of a softener, a penetrating agent and an antistatic agent may be further mixed.

As the softening agent, any known softening agent can be used without limitation as long as it softens the feel of the synthetic leather product and does not cause deterioration of the water repellency. The softening agent may be selected from the group consisting of dimethyl silicone, hydrogen silicone, amino modified silicone, fatty acid amide, Etc. may be used. The softener may be used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the water-repellent coating composition.

In addition, the penetrating agent can be used without limitation as long as it is a known penetrating agent for the purpose of allowing the water-repellent coating composition to permeate into the interior of a thick material which is difficult to penetrate into the high-density synthetic leather, and preferably, Glycol solvents such as butyl diglycol and monoethylene glycol, alcohol solvents such as isopropyl alcohol, butyl cellosolve, and higher alcohol type and lower alcohol type solvents may be used. As the content of the penetrating agent, 100 parts by weight 0.5 part by weight to 10 parts by weight based on 100 parts by weight of the resin.

As the antistatic agent, any known antistatic agent can be used without limitation, and preferably stearylalkyl trimethylammonium methosulfite, laurylalkyltriethylaminoethosulfate, octylalkyltrimethylamino chloride, stearyltrimethylammonium chloride , Stearyldimethylammonium chloride, lauryltrimethylammonium chloride, phosphoric acid ester compounds, guanidine hydrochloride compounds, etc. The antistatic agent content is preferably 0.5 wt% or less based on 100 wt% of the water repellent coating composition To 5 parts by weight.

As the process after the step (i), a mixture of the water repellent coating composition and the crosslinking agent is coated on the synthetic leather product as described above (step (ii)). At this time, the amount to be coated can be easily adjusted depending on the degree of water repellency required. Usually, the amount of the mixture is adjusted in the range of 1.5 to 10 parts by weight. When the coating amount is less than 1.5 parts by weight, the water repellency of the synthetic leather product is not sufficient. When the coating amount exceeds 10 parts by weight, the properties of the raw material may be lost.

The synthetic leather product may be coated by a known method such as dipping, spraying, spraying, or coating. The synthetic leather product to which the water-repellent coating composition has been applied by drying, curing (curing) Can be obtained.

On the other hand, after coating the water repellent coating composition, it can be selectively cured by using heat treatment or the like, and there is no particular limitation on the temperature condition of the heat treatment. In general, for sufficient reaction of the crosslinking agent, It can be carried out for 20 minutes.

The present invention can also provide a water repellent synthetic leather product made by the manufacturing method described in steps (i) and (ii) described above.

The water repellent synthetic leather product thus obtained can exhibit sufficient water repellency even when it is used outdoors for a long period of time, and the water repellent synthetic leather product is environment-friendly because it does not use a fluorine compound, and the peeling between the synthetic leather and the adhesive The strength is not lowered, the adhesive strength is excellent, and sufficient water repellency and wicking property can be exhibited.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for illustrating the present invention, and thus the scope of the present invention should not be construed as being limited by these embodiments.

< Manufacturing example  1>

The component (a1), the component (B), the emulsifying auxiliary agent, the solvent, the chain transfer agent and the component (C) described in the following Table 1 were mixed and stirred in an autoclave and then emulsified and dispersed by ultrasonic waves at 65 占 폚 for several minutes. After replacing the inside of the autoclave with nitrogen, the reactor was sealed and then the component (a2) and azobis (amidine propane) dihydrochloride were added. And then reacted at 60 DEG C for 4 hours to obtain a water repellent coating composition of synthetic leather. The content of each of the above components is as shown in Table 1. At this time, most of the components in Table 1 are generally available, among which glycidyl methacrylate is Mitsubishi Rayon, dodecyl mercaptan is Cebron Phillips Chemical International, and azobis (amidine propane) dihydrochloride is Dupont products were used.

< Manufacturing example  2 to 6>

A water repellent coating composition was prepared in the same manner as in Production Example 1, except that the components and the contents shown in Table 1 below were used.

division Production Example 1
(weight%) Production Example 2
(weight%) Production Example 3
(weight%) Production Example 4
(weight%) Production Example 5
(weight%) Production Example 6
(weight%) Component (a1)



Cetyl acrylate 15.0 15.0 15.0 15.0 13.3 18.3 Stearyl acrylate - - - - 1.7 - Lauryl acrylate - - - - - - Behenyl acrylate - - - - - - Styrene - - - - - - Component (a2)

Vinyl chloride 10.0 10.0 10.0 10.0 10.0 6.7 Glycidyl methacrylate - - - - - - 2-hydroxyethyl acrylate - - - - - - Component (B)





