KR20150049294A - Artificial leather comprising aliphatic polycarbonate resin composition - Google Patents

Abstract

The present invention can provide artificial leather comprising a polyalkylene carbonate resin composition which has an interpenetrating cross-linkage structure and contains: at least one compound selected from aliphatic polycarbonate, aliphatic polycarbonate and polyol compounds, epoxy based compounds, and acryl based compounds, which are obtained by reactions of one or at least two different epoxide compounds selected from the group consisting of (C2-C10)alkylene oxide substituted or unsubstituted with carbon and halogen or alkoxy, (C4-C20)cycloalkyleneoxide substituted or unsubstituted with halogen or alkoxy, and (C8-C20)styreneoxide substituted or unsubstituted with halogen, alkoxy, alkyl, or aryl; and a hardener that can polymerize, cross-link, or react with the same.

Description

[0001] The present invention relates to an artificial leather comprising an aliphatic polycarbonate resin composition,

The present invention relates to an artificial leather comprising a resin composition having an interpenetrating crosslinking structure containing an aliphatic polycarbonate by copolymerization of carbon dioxide with at least one epoxide compound.

Polyurethane or polyvinyl chloride resins used in synthetic leather such as shoes, bags or clothing continue to be studied for substances that can replace them due to environmental problems. In particular, artificial leather is difficult to recycle due to its chemical structure, it is discolored when exposed to ultraviolet rays for a long time, contains not only environmentally harmful substances but also dioxin which is a carcinogen in burning. Therefore, it is necessary to develop materials for environmentally friendly artificial leather.

On the other hand, industrialization of aliphatic polycarbonate is proceeding as a method for reducing the generation of carbon dioxide as a measure against global warming. The aliphatic polycarbonate is a soft rubber-like plastic in nature and has excellent workability and is easy to control the decomposition characteristics, and thus it has been extensively studied as a biodegradable polymer. However, the aliphatic polycarbonate has a low glass transition temperature (Tg) and is easily decomposed at around 200 캜 and has poor heat resistance. In addition, since the elastic modulus is small due to mechanical properties and the film is easily broken in the case of thin film products, its use in various fields is restricted. Accordingly, there is a demand for a technique for improving the glass transition temperature or heat resistance or improving the mechanical strength through blending with various resins. For example, U.S. Patent No. 4,946,884 (Patent Document 2) discloses a resin composition comprising a binder for melt-kneading polypropylene carbonate with polymethyl methacrylate (PMMA) or for molding ceramics or metal powder, U.S. Patent No. 4,912,149 (Patent Document 2) discloses that mechanical properties are improved by melt kneading polyvinyl chloride acetate. However, in these inventions, it is necessary to improve the structural properties because the improvement of the mechanical properties is limited only with the heterogeneous resin and the blend.

IPN (Interpenetrating Polymer Networks) is a multicomponent polymer in which at least one component has a crosslinking structure, and at least one component or more is polymerized or crosslinked in the presence of other components, resulting in interpenetration between polymer chains. It is expected that various physical properties can be improved by having a dual phase continuity structure in which the phase separation which is commonly observed in polymer blends is suppressed and the two components form a continuous phase. In order to overcome the limit of physical properties of the polyalkylene carbonate resin itself and to expand the application range, there is a need to study a technology applying the IPN structure.

United States Patent No. 4,946,884 (1990.08.07) U.S. Patent No. 4,912,149 (Mar. 28, 1990)

It is an object of the present invention to provide an artificial leather which does not contain environmentally harmful substances and is environmentally friendly.

The present invention also relates to an interpenetrating crosslinking agent capable of greatly improving not only mechanical properties but also chemical resistance by applying a polyalkylene carbonate resin to an IPN structure and at the same time maximizing transparency, heat resistance and molding processability due to a uniform molecular structure And an object of the present invention is to provide an artificial leather comprising a polyalkylene carbonate resin composition having a structure.

