KR100547363B1 - Polyolefin resin composition having a good matt property, impact strength and transparency for blow molding and an article using it - Google Patents

Abstract

The present invention relates to a polyolefin resin composition for blow molding having excellent matting properties, impact strength and transparency, and a product manufactured using the same, more specifically, 2 to 10% by weight of ethylene having a melt index of 5 dg / min or less, 40 to 80% by weight of a random polypropylene resin including alpha olefins having 4 to 10 carbon atoms or mixtures thereof; And an ethylene-propylene / alpha olefin copolymer comprising a melt index of 5 dg / min or less and 10 to 30% by weight of propylene, an alpha olefin or a mixture thereof or an ethylene-alphaolefin air comprising 10 to 30% by weight of ethylene. A mixture comprising 60 to 20% by weight of a mixture, and 0.01 to 0.2 parts by weight of a radical generator based on 100 parts by weight of the mixture, and optionally 0.01 to 1 part by weight of silica as a quencher, colorant 1 The polyolefin resin composition for blow molding having excellent matting properties, impact strength and transparency, and the blow molding, injection blow molding, or injection stretching blow molding, further comprising: It relates to a product produced using the method. The product manufactured according to the present invention has excellent matting properties, improves the impact strength, improves the problem of damage to the product which may occur during storage, transportation and use, and has improved transparency and thus improves the productability.

Polyolefin resin composition, random polypropylene resin, ethylene-alpha olefin copolymer resin, matte transparency, blow molding

Description

Polyolefin resin composition having a matte property, impact strength and transparency, and a product produced using the same {Polyolefin resin composition having a good matt property, impact strength and transparency for blow molding and an article using it}

The present invention relates to a polyolefin resin composition having excellent matt properties, impact strength and transparency, and to a product manufactured using the same. More specifically, the product can be manufactured by a blow molding method, and the matte property, impact strength and transparency An excellent polyolefin resin composition and a product made using the same.

In recent years, matte products that have a low surface gloss and impart a soft texture to the film to enhance the merchandise of the packaged material have been widely used as high value-added products. In the method of imparting a matte property to the surface, the glass container is generally treated with a fluoric acid-based corrosion solution after the production of the glass container to impart fine irregularities to the surface, thereby causing diffused reflection of light, thereby forming a matte glass container (frost container). In recent years, due to an increase in burden on facility costs or waste liquid treatment costs for environmental measures, a technique of coating the surface of the container with an inorganic additive to remove the gloss is used, and this technique has been put into practice. In addition, the technique is applied to the production of a polyethylene terephthalate (PET) container having a matte properties, there is a disadvantage that the coating and drying equipment is required, difficult to recycle and expensive.

In order to solve this drawback, a technique has been developed that can produce a container having a matte property using the characteristics of the polyolefin resin brand without post-processing such as corrosion or coating. In general, polypropylene resin is a general-purpose resin having excellent mechanical, thermal, and electrical properties, excellent chemical resistance, and moldability, and is widely used in films, disposable containers, and the like. In addition, polyolefin is a well-balanced resin in terms of price and performance, and is widely used for blow molding in containers such as cosmetics and detergents in the packaging field. Although most of them are polyethylene, the use of PP is increasing due to the advantages of improving the moldability and impact resistance against cold drop and excellent transparency, heat stability and crack resistance compared to polyethylene. In addition, it has excellent moldability and recyclability compared to PET.

For example, Japanese Patent Laid-Open No. 62-277450 describes a resin composition having matt properties using polypropylene and polyethylene resin. According to the patent, homopolypropylene having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 16 or more and a melt index of 0.2 to 100 dg / min, or an alpha-olefin copolymer made of ethylene, butene, 4-methylpentene, or the like Molding a container with a composition of 100 parts by weight of one selected material and 3 to 250 parts by weight of polyethylene having a molecular weight distribution of 16 or more and a melt index of 0.2 dg / min or less can form a container having a small surface gloss.

