KR100780025B1 - Polypropylene-based resin composition - Google Patents

Abstract

The present invention comprises 80 to 99.9% by weight of a polypropylene resin and 0.1 to 20% by weight of an acrylate polymer resin dispersed in a polyolefin, wherein the acrylate polymer resin dispersed in the polyolefin is an alkyl acrylate monomer, A polypropylene resin composition is provided on an acrylate copolymer obtained by absorbing an alkyl methacrylate monomer, a polar group-containing acrylate monomer and a polymerization initiator and then polymerizing the same.

Acrylate polymer resin dispersed in polypropylene, polyolefin, vacuum deposition, coating

Description

Polypropylene-based resin composition

1 is a photograph of the appearance after performing an alcohol-resistant experiment on the vapor-molded article of Experimental Example 1.

2 is a photograph of the appearance after performing an alcohol-resistant experiment on the vapor-molded article of Comparative Example 1.

The present invention relates to a polypropylene resin composition having excellent physical properties and improved surface workability.

Polypropylene-based resins are inexpensive and easy to process such as injection molding and blow molding, and thus the amount of polypropylene-based resins is increasing.However, due to the characteristics of the polypropylene-based resins in the processing of molded products using the polypropylene-based resins, the molded articles Because of the nonpolar surface, direct processing is difficult. Therefore, the method of flame-treating together with the primer on the surface of the molded article is used to impart polarity to the surface of the molded article. However, the complexity of the primer and flame process and the possibility of defects have limited its use.

In particular, in the molded article in which appearance is an important factor such as cosmetic containers, the polypropylene resin cannot be used, and thus, polystyrene resin (ABS series; ABS series) is mainly used. However, such polystyrene-based resins are more expensive than polypropylene resins and have difficulty in blow molding.

In addition, since the chemical resistance of the polystyrene-based resin is poor compared to the polypropylene-based resin, there may be a problem in the alcohol or some of the contents of the cosmetics or household goods. In order to solve the above problems, in the industry, a polypropylene resin is used for the inside of direct contact with the contents, and a double injection, coextrusion, etc. is used to use an ABS resin for the parts requiring deposition or coating. The product has been processed through.

However, in the case of the processing method as described above, problems such as complicated processing process and the production of two or more molds, or failure due to the difference in shrinkage of the resin occurs.

Accordingly, an object of the present invention is to provide a polypropylene resin composition having excellent mechanical properties and improved deposition strength and coating adhesion.

In order to achieve the above object, the present invention provides a polypropylene resin composition comprising 80 to 99.9% by weight of polypropylene resin and 0.1 to 20% by weight of acrylate-based polymer resin dispersed in a polyolefin.

The polypropylene resin composition of the present invention is a polypropylene resin, selected from the group consisting of crystalline polypropylene homopolymers, propylene / ethylene random copolymers, propylene / ethylene block copolymers and ethylene / propylene / α-olefin terpolymers. It may be a polypropylene resin composition characterized in that using one.

The polypropylene resin composition of the present invention may be a polypropylene resin composition, characterized in that the melt index of the polypropylene resin is 0.5 to 80 g / 10 minutes (2.16kg, 230 ℃).

The acrylate polymer resin dispersed in the polyolefin may be an acrylate copolymer obtained by polymerizing a polyolefin by absorbing an alkyl acrylate monomer, an alkyl methacrylate monomer and a polar group-containing acrylate monomer and a polymerization initiator.

Hereinafter, the present invention will be described in detail.

The polypropylene resin composition according to the present invention may include 80 to 99.9 wt% of the polypropylene resin and 0.1 to 20 wt% of the acrylate polymer resin dispersed in the polyolefin.

When the content of the acrylate-based polymer resin dispersed in the polyolefin is less than 0.1% by weight, deposition strength or coating adhesion may be lowered. When the content of the acrylate-based polymer resin exceeds 20% by weight, the physical properties of the molded article using the composition may be deteriorated. The problem of damage arises.