Disclosure of the Invention In order to solve the above-described problems, the present invention provides a (C2-C10) alkylene oxide substituted with carbon dioxide and halogen or alkoxy; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen or alkoxy; And (C8-C20) styrene oxide substituted or unsubstituted by halogen, alkoxy, alkyl or aryl, and a polyol compound obtained by reacting at least two epoxide compounds, which are different from each other, There can be provided an artificial leather comprising a polyalkylene carbonate resin composition having an interpenetrating crosslinking structure comprising at least one compound selected from an epoxy compound and an acrylic compound and a curing agent capable of being polymerized, have.

The artificial leather according to the present invention is produced by blending 5 to 950 parts by weight of a polyol compound with 100 parts by weight of an aliphatic polycarbonate and a polyalkyl having an interpenetrating crosslinking structure containing a curing agent in an amount of 0.9 to 1.2 times the hydroxyl equivalent of the polyol compound And a recarbonate resin composition.

The artificial leather according to an embodiment of the present invention may include an aliphatic polycarbonate represented by the following general formula (1).

[Chemical Formula 1]

(Wherein w is an integer of 2 to 10, x is an integer of 5 to 100, y is an integer of 0 to 100, n is an integer of 1 to 3, R is hydrogen, ) alkyl or _{-CH 2 -O-R '(R} ' is a (C1 ~ C8) alkyl).)

Aliphatic polycarbonate in accordance with an embodiment of the present invention may be a weight-average molecular weight (M _w) of 10,000 to 350,000 (g / mol).

The aliphatic polycarbonate according to an embodiment of the present invention may have a melt index (Melt Index: 150 ° C / 5 kg) of 0.01 to 350.

In the present invention, the polyol compound is at least one selected from the group consisting of a polyester polyol, a polyether polyol and a polycarbonate polyol. In this case, the polyol compound may be a low molecular weight polyol having a weight average molecular weight of 200 to 30,000.

In the present invention, the epoxy compound may be a glycidyl ether, a glycidyl ester, a glycidyl amine, a linear aliphatic compound, a cycloaliphatic compound, Compound, wherein the functional group may be two or more than three.

In the present invention, the acrylic compound may be selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, buthyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, Acrylate or alkyl methacrylate selected from the group consisting of acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl methacrylate and 2-ethylbutyl methacrylate, Compounds may be used, wherein an initiator of peroxide may be added to initiate the reaction.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to an embodiment of the present invention may contain one or more selected from isocyanate, melamine, amine, acid anhydride, imidazole, and multi- Or a mixture of two or more of them may be used.

In the case of urethane IPN, it is preferable that the curing agent is reacted sequentially with an isocyanate-based compound and a melamine-based compound.

In the present invention, the isocyanate curing agent is preferably at least one selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-trilenediisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylene diisocyanate, Diisocyanate, 1,3-bisisocyanate methylcyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, triphenylmethane triisocyanate, and adduct type, biuret type, or trimmer of them, for example, may be used.

In the present invention, the melamine compound may be any one or more selected from the group consisting of hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine and hexahexyloxymethylmelamine .

In the present invention, the amine compound may include linear amines, aliphatic amines, modified aliphatic amines, aromatic amines, secondary amines, and tertiary amines, and specifically includes benzyldimethylamine, triethanolamine, triethylenetetramine, Diethylenetriamine, triethylenamine, dimethylaminoethanol, tridimethylaminomethylphenol, and the like.

In the present invention, the acid anhydride-based compound is selected from the group consisting of phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, Tallow anhydride, etc., may be used alone or in combination.

In the present invention, the imidazole-based compound is at least one compound selected from the group consisting of imidizole, isomimidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidizole, 2,4-dimethyl imidizole, butyl imidizole, 2-methyldimidazole, 2-undecylidimidizole, 1-vinyl-2-methylimidizole, 2-n-heptadecylimidizole, 2- 2-methylimidizole, 1-propyl-2-methylimidizole, 1-cyanoethyl-2-methyl 1-cyanoethyl-2-ethyl-4-methylimidizole, 1-cyanoethyl-2-undecylimidizole, 1-cyanoethyl- 2-methylimidizole, an adduct of imidazole and methylimidizole, an adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidizole, phenylimidazole , Benzylimidizole, 2-methyl-4,5-diphenylimidizole, 2,3,5-triphenylimidizole, 2-styrylimidizole, 1- (dodecylbenzyl) -2- Me Imidazole, 2- (2-hydroxy-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl) 2- (2-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5-diphenylimidazole, 1-benzyl- 2-methylimidizole and 2-p-methoxystyrylimidazole may be used alone or in combination.