In addition, Japanese Patent Laid-Open No. 2-69549 discloses 50 to 90% by weight of impact polypropylene (impact PP) having a melt index of 0.1 to 100 dg / min, a density of at least 0.930 g / cc and a melt index of 5.0 dg / min or less. When the container is molded by using a resin composition which has been reacted and extruded with a resin composition which is formulated from 0.001 to 0.2 parts by weight of a peroxide which is a radical generator with 0.1 to 5.0 parts by weight of a crosslinking aid in a mixture of -50% by weight, a product having a matte property is obtained. It is described that it can be molded.

In Japanese Patent Laid-Open No. 9-141766, in order to give matt characteristics when forming a multilayer container, resins of polyethylene, polypropylene, or polyethylene terephthalate are used for the inner layer and ionomers, which are copolymers of ethylene-methacrylic acid, for the outermost layer. It is described that an ionomer) can be used to form a container having matt properties.

However, since the prior art is not compatible with polypropylene and uses a polyethylene resin having a high crystallinity of medium density or more, that is, a density of 0.930 g / cc or more, the container is filled with contents and then transported, stored and used. There is a problem that the container is easily broken due to the shock that may occur. In addition, the polypropylene and polyethylene used have a disadvantage in that the difference in refractive index due to the difference in crystal form and crystallinity is severe and the transparency of the container is greatly reduced, resulting in inferior commerciality as compared to matte glass and matte PET products.

Simply looking at the properties of glass, PET, and the prior art products of Japanese Patent Laid-Open Nos. 62-277450 and 2-69649, which exhibit conventional matt properties, it can be seen that they are as follows.

Kinds Matte property Impact strength Transparency weight price Matte Glass Great Thirteen Great heavy high price Matte PET Great Thirteen Great light high price Prior art product Good Thirteen Thirteen light low price

Accordingly, the present inventors have studied and researched to solve the above-mentioned problems. As a result, the inventors have found a polyolefin resin composition having a matte property consisting of a random polypropylene resin, an ethylene-alpha olefin copolymer, and a radical generator, and the present invention is based on this. It is finished.

Accordingly, an object of the present invention to solve the problems of the prior art to provide a polyolefin resin composition for blow molding excellent in matt, impact strength and transparency, inexpensive and recyclable.

In addition, another object of the present invention to provide a product for producing the polyolefin resin composition using a method of blow molding, injection blow molding or injection stretch blow molding.

In order to achieve the above object, the polyolefin resin composition for blow molding having excellent matting properties, impact strength and transparency has 2 to 10 wt% of ethylene having an melt index of 5 dg / min or less, alpha olefins having 4 to 10 carbon atoms, or 40 to 80% by weight of a random polypropylene resin comprising a mixture of; And an ethylene-propylene / alpha olefin copolymer comprising 10-30 wt% of propylene, alpha olefin or a mixture thereof or less than 5 dg / min or an ethylene-alpha comprising 10-30 wt% of ethylene. A mixture consisting of 60 to 20% by weight of an olefin copolymer; And 0.01 to 0.2 parts by weight of the radical generator with respect to 100 parts by weight of the mixture.

The product of the present invention for achieving the above another object is a random polypropylene resin 40 to 80 containing 2 to 10% by weight of ethylene, an alpha olefin of 4 to 10 carbon atoms or a mixture thereof having a melt index of 5 dg / min or less weight%; And an ethylene-propylene / alpha olefin copolymer comprising 10-30 wt% of propylene, alpha olefin or a mixture thereof or less than 5 dg / min or an ethylene-alpha comprising 10-30 wt% of ethylene. A mixture consisting of 60 to 20% by weight of an olefin copolymer; And a polyolefin resin composition for blow molding having excellent matting properties, impact strength and transparency, including 0.01 to 0.2 parts by weight of a radical generator, based on 100 parts by weight of the mixture, by using a method of blow molding, injection molding or injection stretching molding. It is manufactured by.

Hereinafter, the present invention will be described in more detail.

