TW201500430A - Polyolefin resin composition - Google Patents

Abstract

The object of the present invention is to provide a polyolefin resin composition with excellent weather resistance. The present invention relates to a polyolefin-based composition comprising a polyolefin-based resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber. Preferably, in relative to 100 parts by mass of the polyolefin resin, the resin composition contains 0.05 to 75 parts by mass of aliphatic polycarbonate resin, 0.01-20 parts by mass of acid-modified polypropylene, and 0.01-5 parts by mass of ultraviolet absorber.

Description

Polyolefin resin composition Field of invention

The present invention relates to a polyolefin resin composition. More specifically, it is a polyolefin-based resin composition excellent in weather resistance, and a molded body formed from the composition.

Background of the invention

Polyolefin-based resins typified by polyethylene and polypropylene are widely used as general-purpose polymers in view of low cost, ease of processing, robustness, lightness, and low cost of production. In particular, polypropylene is used in automotive parts, electrical/electronic machine parts, industrial materials, furniture, stationery, daily/groceries, containers/packaging due to its excellent heat resistance, transparency and good formability. Wide range of uses such as supplies, toys, leisure products and medical supplies.

Among them, polypropylene which is excellent in weather resistance is required for use in automobiles and fields. In order to improve the light resistance and heat resistance of polypropylene, it is known to add various weathering enhancers such as an ultraviolet absorber and a light stabilizer.

However, polyolefin-based resins are difficult to be compatible with ultraviolet absorbers and light stabilizers, and plate-out and bleeding are formed during molding. Out), exudation during storage, etc., and it is difficult to obtain a product which is stable in quality over a long period of time.

Patent Document 1 describes the transmission and the third A combination of a compound and a benzotriazole-based compound is disclosed in Patent Document 2, and a combination of a benzoate-based compound and a benzotriazole-based compound is described. In Patent Document 3, the transmission and the 2,5-double are described. 5-tertiary butyl benzoate Azolyl (2)] thiophene, three The combination of the compound and the benzotriazole-based compound can prevent precipitation during molding, and bleed during molding, storage, and self-molding. However, in Patent Documents 1, 2, and 3, although it is described that the NOx resistance is excellent, the mechanical strength and the stretchability are not described.

Advanced technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2000-136270

Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-159945

Patent Document 3: Japanese Laid-Open Patent Publication No. 2000-191918

Summary of invention

The present invention is intended to provide a polyolefin-based resin composition which is excellent in weather resistance and which does not deteriorate in mechanical strength and stretchability, and a molded article formed from the composition.

The present inventors have intensively studied in order to achieve the above problems. As a result, it was found that the polyolefin resin contains an aliphatic polycarbonate resin. The acid-modified polypropylene and the ultraviolet absorber can obtain a polyolefin-based resin composition which is excellent in weather resistance and which does not deteriorate in mechanical strength and stretchability, and further studies have been completed to complete the present invention. That is, the present invention includes, for example, the subject matter described below.

Item 1. A polyolefin resin composition comprising a polyolefin resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber.

The polyolefin resin composition according to item 1, which comprises 0.05 to 75 parts by mass of the aliphatic polycarbonate resin and 0.01 to 20 parts by mass of the acid-modified polypropylene, based on 100 parts by mass of the polyolefin resin. The ultraviolet absorber is 0.01 to 5 parts by mass.

The polyolefin resin composition according to item 1 or 2, wherein the polyolefin resin is a polypropylene resin.

The polyolefin resin composition according to item 3, wherein the polypropylene resin is at least one selected from the group consisting of polypropylene and a copolymer of propylene and another olefin.

The polyolefin resin composition according to item 4, wherein the copolymer of propylene and another olefin is a propylene-ethylene copolymer.

The polyolefin resin composition according to any one of the items 1 to 5, wherein the aliphatic polycarbonate resin is obtained by polymerizing carbon dioxide and an alkylene oxide in the presence of a metal catalyst.

The polyolefin resin composition according to any one of the items 1 to 6, wherein the aliphatic polycarbonate resin is a polypropylene carbonate.