In the present invention, the mercapto compound is also referred to as polymercaptan, and examples thereof include pentaerythritol, tetrathioglycol, polysulfide, and trioxyantrimethylenemercaptan.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to the present invention can be used in the form of a pigment, a dye, a filler, an antioxidant, an ultraviolet screening agent, an antistatic agent, an antiblocking agent, a slip agent, an inorganic filler, , A modified resin, a leveling agent, a fluorescent whitening agent, a dispersant, a heat stabilizer, a light stabilizer, an ultraviolet absorber and a lubricant.

The present invention can provide an artificial leather comprising a polyalkylene carbonate resin composition having the interpenetrating crosslinking structure.

The artificial leather according to the present invention does not contain environmentally harmful substances and thus has an advantage of being environmentally friendly. The present invention also provides a polyalkylene carbonate resin composition having an interpenetrating crosslinking structure, which can remarkably improve transparency, heat resistance, and chemical resistance, and is excellent in mechanical properties such as impact strength, elastic strain, compression strain and tensile strength So that the artificial leather can be provided.

In addition, the present invention provides a polyalkylene carbonate resin composition having an interpenetrating crosslinking structure, which can be applied to various fields such as sheets, and can be economically advantageous in that the production cost can be reduced by a simple process.

The present applicant has found that by introducing an IPN structure into a polyalkylene carbonate resin, transparency can be ensured through a uniform molecular structure, and mechanical properties such as heat resistance, chemical resistance, tensile strength, elongation, impact resistance and elastic modulus can be improved The present invention has been accomplished on the basis of these findings.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to the present invention is prepared by dissolving a curing agent in an amount of 0.9 to 1.2 times equivalent to the hydroxyl group equivalent of an aliphatic polycarbonate, a polyol compound and a polyol compound in a solvent such as MEK, For a certain period of time, or by reactive extrusion at 120 to 200 < 0 > C.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to the present invention can be produced by dissolving an aliphatic polycarbonate and an epoxy compound in a solvent and then adding a curing agent in an equivalent amount to produce a crosslinked structure or to form an aliphatic polycarbonate, Followed by reaction extrusion at 120 to 220 ° C.

The polyalkylene ketone resin composition having an interpenetrating crosslinking structure according to the present invention can be produced by dissolving an aliphatic polycarbonate and an acrylic compound in a solvent and then adding a reaction initiator or a catalyst in an equivalent amount to produce a crosslinked structure or an aliphatic polycarbonate, An acrylic compound and an initiator, or a catalyst, at 120 to 200 占 폚.

In the present invention, the aliphatic polycarbonate may be one derived from escaping sources (Korean Patent Laid-Open Nos. 2008-0015454, 2009-0090154, 2010-067593 and 2010-0013255).

The aliphatic polycarbonate of the present invention can be obtained by reacting carbon dioxide with carbon dioxide optionally substituted with halogen, (C 1 -C 20) alkyloxy, (C 6 -C 20) aryloxy or (C 6 -C 20) aryl (C 1 -C 20) C2-C20) alkylene oxide; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide and at least one epoxide compound selected from the group consisting of styrene oxide and styrene oxide.