As described above, the composition according to the present invention comprises a random polypropylene resin (first component) comprising 2 to 10% by weight of ethylene, an alpha olefin having 4 to 10 carbon atoms or a mixture thereof having a melt index of 5 dg / min or less. 40 to 80% by weight; And an ethylene-propylene / alpha olefin copolymer comprising a melt index of 5 dg / min or less and 10 to 30% by weight of propylene, an alpha olefin or a mixture thereof or an ethylene-alphaolefin air comprising 10 to 30% by weight of ethylene. A mixture (second component) consisting of 60 to 20% by weight of coalescing; And 0.01 to 0.2 parts by weight of a radical generator (third component) based on 100 parts by weight of the mixture. Further, optionally, as a matting agent, 0.01 to 1 part by weight of silica (SiO ₂ ) (fourth component) and / or colorant (fifth component) 1 having an average particle size of 1 to 10 µm or less with respect to 100 parts by weight of the mixture. It may further include a weight part or less, and may further include 1 part by weight or less of an organic nucleating agent (sixth component) consisting of sorbitol and rosin.

In the above resin mixture, a random polypropylene resin having a melt index (ASTM D1238) as a first component of 5 dg / min or less and containing 2 to 10% by weight of ethylene, an alpha olefin having 4 to 10 carbon atoms, or a mixture thereof It contains 40 to 80% by weight, but if the melt index exceeds 5dg / min, the workability during manufacturing the product is difficult to manufacture. In addition, when the content is less than 40% by weight or more than 80% by weight, there is a problem that the matte characteristics are lost, and preferably 50 to 70% by weight. On the other hand, the content of the alpha olefin contained in the random polypropylene is 2 to 10% by weight, but if the content is less than 2% by weight, the impact strength of the product is lowered. .

A melt index of less than 5 dg / min and a propylene of 10 to 30% by weight of propylene, an alpha olefin of 4 to 10 carbon atoms, or mixtures thereof, which are related to the transparency of the product, determined by the phase separation of the primary mixed resin and the difference in refractive index. The second component of the ethylene-propylene / alpha olefin copolymer containing or the ethylene-alpha olefin copolymer containing 10 to 30% by weight of ethylene is, for example, an ethylene-propylene copolymer or an ethylene-butene-1 copolymer. And ethylene-octene-1 copolymers, and the like amount thereof is 60 to 20% by weight. It is preferable that phase separation does not occur for transparency, but in this case, matt characteristics cannot be expected. In the case of phase separation, the smaller the difference in refractive index of the mixed resin, the better the permeability. Therefore, the comonomer content in the first component and the second component minimizes the difference in refractive index between the two components and can maintain the strength of the product. Content. Therefore, if the content of the comonomer of the second component is less than 10% by weight, there is a problem that the impact strength of the product decreases and transparency due to the difference in refractive index is lowered. When the content of the comonomer exceeds 30% by weight, the hardness of the product is lowered. The commercial property as it will fall. If the melt index exceeds 5dg / min, there is a problem that the matte characteristics disappear. In addition, since the second component has a lower crystallinity than the first component, the second component plays a role of shock absorption to improve the impact strength of the product.

On the other hand, the matte properties of the resin is primarily because the greater the difference between the melt index of the first component and the second component, the better the matte characteristics due to the phase separation and surface roughness due to the difference in viscosity and flowability.

By generating radicals in the mixture manufacturing process (reaction extruding), the melt index of the first component is increased and the melt index of the second component is decreased, thereby improving the matting properties and increasing the kneading properties of the two resins, thereby increasing the matting properties. The third component which improves the soft and fine feel without being used is 0.01 to 0.2 parts by weight of a radical generator with respect to 100 parts by weight of the mixture, for example Dicumylperoxide, 2-5-dimethyl-2,5- And di (tetrabutylperoxy) hexane. If the content is less than 0.01 parts by weight, no effect is generated, and if it exceeds 0.2 parts by weight, problems such as unmelted gel and odor are generated.

In addition, in the present invention, 0.01 to 1% by weight of silica (SiO ₂ ) having an average particle size of 1 to 10 μm of the fourth component used as the matting agent is added, but when the average particle size is less than 1 μm or less than 0.01 part by weight, There is no effect, and if it exceeds 10 mu m or more than 1 part by weight, it may cause a problem of dispersion. On the other hand, the fifth component used as a colorant may be TiO ₂ , iron oxide (iron oxide), titanium yellow (titanium yellow), the amount of use is less than 1 part by weight, if more than 1 part by weight is the problem that the transparency is lowered May result.