The polyolefin-based resin composition according to any one of items 1 to 7, wherein the acid-modified polypropylene-based maleic acid-modified polypropylene or maleic anhydride-modified polymer Propylene.

The polyolefin resin composition according to any one of items 1 to 8, wherein the ultraviolet absorber is a benzoate-based ultraviolet absorber.

Item 10. A molded article obtained by molding the polyolefin resin composition according to any one of Items 1 to 9.

The polyolefin-based resin composition of the present invention contains an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber in addition to the polyolefin-based resin, and has excellent weather resistance and maintains mechanical strength and stretchability. . In particular, the polyolefin-based resin composition of the present invention contains a specific ratio of the aliphatic polycarbonate resin, the acid-modified polypropylene, and the ultraviolet absorber in the polyolefin-based resin, and the weather resistance is further improved. Mechanical strength, stretchability, and the like can be preferably maintained.

Form for implementing the invention

Hereinafter, the polyolefin-based resin composition of the present invention will be specifically described.

The polyolefin-based resin composition of the present invention contains an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber in addition to the polyolefin-based resin, and preferably contains an aliphatic polycarbonate resin in a specific ratio. Acid modified polypropylene and UV absorber.

The polyolefin-based resin which can be used in the present invention contains a derived from an alkene A polymer of monomer units of a hydrocarbon. For example, a polyethylene resin, an ethylene-carboxylic acid alkenyl ester copolymer resin, an ethylene-unsaturated carboxylic acid alkyl ester copolymer resin, a polypropylene resin, a polybutene resin, and a poly(4-methyl group) can be exemplified. A ketone-1-pentene resin or the like.

As the polyethylene resin, polyethylene is preferably exemplified. The polyethylene is not particularly limited, and examples thereof include low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene.

The "carboxylic acid alkenyl ester" of the ethylene-carboxylic acid alkenyl ester copolymer resin may, for example, be vinyl acetate, vinyl propionate, vinyl butyrate, isopropenyl acetate or allyl acetate. Among them, vinyl acetate is preferred. As the ethylene-carboxylic acid alkenyl ester copolymer resin, specifically, an ethylene-vinyl acetate copolymer is particularly preferable.

The "unsaturated carboxylic acid alkyl ester" of the ethylene-unsaturated carboxylic acid alkyl ester copolymer resin may, for example, be methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate or ethyl methacrylate. , propyl methacrylate and the like. Among them, methyl acrylate and methyl methacrylate are preferred. As the ethylene-unsaturated carboxylic acid alkyl ester copolymer resin, specifically, an ethylene-methyl acrylate copolymer or an ethylene-methyl methacrylate copolymer is particularly preferable.

As the polypropylene-based resin, polypropylene or a copolymer of propylene and another olefin is preferably exemplified. The "other olefin" herein is preferably ethylene, butene, pentene, hexene, octene or the like. These "other olefins" may be used singly or in combination of two or more kinds (that is, a copolymer with propylene). As a polypropylene resin, more specifically, a polypropylene An olefin, or a propylene-ethylene copolymer, a propylene-ethylene-butene copolymer, a propylene-butene copolymer, a propylene-hexene copolymer, a propylene-octene copolymer, etc., particularly preferably propylene or propylene-ethylene Copolymers are preferred.

The polyolefin resin may be used singly or in combination of two or more. Among the polyolefin-based resins, a polypropylene-based resin is preferred from the viewpoint of excellent compatibility with an aliphatic polycarbonate resin, and is preferably selected from polypropylene, and propylene and other olefins. At least one substance of the group consisting of copolymers, a propylene-ethylene copolymer is more suitably used.

The method for producing the polyolefin-based resin may be a method of radically polymerizing an olefin using an initiator such as a peroxide, or a method of polymerizing an olefin by a vapor phase method, a solution method or the like in the presence of a polymerization catalyst. As the polymerization catalyst, a Ziegler-Natta catalyst, an organic metallocene catalyst, or the like can be used.

The molecular weight of the above polyolefin-based resin is not particularly limited, and is, for example, a weight average molecular weight of from 20,000 to 6,000,000, preferably from 30,000 to 6,000,000, more preferably from 100,000 to 5,000,000.