The polypropylene resin may be a crystalline polypropylene homopolymer, a propylene / ethylene random copolymer, a propylene / ethylene block copolymer, an ethylene / propylene / α-olefin terpolymer (ter -polymer) and the like, of which propylene / ethylene block copolymer is particularly preferable.

The polypropylene resin is preferably a melt index of 0.5 to 80g / 10 minutes (2.16kg, 230 ℃). If the melt index is less than 0.5g / 10 minutes (2.16kg, 230 ℃) may be poor workability during injection molding or blow molding, when the melt index exceeds 80g / 10 minutes (2.16kg, 230 ℃) The mechanical properties of the final molded product can be lowered.

The acrylate polymer resin dispersed in the polyolefin may be an acrylate copolymer obtained by polymerizing the polyolefin by absorbing an alkyl acrylate monomer, an alkyl methacrylate monomer, a polar group-containing acrylate monomer and a polymerization initiator.

Examples of the polyolefin include high density polyethylene, low density polyethylene, linear low density polyethylene, polyethylene copolymers, polyethylene in which functional groups are introduced by chemical bonds into the main chain, or polyethylene in which functional groups are introduced by chemical bonds.

In the polyethylene copolymer, comonomers include propylene, butene, pentene, octene, butadiene, ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, methyl acrylate, ethyl acrylate, butyl acrylate, Glycidyl methacrylate, acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, itaconic anhydride, acrylonitrile, acrylamide, and the like may be exemplified, but are not limited thereto.

Examples of the functional group include maleic anhydride, itaconic anhydride, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, vinyl pyrrolidone, styrene, and the like, but are not limited thereto.

Further, the polyolefin includes polypropylene, polypropylene copolymer, polypropylene in which functional groups are introduced by chemical bonds in the main chain, or polypropylene in which functional groups are introduced by chemical bonds in branches. In the polypropylene copolymer, comonomers include, but are not limited to, ethylene and butylene. Examples of the functional group include maleic anhydride, itaconic anhydride, acrylic acid, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, vinyl pyrrolidone, styrene, and the like, but are not limited thereto.

In addition, the polyolefin may be a polyolefin alone or a blend of two or more polyolefins. When using a blend of two or more polyolefins, it is preferable to use a blend of polyolefin and polyethylene copolymer. Polyethylene copolymers used in the polyolefin blend include poly (ethylene-co-methylacrylate), poly (ethylene-co-ethylacrylate), poly (ethylene-co-butylacrylate), and poly (ethylene-co-acrylic acid ), Poly (ethylene-co-methacrylic acid), poly (ethylene-co-glycidyl methacrylate), poly (ethylene-co-maleic acid), poly (ethylene-co-vinylacetate), poly (ethylene -Co-acrylamide), poly (ethylene-co-acrylonitrile) and the like, but are not limited thereto.

The alkyl acrylate monomers are alkyl acrylates having at least one, preferably at least two, carbon atoms in the alkyl chain. Examples of the alkyl acrylate used in the present invention include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.

The amount of the alkyl acrylate monomer is preferably 65 to 455 parts by weight based on 100 parts by weight of the polyolefin. When the amount of the alkyl acrylate monomer is less than 65 parts by weight, the mechanical properties are poor, and when the amount of the alkyl acrylate monomer is greater than 455 parts by weight, the workability may be reduced during surface processing.

The alkyl methacrylate monomer preferably has 1 to 18 carbon atoms in the alkyl chain. In particular, since the alkyl methacrylate has a function of improving the flowability of the thermoplastic polymer and reducing side reactions such as crosslinking reaction in the molecule, it is more preferable to have 1 to 4 carbon atoms in order to exhibit such an effect. Examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like, but are not limited thereto.

The amount of the alkyl methacrylate monomer is preferably 15 to 240 parts by weight based on 100 parts by weight of the polyolefin. If the amount of the alkyl methacrylate monomer is less than 15 parts by weight, the mechanical properties may be lowered. If it exceeds 240 parts by weight, the surface workability is lowered.