In addition, as a sixth component, in order to further improve transparency, the organic nucleating agent, which is composed of sorbitol and rosin, may be further included in an amount of 1 part by weight or less. In this case, when the content of the nucleating agent exceeds 1 part by weight, the transparency is no longer improved. .

The surface of the product is manufactured by a conventional blow molding, injection blow molding, and injection stretching blow molding method in which a composition according to the present invention as described above has a single layer structure or a laminated structure having two or more layers using the composition as a surface layer. It has fine irregularities on the surface and thus gives the product a matte characteristic by diffuse reflection of light, so it has excellent impact strength and transparency. The products thus produced include disposable containers, cosmetic containers and detergent containers.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Examples 1-5

The resin composition containing each component according to Table 1 was kneaded at 220 ° C. using a 30ψ twin screw compounder, and melt-extruded to prepare a product using a conventional blow molding machine. To produce a matt container. At this time, the extrusion temperature in the blow molding machine was 220 ℃, the mold temperature was 16 ℃. The first component was a random polypropylene resin having a melt index of 1.8 dg / min and 3.5 dg / min, and the second component was an ethylene-octene copolymer and a butene-propylene copolymer.

In order to measure the physical properties of the prepared matt container, the gloss characteristics (gloss) with a gloss detector (gloss), the result of measuring the impact strength with the Izod impact strength is shown in Table 1 below. At this time, the matte property is the value when light is reflected on the test material at a certain angle (45 °) and the reflected light is received at the same angle as the incident light. ). Transparency is measured by the Haze value, and haze is the ratio of light scattered by more than 2.5 ° through the object, the lower the value, the better the transparency. In particular, in the case of impact strength, when the impact on the specimen as a value measured at room temperature (23 ° C.) according to ASTM D 256, the specimen is not broken and is attached as “no damage” (ie, , The test method according to ASTM D 256 means that the strength is so high that it can not be measured), the impact strength at the time of fracture is indicated.

Example Composition ratio Matte characteristics Impact strength (kg.cm/cm) Transparency (haze) First component (wt%) Second component (wt%) Tertiary component (ppm) 4th ingredient (ppm) Fifth component (ppm) One 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 0.8) 500 - - 4.7 No damage 65 2 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 0.8) 500 - Sorbitol 2,500 4.5 No damage 62 3 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 3.0) 500 - - 15 No damage 65 4 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 3.0) 1,000 - - 4.1 No damage 62 5 60%, C ₂ = 2.5%, C ₄ = 5.0% (MI = 3.5) 40%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 0.8) 500 6μm silica 3,000 - 5.5 No damage 73

Comparative Examples 1 to 10

Comparative Example 1 is a matte glass by conventional corrosion, Comparative Example 2 is a conventional matte PET, in the case of Comparative Examples 3 to 6, the first component is a group consisting of homopolypropylene, impact polypropylene, and random polypropylene The second component was selected from linear high density polyethylene (homopolymer). In addition, the comparative example 7 is a case where the radical generator which is a 3rd component is not used in this invention, and the comparative examples 8-10 use the 1st component in excess compared with this invention (comparative example 8), or 2nd The comonomer content in the component is outside the range defined in the present invention (Comparative Example 9) or when the second component does not contain ethylene as a comonomer (Comparative Example 10). The composition characteristics and physical property test results of the blend used in the comparative example are shown in Table 2 below.

Comparative example Composition ratio Glossiness Impact Strength (kgcm / cm) Transparency (haze) First ingredient Second ingredient Third ingredient One Matte Glass (Corrosion) 7.5 0 50 2 Matte PET (Coating) 7.0 5 67 3 Random PP 50% (MI = 1.8) HDPE 50% (MI = 0.3) - 4.7 18 91 4 Homo PP 50% (MI = 1.8) HDPE 50% (MI = 0.3) - 4.4 12 95 5 Impact PP 50% (MI = 1.8) HDPE 50% (MI = 3.0) 400 ppm 4.2 88 90 6 Random PP 50% (MI = 1.8)) HDPE 50% (MI = 3.0) 400 ppm 9.0 60 86 7 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 0.8) - 32 No damage 50 8 90%, C ₂ = 3.5% (MI = 1.8) 10%, C ₂ / C ₈ copolymer (C ₈ = 15%, MI = 0.8) 500 ppm 21 25 42 9 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₂ / C ₈ copolymer (C ₈ = 35%, MI = 0.8) 500 ppm 5.5 No damage 83 10 60%, C ₂ = 3.5% (MI = 1.8) 40%, C ₄ / C ₃ copolymer (C ₃ = 15%, MI = 0.8) 500 ppm 15 No damage 85