If the weight average molecular weight of the polyolefin-based resin is 20,000 or more, the weather resistance of the obtained polyolefin-based resin composition can be further improved. In addition, when the weight average molecular weight of the polyolefin resin is 6,000,000 or less, the molding process of the obtained polyolefin resin composition can be made easier.

In addition, the weight average molecular weight is a value calculated by preparing a chloroform solution having a concentration of a polyolefin resin of 0.5% by mass, and measuring it by high performance liquid chromatography and measuring the weight under the same conditions. The average molecular weight is compared to polystyrene. Furthermore, the measurement conditions are as follows Said.

Column: GPC column

(trade name of Tosoh Corporation, TSK GEL Multipore H _XL -M)

Column temperature: 40 ° C

Effervescent solution: chloroform

Flow rate: 1mL/min

The fluidity of the resin is represented, for example, by a melt flow rate (MFR, unit: g/10 minutes) measured by a method specified in JIS K 7210:1999. The polyolefin-based resin used in the present invention is a value measured by a temperature of 230 ° C and a load of 2.16 kg, preferably in the range of 0.5 to 100 (g/10 minutes), more preferably 1 to 1 by the method. 75 (g/10 points) range. When the value of the MFR of the polyolefin-based resin is 0.5 or more, the fluidity of the obtained polyolefin-based resin composition is not too low, and it can be preferably molded by an injection molding method or the like. In addition, if the MFR value of the polyolefin resin is 100 or less, the weather resistance of the obtained polyolefin resin composition can be further improved.

The aliphatic polycarbonate resin used in the present invention is not particularly limited. For example, it is preferred to use a polymerization reaction between an alkylene oxide and carbon dioxide in the presence of a metal catalyst.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, epoxy isobutane, 1-epoxypentane, and 2-epoxypentane. Alkane, 1-epoxyhexane, 1-epoxyoctane, 1-epoxydecane, epoxycyclopentane, epoxycyclohexane, epoxy styrene, vinyl epoxy cyclohexane, 3- benzene Propylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthyl propylene oxide, 3-phenoxy propylene oxide, 3-naphthyloxy propylene oxide, butadiene monooxide, 3-vinyloxy propylene oxide, 3-trimethyldecyloxy propylene oxide, and the like. Among these alkylene oxides, ethylene oxide and propylene oxide are suitably used from the viewpoint of having high polymerization reactivity with carbon dioxide, and propylene oxide is more preferably used. Further, these alkylene oxides may be used singly or in combination of two or more. For example, when the ethylene oxide is used alone, the aliphatic polycarbonate resin is polyethylene carbonate; further, when the propylene oxide is used alone, the aliphatic polycarbonate resin is polypropylene carbonate.

Examples of the metal catalyst include an aluminum catalyst and a zinc catalyst. Among these, a zinc catalyst is preferably used because of high polymerization activity in the polymerization reaction between alkylene oxide and carbon dioxide, and an organic zinc catalyst is preferably used among the zinc catalyst.

Examples of the organic zinc catalyst include an organic zinc catalyst such as zinc acetate, diethyl zinc, and dibutyl zinc; and a primary amine, a dihydric phenol, a divalent aromatic carboxylic acid, and an aromatic An organic zinc catalyst obtained by reacting a compound such as a hydroxy acid, an aliphatic dicarboxylic acid or an aliphatic monocarboxylic acid with a zinc compound. Among these organic zinc catalysts, an organic zinc catalyst obtained by reacting a zinc compound or an aliphatic dicarboxylic acid with an aliphatic monocarboxylic acid is preferably used because of its high polymerization activity.

The amount of the metal catalyst used in the polymerization reaction is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the alkylene oxide. If the amount of the metal catalyst used is 0.001 part by mass or more, the polymerization reaction can be more preferably carried out. Also, if it is made of metal catalyst When the amount is 20 parts by mass or less, the effect corresponding to the amount used is preferably obtained.