The polar group-containing acrylate monomer may include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, aminoalkyl acrylate, aminoalkyl methacrylate, acrylic acid, methacrylic acid, and the like. The polar group-containing acrylate monomer is preferably 1 to 18 carbon atoms in the alkyl chain, in order to improve the flowability of the thermoplastic polymer and to reduce side reactions such as intramolecular crosslinking reaction, 1 to 4 carbon atoms It is more preferable to have.

The amount of the polar group-containing acrylate monomer is preferably 15 to 300 parts by weight based on 100 parts by weight of the polyolefin. When the amount of the polar group-containing acrylate monomer is less than 15 parts by weight, the surface workability is lowered, and when the amount of the polar group-containing acrylate monomer is greater than 300 parts by weight, an unexpected side reaction such as intramolecular cross-linking reaction or chemical reaction occurs during the processing. Cannot be achieved.

The polymerization initiator is a free radical reaction of the acrylate monomer to obtain a polymer, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, t-butyl peroxide, dicumyl peroxide, t-butyl Peracetate, 2,2-bis (t-butylperoxy) butane, 2,5-bis (t-butylperoxy) -2,5-dimethyl-3-hexyne, 2,5-bis (t-butylper And compounds such as oxy) -2,5-dimethylhexane and the like. In the present invention, it can be selected from the polymerization initiator according to the type of the selected polyolefin and the kind of acrylate monomer.

The amount of the polymerization initiator is preferably added to 0.5 to 2.0 mol% based on the sum of the number of moles of the monomers and the number of moles of the polymerization initiator. If the amount of the polymerization initiator is less than 0.5 mol% to obtain a final product poor workability, if the amount exceeds 2.0 mol% it is difficult to control the physical properties of the final product.

The acrylate-based polymer resin dispersed in the polyolefin is preferably dispersed in 95 to 995 parts by weight of the acrylate-based polymer resin with respect to 100 parts by weight of the polyolefin. When the acrylate-based polymer resin is dispersed in less than 95 parts by weight, the processability of the final molded product may be lowered, and when dispersed in more than 995 parts by weight, problems such as odor and drying occur.

The polypropylene resin composition of the present invention is a range in which ordinary various additives such as reinforcing materials, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, pigments, dyes, etc. do not deviate from the characteristics of the present invention. May be added further within. Specific examples of such additives include talc, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydroxide, zeolite, barium sulfate, and the like.

The polypropylene resin composition according to the present invention may be prepared by mixing the polypropylene resin and the acrylate polymer resin dispersed in the polyolefin at an appropriate temperature, and in the following, the preparation of the acrylate polymer resin dispersed in the polyolefin The method will be described in detail.

(First polymerization)

A polyolefin, an alkyl acrylate monomer, water and a polymerization initiator are added to a reactor equipped with a stirrer, a heating device and a cooling device, and then the reactor is sealed.

While stirring the added resins, the sealed reactor is filled with high pressure nitrogen gas and discharged to remove oxygen. Thereafter, the temperature of the reactor is increased to a temperature of 45 to 120 ° C. according to the characteristics of the polymerization initiator, in which the alkyl acrylate monomer and the polymerization initiator are absorbed into the polyolefin pellets. The absorption time is 1 hour to 5 hours depending on the type of polyolefin and the type of alkyl acrylate monomer.

The alkyl acrylate monomer is first polymerized by the polymerization initiator to form polyacrylate. The polymerization reaction time is 3 to 10 hours depending on the type of the polyolefin, the alkyl acrylate monomer and the polymerization initiator.

The alkyl acrylate monomer is preferably added 50 to 200 parts by weight based on 100 parts by weight of the polyolefin. When the alkyl acrylate monomer is added in less than 50 parts by weight, impregnation of the monomer for secondary polymerization is poor, and when added in excess of 200 parts by weight, the content of the monomer that is not absorbed in the polyolefin substrate is high yield Falls and the problem of wastewater treatment for polymerization residues arises.

The polymerization initiator is preferably added 0.5 to 2.0 mol% based on the sum of the mole number of the acrylate monomer and the mole number of the polymerization initiator. When the amount of the polymerization initiator is less than 0.5 mol%, too high a molecular weight polyacrylate polymer may be produced, and when it exceeds 2.0 mol%, an ultra low molecular weight polyacrylate polymer is formed to give physical properties of the final product. It can be degraded.