The epoxide compound may be selected from the group consisting of ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, 2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, glycyryl methyl ether, glycidyl ethyl ether, glycidyl n-propyl ether, glycidyl secondary butyl Ether, glycidyl or isopentyl ether, glycidyl n-hexyl ether, glycidyl n-heptyl ether, glycidyl n-octyl or 2-ethyl-hexyl ether, glycidyl normal or isononyl ether, glycidyl N-decyl ether, glycidyl nordodecyl ether, glycidyl n-tetradecyl ether, glycidyl n-hexadecyl ether, Butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, , Cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxide norbornene, limonene oxide, dieldrin, 2,3-epoxide propylbenzene, styrene Methylphenyl ether, chlorophenyl-2, 3-phenoxypropane, benzyloxymethyloxirane, glycidyl-methylphenyl ether, 3-epoxide propyl ether, epoxypropyl methoxyphenyl ether biphenyl glycidyl ether, glycidyl naphthyl ether, glycidol acetic acid ester, glycidyl Glycidyl hexanoate, glycidyl n-octanoate, glycidyl n-octanoate, glycidyl 2-ethylhexaate, glycidyl norbornene octanoate, Glycidyl norbornene decanoate, glycidyl norbornene decanoate, glycidyl norbornene decanoate, glycidyl norbornene decanoate, glycidyl norbornadecanoate, glycidyl norbornene decanoate, glycidyl norbornene decanoate, Decanoate, and glycidyl isocanoate. These may be used alone or in combination of two or more.

The aliphatic polycarbonate of the present invention may be a polyalkylene carbonate represented by the following formula (1).

[Chemical Formula 1]

(Wherein w is an integer of 2 to 10 and x is an integer of 5 to 100

Said, y is an integer from 0 to 100, n is an integer from 1 to 3, R is hydrogen, (C1 ~ C4) alkyl or _{-CH 2 -O-R '(R} ' is a (C1 ~ C8) alkyl) to be.)

Here, in the polyalkylene carbonate, the alkylene includes, but is not limited to, ethylene, propylene, 1-butylene, cyclohexene oxide, alkyl glycidyl ether, n-butyl and n-octyl.

(C 1 -C 20) alkyloxy, (C 6 -C 20) aryloxy or (C 6 -C 20) aryloxy or a (C6-C60) aryloxy group in the presence of a polymer containing a terminal hydroxyl group or a side chain, (C2-C20) alkylene oxide substituted or unsubstituted with (C1-C20) aralkyloxy; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- -C20) styrene oxide, and carbon dioxide.

(2)

[In the formula (2)

M is a cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ¹ To R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R ¹ To R ¹⁰ medium Two of which may be connected to each other to form a ring;

The R ¹ To At least one of the hydrogen atoms contained in R ¹⁰ and Q is a proton residue selected from the group consisting of the following formulas a, b and c;

X ^- are independently of one another a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

Z is a nitrogen or phosphorus atom;

R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ²¹ , R ²² and R ²³ or R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Two of which may be connected to each other to form a ring;

R ⁴¹ , R ⁴² and R ⁴³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ⁴¹ , R ⁴² and R ⁴³ may be connected to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R wherein R is (C1-C20) alkyl;

n is < ^{RTI ID =} To R < ¹⁰ > and Q plus 1 to the total number of protons included;

X ^- may coordinate to M;

The nitrogen atom of the imine can be decarboxylated to M.]

The polyalkylene carbonate resin according to one embodiment of the present invention may preferably be polypropylene carbonate copolymerized with propylene oxide and carbon dioxide.

Polyalkylene carbonate according to one embodiment of the present invention is characterized in that 10,000 to 350,000 weight-average molecular weight (M _w), preferably, 30,000 to 250,000. The polyalkylene carbonate resin may have a glass transition temperature (Tg) of 20 to 105 ° C and a melt index (Melt Index, 150 ° C / 5 kg) of 0.01 to 350. Use of a polyalkylene carbonate resin having the above range is advantageous for processing into a pellet form.

The polyalkylene carbonate according to one embodiment of the present invention has a specific gravity of 1.15 to 1.35 g / cm < ³ > And if it is out of the above range, it may be difficult to exhibit the effect as described above.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to an embodiment of the present invention is prepared by mixing 5 to 950 parts by weight of a polyol compound and 0.9 to 1.2 equivalents of a hydroxyl group equivalent of a polyol with respect to 100 parts by weight of an aliphatic polycarbonate Of a curing agent. Outside of the above range, the unreacted polyisocyanate remains or the degree of crosslinking due to curing is insufficient.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to an embodiment of the present invention may be a mixture of one or more selected from isocyanate-based and melamine-based compounds as a curing agent.