In the above polymerization reaction, the method of reacting the alkylene oxide with carbon dioxide in the presence of a metal catalyst is not particularly limited. For example, in the autoclave, the above-mentioned alkylene oxide and metal catalyst are charged. And, if necessary, charging the reaction solvent and mixing, then injecting carbon dioxide and reacting it.

The reaction solvent to be used as needed in the above polymerization reaction is not particularly limited, and various organic solvents can be used. Specific examples of the organic solvent include an aliphatic hydrocarbon solvent such as pentane, hexane, octane, decane or cyclohexane; an aromatic hydrocarbon solvent such as benzene, toluene or xylene; and methyl chloride; Dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1- a halogenated hydrocarbon solvent such as chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chlorobenzene or bromobenzene; a carbonate solvent such as dimethyl carbonate, diethyl carbonate or propylene carbonate; .

The reaction solvent is preferably used in an amount of from 300 to 10,000 parts by mass based on 100 parts by mass of the alkylene oxide from the viewpoint of allowing the reaction to proceed smoothly.

The working pressure of the carbon dioxide used in the above polymerization reaction is not particularly limited, but is usually 0.1 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 0.1 to 5 MPa.

The polymerization temperature in the above polymerization reaction is not particularly limited, and is preferably from 30 to 100 ° C, preferably from 40 to 80 ° C. If the polymerization temperature is 30 ° C or more, the polymerization reaction can be carried out in a short time. Also, if you gather When the reaction temperature is 100 ° C or lower, side reactions are less likely to occur, and the yield can be further improved. Although the polymerization reaction time varies depending on the polymerization temperature, it cannot be generalized, and it is usually 2 to 40 hours.

After the completion of the polymerization reaction, the mixture is filtered and separated by filtration or the like, and if necessary, it is washed with a solvent or the like and then dried to obtain an aliphatic polycarbonate resin. In the present invention, the aliphatic polycarbonate resin may be used singly or in combination of two or more.

The aliphatic polycarbonate resin used in the present invention preferably has a weight average molecular weight of 10,000 to 2,000,000, preferably 20,000 to 1,000,000, more preferably 20,000 to 750,000. In addition, the weight average molecular weight is a chloroform solution having a concentration of an aliphatic polycarbonate resin of 0.5% by mass, and the measured value is the same as the method for measuring the weight average molecular weight of the polyolefin resin.

When the weight average molecular weight of the aliphatic polycarbonate resin is less than 10,000, the weather resistance of the polyolefin resin composition obtained by exuding the aliphatic polycarbonate resin from the polyolefin resin is lowered. In addition, when the weight average molecular weight of the aliphatic polycarbonate resin is 2,000,000 or less, the dispersibility to the polyolefin resin is further improved, and the weather resistance of the obtained polyolefin resin composition can be further enhanced.

In the polyolefin-based resin composition of the present invention, the content of the aliphatic polycarbonate resin is preferably 0.05 parts by mass or more, and more preferably 0.5 mass, based on 100 parts by mass of the polyolefin resin. The amount is preferably 1.0 part by mass or more, more preferably 20 parts by mass or more, and more preferably 40 parts by mass or more. Also, as an upper limit thereof, relative to a polyolefin resin 100 parts by mass is preferably 75 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less. The content of the aliphatic polycarbonate resin is preferably 0.05 to 75 parts by mass, more preferably 0.5 to 75 parts by mass, still more preferably 1.0 to 70 parts by mass, more preferably 100 parts by mass of the polyolefin resin. It is 20 to 60 parts by mass, and 40 to 60 parts by mass.

As the acid-modified polypropylene used in the present invention, for example, a polypropylene which is graft-modified with a dicarboxylic acid or an anhydride thereof, a derivative of an unsaturated carboxylic acid or the like is preferably used.

Examples of the dicarboxylic acid include maleic acid, fumaric acid, and itaconic acid. Further, examples of the anhydride of the dicarboxylic acid include maleic anhydride, fumaric anhydride, and itaconic anhydride. As a derivative of the unsaturated carboxylic acid: monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monoethyl itaconate, diethyl itaconate, Monodecylamine maleate, diammonium maleate, monodecyl fumarate, diammonium fumarate, monoammonium iconate, diammonium itaconate, and the like. Among these, maleic acid-modified polypropylene and maleic anhydride-modified polypropylene are suitably used from the viewpoint that the moldability is excellent and the molding process of the polyolefin-based resin composition is easy. The acid-modified polypropylene may be used singly or in combination of two or more.