(Secondary polymerization)

After the completion of the first polymerization reaction, the temperature of the reactor is lowered to room temperature, and an alkyl acrylate monomer, a polar group-containing acrylate monomer, an alkyl methacrylate monomer and a polymerization initiator are added to the reactor in the first polymerization product. Thereafter, secondary polymerization is performed in the same manner as primary polymerization.

The amount of the alkyl acrylate monomer is preferably 10 to 85 parts by weight based on 100 parts by weight of the primary polymerization product. At this time, if less than 10 parts by weight of the alkyl acrylate monomer is poor in workability to achieve the object of the present invention, if more than 85 parts by weight of the paint adhesion improver effect of the present invention is reduced.

The amount of the alkyl methacrylate monomer is preferably 10 to 80 parts by weight based on 100 parts by weight of the primary polymerization product. If less than 10 parts by weight of the alkyl methacrylate monomer is added, the processability of the final product is poor, and the object of the present invention cannot be achieved, and if it is added more than 80 parts by weight, the effect of improving paint adhesion is lowered.

The amount of the polar group-containing acrylate monomer is preferably 10 to 100 parts by weight based on 100 parts by weight of the primary polymerization product. When the amount of the polar group-containing acrylate monomer is less than 10 parts by weight, the paint adhesion improvement effect is lowered, and when the amount is added over 100 parts by weight in the reaction process unexpected reactions such as intramolecular crosslinking reaction or chemical reaction occurs It is not possible to achieve the object of the present invention.

The polymerization initiator is preferably added in an amount of 0.5 to 2.0 mol% based on the sum of the number of moles of the monomers, that is, the alkyl acrylate monomer, the alkyl methacrylate monomer, and the polar group-containing acrylate monomer. Do. If the amount of the polymerization initiator is less than 0.5 mol% to obtain a final product poor workability, if it exceeds 2.0 mol%, the physical properties of the final product is reduced and there is difficulty in process management.

After the polymerization reaction is completed, the reactor is sufficiently cooled and the reaction liquid in the reactor is filtered to obtain pellets. The obtained pellet is in a state in which the absorbed acrylate monomers are copolymerized in the pellet and swollen. When the obtained pellets are dried in a hot air oven, an acrylate polymer resin dispersed in the polyolefin substrate can be obtained.

Experimental Example 1

A polypropylene resin composition was prepared by mixing 90% by weight of a propylene-ethylene random copolymer having a melt index of 2g / 10 minutes (2.16kg, 230 ° C) and 10% by weight of an acrylate polymer resin dispersed in a polyolefin. The acrylate-based polymer resin is a copolymer of butyl acrylate, hydroxypropyl acrylate and methyl methacrylate, and 300 parts by weight based on 100 parts by weight of the polyolefin is dispersed.

The polypropylene resin composition was molded into a 25 ml cosmetic container using a blow molding machine, and then deposition and coating were performed using aluminum.

Experimental Example 2

A polypropylene resin composition was prepared by mixing 95% by weight of a propylene-ethylene block copolymer having a melt index of 40 g / 10 minutes (2.16 kg, 230 ° C) and 5% by weight of an acrylate polymer resin dispersed in a polyolefin. The acrylate polymer resin is a copolymer of butyl acrylate, hydroxypropyl acrylate and methyl methacrylate, and 300 parts by weight of the acrylate polymer resin is dispersed in 100 parts by weight of polypropylene.

In the composition, an injection molding machine (SELEX E150, manufactured by Woojin Serex Co., Ltd.) was used to inject and mold 110 mm × 70 mm × 3 mm sized plate-shaped specimens at an injection temperature of 200 to 220 ° C. and a mold temperature of 30 ° C., and deposited using aluminum. Treatment and coating treatments were performed.