Polyoxyalkylene branched alkyl ether (HLB: 10.5) 1.7 1.7 1.7 - 1.7 1.7 Polyoxyalkylene branched alkyl ether (HLB: 12.5) 0.3 0.3 0.3 - 0.3 0.3 Polyoxyalkylene branched alkyl ether (HLB: 14.0) 0.3 0.3 0.3 - 0.3 0.3 Polyoxyalkylene branched decyl ether (HLB: 14.7) - - - 1.0 - - Polyoxyalkylene branched decyl ether (HLB: 18.3) - - - 1.0 - - Polyoxyalkylene branched oleyl ether (HLB: 7.9) - - - 0.3 - - The polyoxyalkylene branched alkyl ether (HLB: 7.3) - - - - - - Emulsifying agent
Stearyldimethylamine hydrochloride - 1.0 1.0 - - - Glycolic acid - - 0.2 - - - Organic solvent Tripropylene glycol 8.0 8.0 8.0 8.0 8.0 8.0 Chain transfer agent Dodecyl mercaptan 0.1 0.1 0.1 0.1 0.1 0.1 Component (C) water 64.3 63.3 63.1 64.3 64.3 64.3 Initiator Azobis (amidine propane) dihydrochloride 0.3 0.3 0.3 0.3 0.3 0.3

< Manufacturing example  7 to 12>

A water repellent coating composition was prepared in the same manner as in Production Example 1 except that the components and the contents shown in Table 2 were used.

division Production Example 7
(weight%) Production Example 8
(weight%) Production Example 9
(weight%) Production Example 10
(weight%) Production Example 11
(weight%) Production Example 12
(weight%) Component (a1)



Cetyl acrylate 13.3 13.3 13.3 13.3 13.3 11 Stearyl acrylate - - 1.7 1.7 14 Lauryl acrylate 1.7 - - - - - Behenyl acrylate - 1.7 - - - - Styrene - - - - - - Component (a2)

Vinyl chloride 10.0 10.0 10.0 10.0 11.7 10.0 Glycidyl methacrylate - - - - - - 2-hydroxyethyl acrylate - - - - - - Component (B)





Polyoxyalkylene branched alkyl ether (HLB: 10.5) 1.7 1.7 1.7 1.7 1.7 1.7 Polyoxyalkylene branched alkyl ether (HLB: 12.5) 0.3 0.3 0.3 0.3 0.3 0.3 Polyoxyalkylene branched alkyl ether (HLB: 14.0) 0.3 0.3 0.3 0.3 0.3 0.3 Polyoxyalkylene branched decyl ether (HLB: 14.7) - - - - - - Polyoxyalkylene branched decyl ether (HLB: 18.3) - - - - - - Polyoxyalkylene branched oleyl ether (HLB: 7.9) - - - - - - The polyoxyalkylene branched alkyl ether (HLB: 7.3) - - - - - - oil paint
Supplements
Stearyldimethylamine hydrochloride - - 1.0 1.0 - - Glycolic acid - - - 0.2 - - Organic solvent Tripropylene glycol 8.0 8.0 8.0 8.0 8.0 8.0 Chain transfer agent Dodecyl mercaptan 0.1 0.1 0.1 0.1 0.1 0.1 Component (C) water 64.3 64.3 63.3 63.1 64.3 64.3 Initiator Azobis (amidine propane) dihydrochloride 0.3 0.3 0.3 0.3 0.3 0.3

< Comparative Manufacturing Example  1 to 4>

A water repellent coating composition was prepared in the same manner as in Production Example 1 except that the components and the contents shown in Table 3 were used.

division
Comparative Preparation Example 1
(weight%) Comparative Production Example 2
(weight%) Comparative Production Example 3
(weight%) Comparative Production Example 4
(weight%) Component (a1)



Cetyl acrylate 25.0 9 23 3.9 Stearyl acrylate - - - - Lauryl acrylate - - - - Behenyl acrylate - - - - Styrene - - - - Component (a2)

Vinyl chloride - 16 2 1.0 Glycidyl methacrylate - - - - 2-hydroxyethyl acrylate - - - - Component (B)





Polyoxyalkylene branched alkyl ether (HLB: 10.5) 1.7 1.7 1.7 1.7 Polyoxyalkylene branched alkyl ether (HLB: 12.5) 0.3 0.3 0.3 0.3 Polyoxyalkylene branched alkyl ether (HLB: 14.0) 0.3 0.3 0.3 0.3 Polyoxyalkylene branched decyl ether (HLB: 14.7) - - - - Polyoxyalkylene branched decyl ether (HLB: 18.3) - - - - Polyoxyalkylene branched oleyl ether (HLB: 7.9) - - - - The polyoxyalkylene branched alkyl ether (HLB: 7.3) - - - - oil paint
Supplements Stearyldimethylamine hydrochloride - - - - Glycolic acid - - - - Organic solvent Tripropylene glycol 8.0 8.0 8.0 8.0 Chain transfer agent Dodecyl mercaptan 0.1 0.1 0.1 0.1 Component (C) water 64.3 64.3 64.3 85.6 Initiator Azobis (amidine propane) dihydrochloride 0.3 0.3 0.3 0.3

< Example  1 to 14 and Comparative Example  1 to 4>

The components and contents described in Table 4 below were mixed and then immersed in a PET Tricot suede of A4 size. At this time, the pick up was treated at a pressure of 1.2 Kg / cm ² at about 60%, and then cured at 150 ° C for 10 minutes without drying.