At this time, the curing agent may preferably be reacted sequentially with isocyanate and melamine compound. At the same time, when two or more curing agents are added to perform curing crosslinking reaction, it is difficult to control the desired structure because the structure of the IPN structure changes depending on the reaction rate of the two curing agents. Therefore, it is possible to obtain an IPN having a uniform structure by reacting using one kind of curing agent and then sequentially reacting with another curing agent.

In the present invention, the isocyanate curing agent is preferably at least one selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-trilenediisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylene diisocyanate, Diisocyanate, 1,3-bisisocyanate methylcyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and triphenylmethane triisocyanate can be used.

In the present invention, the melamine compound may be any one selected from the group consisting of hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine. .

In the present invention, the polyol compound may be any one selected from the group consisting of polyester polyols, polyether polyols and polycarbonate polyols.

Here, the polyol compound is characterized by containing a low molecular weight polyol having a weight average molecular weight of 200 to 30,000. If it is out of the above range, crosslinking by the curing reaction is not easy. If the molecular weight is too low, the molecular weight of the polymer produced by the curing reaction is less than 50,000, and if the polyol having a molecular weight of 30,000 or more is used, effective penetration of polyalkylene carbonate molecules hardly occurs, and it may be difficult to obtain an effective IPN structure after the curing reaction.

The polyalkylene carbonate resin composition according to an embodiment of the present invention is an epoxy compound selected from an aliphatic polycarbonate, a glycidyl ether, a glycidyl ester, a glycidyl amine, a linear aliphatic or an alicyclic compound, And a curing agent that can be polymerized, crosslinked or reacted with the epoxy resin, wherein the epoxy compound has a weight average molecular weight of 100 to 10,000, and the low molecular weight epoxy resin has a low permeability to aliphatic polycarbonate molecules And can have a good IPN structure after the curing reaction.

The polyalkylene carbonate resin composition according to an embodiment of the present invention may include an aliphatic polycarbonate and at least one of methyl acrylate, ethyl acrylate, propyl acrylate, buthyl acrylate, , Heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl methacrylate and 2-ethyl butyl methacrylate. Or an alkyl methacrylate, and a curing agent that can be polymerized, crosslinked or reacted with the acrylic compound, wherein the epoxy compound has a weight average molecular weight of 100 Lt; RTI ID = 0.0 > 10,000 < / RTI > The projection can have a good structure after IPN efficiently up the curing reaction.

A polyalkylene carbonate resin composition having an interpenetrating cross-linking structure comprising at least one compound selected from the aliphatic polycarbonate, the polyol compound, the epoxy compound and the acrylic compound, and a curing agent capable of being polymerized, crosslinked or reacted therewith Preferably has an interpenetrating cross-linking structure by reaction extrusion, and may be formed by a solution reaction, but is not limited thereto.

The polyalkylene carbonate resin composition having an interpenetrating crosslinking structure according to an embodiment of the present invention may contain at least one selected from the group consisting of pigments, dyes, fillers, antioxidants, ultraviolet screening agents, antistatic agents, anti-blocking agents, slip agents, inorganic fillers, , A tackifier resin, a modified resin, a leveling agent, a fluorescent whitening agent, a dispersant, a heat stabilizer, a light stabilizer, an ultraviolet absorber and a lubricant.

The present invention can provide an artificial leather comprising a polyalkylene carbonate resin composition having the interpenetrating crosslinking structure described above.

In addition, a sheet or film containing the composition can be provided.

Hereinafter, the present invention will be better understood by reference to the following examples, and the following examples are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

 [Examples 1 to 8]

Polypropylene carbonate (PPC), polyester diol (U1420, union-forming property, MW: 2,000) and polycarbonate diol (PCDL, G3452, Asahi Kasei, MW: 2,000) having a weight average molecular weight of 89,000 and an ether linkage of 0.5% , And a resin composition having an IPN structure according to the present invention was prepared with the contents (parts by weight) shown in Table 1 below. Hardening was carried out using H12MDI (4,4'-Dicyclohexyl-methane diisocyanate). Tg, Tm, strain at break and strain at break were measured by UTM (Universal Test Machine), and the results are shown in Table 2.