Experimental Example 3

A polypropylene composition was prepared from 99% by weight of a propylene-ethylene block copolymer having a melt index of 40 g / 10 minutes (2.16 kg, 230 ° C) and 1% by weight of an acrylate polymer resin dispersed in a polyolefin. The acrylate-based polymer resin is a copolymer of butyl acrylate, hydroxypropyl acrylate and methyl methacrylate, and 300 parts by weight of 100 parts by weight of polypropylene is dispersed.

Using the injection molding machine (SELEX E150, Woojin Serex Co., Ltd.) to prepare a plate-shaped specimen of 110mm × 70mm × 3mm size at an injection temperature of 200 ~ 220 ℃, a mold temperature of 30 ℃, and then flame-treated aluminum The deposition process was performed.

(Comparative Example 1)

90% by weight of a propylene-ethylene random copolymer having a melt index of 2g / 10 minutes (2.16kg, 230 ° C) and maleic anhydride grafted polypropylene (polybond 3200 from Uniroyal, 1% graft ratio, melt index 100) 10 weight% was mixed to prepare a composition. Then, the composition was molded into a 25 ml cosmetic container using the same blow molding machine as Experimental Example 1.

(Comparative Example 2)

A composition was prepared by mixing 95% by weight of a propylene-ethylene block copolymer having a melt index of 40 g / 10 minutes (2.16 kg, 230 ° C.) and 5% by weight of an ethylene methylacrylic acid copolymer (Dawsa, Primeco 3004). . Then, a plate-like specimen was prepared in the same manner as in Experiment 2.

Table 1 is a table showing the deposition peeling area ratio and the coating peeling area ratio of the vapor deposition treatment and coating treatment of the Experimental Examples 1, 2, 3 and Comparative Examples 1, 2, respectively. The peeling area ratio was expressed as 4 when the peeled area is 0 to 5%, 1 to 5 to 10%, 2 to 10 to 30%, and 3 to 30% or more.

Creation costs Deposition area ratio Coating Peel Area Ratio Experimental Example One 90% by weight polypropylene resin 10% by weight of acrylate polymer resin One One 2 95% by weight of polypropylene resin 5% by weight of acrylate polymer resin One One 3 99% by weight of polypropylene resin 1% by weight of acrylate polymer resin One One Comparative example One 90% by weight polypropylene resin Maleic Anhydride Graft Polypropylene 10% by weight 4 3 2 95% by weight of polypropylene resin 5 wt% ethylene methylacrylic acid copolymer 2 3

* Peel Area Ratio (%) = (Peeled Area / Total Area) X 100

Referring to Table 1, the peeled area ratio of the molded articles of Experimental Examples 1, 2, and 3 were all 1 and only 0 to 5% of the area was peeled off, whereas the molded articles according to Comparative Examples 1 and 2 were peeled off. It can be seen that the area ratio of 2 to 4 shows very low deposition strength. Therefore, it can be seen that the resin composition according to the embodiment of the present invention is capable of depositing a metal without an additional flame treatment or primer treatment and has excellent deposition strength.

Table 2 is a saline test and Experimental Examples 1, 2, which test the surface state by leaving the molded products of Experimental Examples 1, 2, 3 and Comparative Examples 1, 2 in salt water (NaCl 5% by weight) for 24 hours 3 and Comparative Examples 1 and 2 were left in a 50% by volume ethanol solution for 24 hours, and then subjected to an alcohol-resistant test to observe the surface state.

Salt water test Alcohol test Experimental Example 1 No change No change Experimental Example 2 No change No change Experimental Example 3 No change No change Comparative Example 1 Some peeling Peeling Comparative Example 2 Some peeling Peeling

Referring to the above Table 2, Experimental Example 1, 2, 3 of the deposition-processed molding according to the present invention is stable to both the salt water test and the alcohol test, it can be seen that the deposition strength is very excellent. However, the vapor-deformed molded articles of Comparative Examples 1 and 2 are partially peeled off in the salt water test, and the peeling degree is more severe in the alcohol test, so that the deposition strength is very low.

1 and 2 are photographs of the appearance after performing an alcohol-resistant experiment for the vapor-molded article of Experimental Example 1 and Comparative Example 1, and.