As the crosslinking agent used, NK ASSIST FU (aromatic isocyanate type) of Nikaka Chemical Co., Ltd., and NK ASSIST NY-30 (linear diisocyanate type) of Nikka Chemical Co., Ltd. were used as the isocyanate MEK oxime block. , And an isocyanate-based nonblocking agent was Aldrich's reagent (linear diisocyanate-based).

The wicking properties of the synthetic leather prepared in Examples 1 to 14 and Comparative Examples 1 to 4 were measured and are shown in Table 4 below. The wicking property measurement was carried out in the same manner as in Examples 1 to 14 and Comparative Examples 1 to 4 except that a non-fluorine water repellent treated fabric was prepared in a size of 25 mm x 60 mm, followed by treatment with a bally penetrometer, followed by drying for one day. The dried fabric was immersed in a solution of a water-soluble ink (dissolved in a dye to confirm the ascension of water) for 2 hours, and then taken out to measure the height of the water rises.

division
Water repellent coating composition Type and content (g)
Crosslinking agent (g) Wickedness
Measurement (mm) Isocyanate-based MEK oxime block Isocyanate-based pyrazole block Isocyanate-based non-block Example 1 Preparation Example 1: 10 g 1.0 - - One Example 2 Production Example 2: 10 g 1.0 - - 2 Example 3 Production Example 3: 10 g 1.0 - - 4 Example 4 Production Example 4: 10 g 1.0 - - 6 Example 5 Production Example 5: 10 g 1.0 - - 6 Example 6 Production Example 6: 10 g 1.0 - - 3 Example 7 Production Example 7: 10 g 1.0 - - 4 Example 8 Production Example 8: 10 g 1.0 - - 5 Example 9 Production Example 9: 10 g 1.0 - - 4 Example 10 Production Example 10: 10 g 1.0 - - 5 Example 11 Production Example 11: 10 g 1.0 - - 11 Example 12 Production Example 12: 10 g 1.0 - - 13 Example 13 Preparation Example 1: 10 g - 1.0 - 2 Example 14 Preparation Example 1: 10 g - - 1.0 0 Comparative Example 1 Comparative Preparation Example 1: 10 g 1.0 - - 35 Comparative Example 2 Comparative Preparation Example 2: 10 g 1.0 - - 50 Comparative Example 3 Comparative Preparation Example 3: 10 g 1.0 - - 50 Comparative Example 4 Comparative Preparation Example 4: 10 g 1.0 - - 50

As shown in Table 4, it can be seen that Examples 1 to 14 can provide a synthetic leather product having superior wicking properties than Comparative Examples 1 to 4.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

A water repellent coating composition of synthetic leather comprising at least components (A), (B) and (C)
The component (A) is an ester monomer (a1) selected from (meth) acrylic acid esters having a carbon number of 16 to 22 in the ester moiety and a mixture thereof; And a halogen-containing alkene monomer (a2) selected from a mixture of alkenes having 2 to 10 carbon atoms and a mixture of at least one halogen atom with a vinyl group and a mixture thereof, as non-fluorinated polymers,
The component (B) is a nonionic surfactant having a hydrophile-lipophile balance (HLB) of 7 to 19,
The component (C) is water,
Wherein the component (A) comprises 40 wt% to 90 wt% of component (a1) and 10 wt% to 60 wt% of component (a2), based on the total weight of the non-fluorinated polymer Composition.
The method according to claim 1,
Wherein the component (A) comprises 55 wt% to 75 wt% of component (a1) and 25 wt% to 45 wt% of component (a2), based on the total weight of the non-fluorinated polymer .
The method according to claim 1,
Characterized in that the water repellent coating composition of synthetic leather comprises 5 wt% to 30 wt% of component (A), 1 wt% to 20 wt% of component (B) and 55 wt% to 80 wt% of component (C) A water repellent coating composition of synthetic leather.
The method according to claim 1,
The water-repellent coating composition for synthetic leather according to (a1), wherein the cetyl (meth) acrylate ester having a carbon number of 16 is 70 wt% or more based on the total weight of the ester monomer (a1).
The method according to claim 1,
The water-repellent coating composition for synthetic leather according to claim 1, wherein the component (a1) has a cetyl (meth) acrylate ester having a carbon number of 16 in an amount of 85 wt% or more based on the total weight of the ester monomer (a1).
The method according to claim 1,
Wherein the component (a2) is vinyl chloride or vinylidene chloride.
The method according to claim 1,
Wherein the component (B) is a surfactant containing a polyoxyalkylene group.
(i) mixing a water repellent coating composition of the synthetic leather of any one of claims 1 to 7 and a crosslinking agent; And
(ii) coating the mixture on the surface of the artificial leather.
9. The method of claim 8,
Wherein the crosslinking agent comprises a compound having a block isocyanate group or an isocyanate group.
A water repellent synthetic leather product produced by the method of claim 8.