As a result of comparing Example 1 and Comparative Example 7, it was confirmed that the presence or absence of the use of a radical generator as a third component in the present invention on the matt properties of the molded article according to the present invention. Further, in view of the results of Comparative Examples 8 to 10, any one of the selection of the first component and the second component, the content in each of these compositions, and the comonomer content in the first component and the second component is When it is out of the range, it has been confirmed that the characteristics of the present invention can be achieved to improve the matting properties, impact strength, and transparency at the same time or more than the prior art.

As can be seen through the above examples and comparative examples, the product manufactured using the composition according to the present invention after forming the container, to form fine irregularities on the surface without post-processing, such as corrosion or coating, the light is diffusely reflected It has a matte property, and the problem of poor transparency, which is a problem of the prior art using polyolefin, is remarkably improved to have a transparency level of a coated PET container or a Frost glass container, and a container that can be generated during storage, transportation, or use due to its excellent impact strength. Can solve the problem of breakage.

Claims (8)

40 to 80 weight percent of a random polypropylene resin comprising 2 to 10 weight percent ethylene, 4 to 10 carbon olefins or a mixture thereof having a melt index of 5 dg / min or less; And Ethylene-propylene / alphaolefin copolymers having a melt index of 5 dg / min or less and containing 10 to 30% by weight of propylene, alphaolefins or mixtures thereof, or ethylene-alphaolefin copolymers containing 10 to 30% by weight of ethylene. A mixture consisting of 60 to 20% by weight; And A polyolefin resin composition for blow molding having excellent matting properties, impact strength and transparency, comprising 0.01 to 0.2 parts by weight of a radical generator with respect to 100 parts by weight of the mixture. The method of claim 1, wherein the composition further comprises 0.01 to 1 part by weight of silica (SiO ₂ ) and / or 1 part by weight or less of a colorant having an average particle size of 1 to 10 µm or less with respect to 100 parts by weight of the mixture. Blow molding polyolefin resin composition excellent in matt properties, impact strength and transparency. The polyolefin resin composition of claim 1, wherein the composition further comprises 1 part by weight or less of an organic nucleating agent consisting of sorbitol and rosin based on 100 parts by weight of the mixture. . 40 to 80 weight percent of a random polypropylene resin comprising 2 to 10 weight percent ethylene, 4 to 10 carbon olefins or a mixture thereof having a melt index of 5 dg / min or less; And an ethylene-propylene / alpha olefin copolymer comprising a melt index of 5 dg / min or less and 10 to 30% by weight of propylene, an alpha olefin or a mixture thereof or an ethylene-alphaolefin air comprising 10 to 30% by weight of ethylene. A mixture consisting of 60 to 20% by weight of the copolymer; And a polyolefin resin composition having excellent matting properties, impact strength and transparency comprising 0.01 to 0.2 parts by weight of a radical generator with respect to 100 parts by weight of the mixture, by using a method of blow molding, injection blow molding or injection stretch blow molding. Product characterized in that. The product according to claim 4, wherein the product has a single layer structure or a laminated structure of two or more layers having the composition as a surface layer. The polyolefin resin composition according to claim 4, wherein the polyolefin resin composition further comprises 0.01 to 1 part by weight of silica (SiO ₂ ) having an average particle size of 1 to 10 µm or less and / or 1 part by weight or less to 100 parts by weight of the mixture. Product made with. The product according to claim 4, wherein the polyolefin resin composition further comprises 1 part by weight or less of an organic nucleating agent consisting of sorbitol and rosin based on 100 parts by weight of the mixture. The product of claim 4, wherein the product comprises a disposable container, a cosmetic container, and a detergent container.