1 and 2, the deposition-molded article according to Experimental Example 1 has almost no change in appearance, but the deposition-molded article according to Comparative Example 1 can be seen that the surface is extremely peeled off.

Therefore, since the resin composition according to the embodiment of the present invention can be deposited without a separate flame treatment or primer treatment, cost reduction and productivity are improved. In addition, since the resin composition according to the embodiment of the present invention is capable of depositing strength during metal deposition, it is possible to manufacture a molded article having excellent physical properties and excellent surface workability.

While the embodiments of the present invention have been described above, it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, since the embodiments described above are provided to fully inform the scope of the invention to those skilled in the art, it should be understood that they are exemplary in all respects and not limited. The invention is only defined by the scope of the claims.

As described above, the present invention can provide a resin composition having excellent physical properties and capable of surface processing without a separate treatment. Therefore, the present invention has the effect of reducing the production cost and increasing the production yield while providing a resin composition having excellent surface workability.

Claims (13)

Polypropylene resin composition comprising 80 to 99.9% by weight of polypropylene resin and 0.1 to 20% by weight of acrylate-based polymer resin dispersed in a polyolefin. The method of claim 1, The polypropylene resin is any one or more selected from the group consisting of crystalline polypropylene homopolymer, propylene / ethylene random copolymer, propylene / ethylene block copolymer and ethylene / propylene / α-olefin terpolymer. The method of claim 1, Melt index of the polypropylene resin is a polypropylene resin composition, characterized in that 0.5 to 80g / 10 minutes (2.16kg, 230 ℃). The method of claim 1, The acrylate polymer resin dispersed in the polyolefin is a polypropylene resin that is in the form of an acrylate copolymer obtained by absorbing an alkyl acrylate monomer, an alkyl methacrylate monomer, a polar group-containing acrylate monomer, and a polymerization initiator into a polyolefin. Composition. The method of claim 4, wherein The polyolefin is a polypropylene resin composition of polyolefin alone or two or more polyolefin blends. The method of claim 5, The polyolefin blend is a polypropylene resin composition is a blend of polyolefin and polyethylene copolymer. The method of claim 6, The polyethylene copolymer is poly (ethylene-co-methylacrylate), poly (ethylene-co-ethylacrylate), poly (ethylene-co-butylacrylate), poly (ethylene-co-acrylic acid), poly (ethylene Co-methacrylic acid), poly (ethylene-co-glycidyl methacrylate), poly (ethylene-co-maleic acid), poly (ethylene-co-vinylacetate), poly (ethylene-co-acrylamide) And poly (ethylene-co-acrylonitrile) is at least one polypropylene resin composition selected from the group consisting of. The method of claim 4, wherein The amount of the alkyl acrylate monomer is 65 to 455 parts by weight based on 100 parts by weight of the polyolefin polypropylene resin composition. The method of claim 4, wherein The amount of the alkyl methacrylate monomer is 15 to 240 parts by weight based on 100 parts by weight of the polyolefin polypropylene resin composition. The method of claim 4, wherein The amount of the polar group-containing acrylate monomer is 15 to 300 parts by weight based on 100 parts by weight of the polyolefin polypropylene resin composition. The method of claim 4, wherein The amount of the polymerization initiator is a polypropylene resin composition is 0.5 to 2.0 mol% based on the sum of the number of moles of the monomers and the number of moles of the polymerization initiator. The method of claim 4, wherein The acrylate-based polymer resin dispersed in the polyolefin absorbs the alkyl acrylate monomer and the polymerization initiator into the polyolefin dispersed in water, and then polymerizes the alkyl acrylate, and then the alkyl acrylate monomer and the alkyl meta to the product by the polymerization. A polypropylene resin composition characterized in that the acrylate copolymer obtained by absorbing a acrylate monomer, a polar group-containing acrylate monomer and a polymerization initiator and then polymerizing the monomers two or more times. The method of claim 1, The acrylate-based polymer resin dispersed in the polyolefin is a polypropylene resin composition in which 95 to 995 parts by weight of the acrylate copolymer is dispersed with respect to 100 parts by weight of polyolefin.

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