Table 1. PU-IPN compounding ratio

Table 2. UTM measurement results

[Examples 9 to 12]

Polypropylene carbonate (PPC), epoxy compound (National Chemical Co., Ltd. YD-128) and polyamide type curing agent (National Chemical G-640) having a weight average molecular weight of 89,000 and an ether linkage of 0.5% Thereby preparing a resin composition having an IPN structure according to the present invention. The lap shear strength was measured using a UTM machine. Polycarbonate was used as the adherend. Two specimens of a certain size (1 inch x 4 inch x 0.5 mm = width x length x thickness) were cut into 1 inch x 1 inch And the adhesive strength was measured after one week after the adhesive material was applied between the overlapped surfaces. The adhesive strength was measured at room temperature and 70 ° C. The adhesive strength was measured at 70 ° C for 2 hours at 70 ° C using a UTM equipped with a temperature controllable chamber. The specimens were pulled at a speed of 50 mm / min to measure the shear strength. The results are shown in Table 4 below.

Table 3. Epoxy-IPN compounding ratio

Table 4. Adhesion measurement results

[Examples 13 to 16]

2,2-azobis-isoburyronityronitrile (AIBN, purified gold) as a reaction initiator and polypropylene carbonate (PPC), acrylic compound (MMA, purified water) having a weight average molecular weight of 89,000 and an ether linkage of 0.5% 4-methoxyphenol (MPh, Junsei Chemical) was used as a reaction inhibitor. The above solution was applied on the PET film at a uniform thickness of 5 to 7 μm at a rate of 5 to 100 mm / sec. The coated film was allowed to stand at room temperature for 30 minutes, dried at 70 ° C, and then its surface hardness was measured. The surface hardness was measured with a pencil hardness tester (COAD606, Ocean Science).

Table 5. Acryl-IPN compounding ratio

Table 6. Hardness measurement result

As shown in Table 2, the embodiment according to the present invention has an IPN structure, which shows that Tm is generated in addition to Tg, thereby changing the molecular structure. The formation of such an IPN structure has an advantage that not only the mechanical strength is improved by introducing the crystalline portion into the amorphous polymer but also the stability of the cell is secured when the foam is formed. Further, in the case of having a 100% amorphous structure even after the IPN, the chemical resistance can be improved while the transparency of the polyalkylene carbonate is not greatly impaired. Therefore, the artificial leather according to the present invention is advantageous not only in transparency but also in heat resistance, molding processability and chemical resistance. In addition, it has an advantage of increasing the chromaticity when applied to binders such as paints and inks, and can provide a base for securing desired physical properties through changes in composition of various polyols and changes in curing method.

As shown in Table 4, by having the IPN structure according to the present invention, it is possible to improve the heat resistance and adhesion performance, and thereby it can be applied to paints or adhesives.

As shown in Table 6, it can be confirmed that the hardness is increased by having the IPN structure according to the present invention. As described above, there is an advantage that it can be applied not only to artificial leather having such a property-enhancing effect but also to an injection field such as a high-performance film, sheet or case.

Claims (19)

(C2-C10) alkylene oxide substituted with carbon dioxide and halogen or alkoxy; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen or alkoxy; And (C8-C20) styrene oxide substituted or unsubstituted by halogen, alkoxy, alkyl or aryl, and a polyol compound obtained by reacting at least two epoxide compounds, which are different from each other, A polyalkylene carbonate resin composition having an interpenetrating crosslinking structure comprising at least one compound selected from an epoxy compound and an acrylic compound and a curing agent capable of being polymerized or crosslinked therewith. The method according to claim 1,
Wherein the aliphatic polycarbonate has an interpenetrating crosslinking structure having a weight average molecular weight of 30,000 to 350,000. The method according to claim 1,
Wherein the aliphatic polycarbonate has a melt index (Melt Index, 150 DEG C / 5 kg) of from 0.01 to 350. The method according to claim 1,
Wherein the aliphatic polycarbonate is polypropylene carbonate or polyethylene carbonate. The method according to claim 1,
Wherein the polyalkylene carbonate resin composition is represented by the following formula (1).
[Chemical Formula 1]

Wherein w is an integer of 2 to 10, x is an integer of 5 to 100, y is an integer of 0 to 100, n is an integer of 1 to 3, R is hydrogen, ) alkyl or _{-CH 2 -O-R '(R} ' is a (C1 ~ C8) alkyl); The method according to claim 1,
Wherein the polyol compound is at least one selected from the group consisting of a polyester polyol, a polyether polyol, and a polycarbonate polyol. The method according to claim 1,
Wherein the epoxy compound is at least one selected from glycidyl ether, glycidyl ester, glycidyl amine, linear aliphatic compound and alicyclic compound. The method according to claim 1,
The acrylic compound is preferably selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl Methacrylate, and 2-ethylbutyl methacrylate. The method according to claim 1,
Wherein the curing agent is at least one selected from isocyanate-based, melamine-based, amine-based, acid anhydride-based, imidazole-based and multi-capped compounds. 10. The method of claim 9,
The isocyanate curing agent is preferably at least one selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-trilenediisocyanate, hydrogenated trilene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane- , 4-diisocyanate, 1,3-bisisocyanate methylcyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Methylene diisocyanate, and triphenylmethane triisocyanate. 10. The method of claim 9,
Wherein the melamine-based curing agent is at least one selected from the group consisting of hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine. 10. The method of claim 9,
Wherein the amine-based curing agent is at least one selected from benzyldimethylamine, triethanolamine, triethylenetetramine, diethylenetriamine, triethylenamine, dimethylaminoethanol, and tridimethylaminomethylphenol. 10. The method of claim 9,
The acid anhydride-based curing agent may be at least one selected from the group consisting of a phthalic anhydride, a maleic anhydride, a trimellitic anhydride, a pyromellitic anhydride, a hexahydrophthalic anhydride, a tetrahydrophthalic anhydride, a methylnadic anhydride, a nadic anhydride and a methylhexahydrophthalic And anhydrides. 10. The method of claim 9,
The imidazole-based curing agent may be at least one selected from the group consisting of imidazole, isomimidazole, 2-methylimidazole, 2-ethyl-4-methylimidizole, 2,4-dimethylimidizole, butylimidizole, 2- 2-methylimidazole, 2-methylimidizole, 2-undecylidimidizole, 1-vinyl-2-methylimidizole, 2-n-heptadecylimidizole, 2-undecylimidizole , 2-heptadecylimidizole, 2-phenylimidizole, 1-benzyl-2-methylimidizole, 1-propyl-2-methylimidizole, 1-cyanoethyl- 1-cyanoethyl-2-ethyl-4-methylimidizole, 1-cyanoethyl-2-undecylimidizole, 1-cyanoethyl- Ethyl-2-methylimidizole, an adduct of imidazole and methylimidizole, an adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole, phenylimidazole, benzyl Imidizole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidizole, 2-styrylimidizole, 1- (dodecylbenzyl) Midi 2- (2-methoxyphenyl) -4,5-diphenylimidazole, 2- (2-hydroxyphenyl) -4,5- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) -4,5-diphenylimidazole, 2- Diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5-diphenylimidazole, 1-benzyl- -Methylimidizole, and 2-p-methoxystyrylimidazole. 10. The method of claim 9,
Wherein the multicompactant hardener is at least one selected from pentaerythritol, tetracylglycol, polysulfide, and trioxytrimethylene mercaptan. The method according to claim 1,
5 to 950 parts by weight of a polyol compound and 0.9 to 1.2 equivalents of a curing agent based on 100 parts by weight of the aliphatic polycarbonate, based on the hydroxyl equivalent of the polyol. 17. The method of claim 16,
Wherein the polyol compound comprises a low molecular weight polyol having a weight average molecular weight of 200 to 30,000. 17. The method of claim 16,
Wherein the curing agent is an isocyanate compound and a melamine compound are sequentially reacted. The method according to claim 1,
A pigment, a dye, a filler, an antioxidant, an ultraviolet screening agent, an antistatic agent, an antiblocking agent, a slip agent, an inorganic filler, a kneader, a stabilizer, a tackifier resin, a modifying resin, a leveling agent, a fluorescent whitening agent, , Ultraviolet absorber (s), and lubricant (s).