The molecular weight of the acid-modified polypropylene is not particularly limited as long as it does not impair the effect of the present invention. For example, the weight average molecular weight is preferably 10,000 to 1,000,000, preferably 20,000 to 750,000, more preferably 30,000 to 500,000. Within the scope.

If the weight average molecular weight of the acid-modified polypropylene is 10,000 or more, the obtained aliphatic resin in the polyolefin resin composition The dispersed state of the resin can be made more uniform, and the weather resistance of the polyolefin-based resin composition can be further improved. In addition, if the weight average molecular weight of the acid-modified polypropylene is 1,000,000 or less, the molding process of the obtained polyolefin-based resin composition can be made easier.

In addition, the weight average molecular weight is a chloroform solution having a concentration of 0.5% by mass of the acid-modified polypropylene, and the value is measured in the same manner as the method for measuring the weight average molecular weight of the polyolefin resin.

The value of the MFR of the acid-modified polypropylene (measured by the method specified in JIS K 7210:1999) is 1 to 100 (g/10 minutes) at a temperature of 230 ° C and a load of 2.16 kg, preferably 2 to 2 50 (g/10 points) range. If the value of the MFR of the acid-modified polypropylene is 1 or more, the molding process of the obtained polyolefin-based resin composition can be made easier. In addition, when the value of the MFR of the polyolefin-based resin is 100 or less, the dispersion state of the aliphatic polycarbonate resin in the obtained polyolefin-based resin composition can be made more uniform, and the polyolefin-based resin composition can be weather-resistant. Sex can be improved.

In the polyolefin resin composition of the present invention, the content of the acid-modified polypropylene is preferably 0.01 parts by mass or more, preferably 0.1 parts by mass, based on 100 parts by mass of the polyolefin resin. More preferably, it is 0.2 mass part or more. In addition, the upper limit is preferably 20 parts by mass or less, and preferably 18 parts by mass or less, based on 100 parts by mass of the polyolefin resin. The content of the acid-modified polypropylene is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.2 to 18 parts by mass, per 100 parts by mass of the polyolefin-based resin.

If the content of the acid-modified polypropylene is 20 parts by mass or less, It is economical to be able to obtain an effect corresponding to the amount of use. In addition, when the content of the acid-modified polypropylene is 0.01 parts by mass or more, the dispersion state of the aliphatic polycarbonate resin in the obtained polyolefin-based resin composition can be made more uniform, and the polyolefin-based resin composition is Weather resistance can be improved.

As the ultraviolet absorber, for example, a benzotriazole-based ultraviolet absorber, three can be suitably used. It is a UV absorber, a benzophenone-based UV absorber, and a benzoate-based UV absorber.

Specific examples of the benzotriazole-based ultraviolet absorber include 2-(5-methyl-2-hydroxyphenyl)benzotriazole and 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-tri-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5 -di-tertiary pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tris-octylphenyl)benzotriazole, 2,2'-methylene Bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol].

As three Specific examples of the ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-three -2-yl]-5-(octyloxy)-phenol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tertiary butylanilino)- 1,3,5-three Wait.

Specific examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, and 4-ethoxy-2-hydroxybenzophenone. Ketone, 4-propoxy-2-hydroxybenzophenone, 4-butoxy-2-hydroxybenzophenone, 4-octyloxy-2-hydroxybenzophenone and the like.

Specific examples of the benzoate-based ultraviolet absorber include 2,4-di-tert-butylphenyl-3',5'-di-tertiarybutyl-4'-hydroxybenzoic acid. Ester, 2-hydroxybenzoic acid ester, 4-tris-butylphenyl salicylate, 4-trioctylphenyl salicylate, and the like.

Among these, a benzoate-based ultraviolet absorber which exhibits a high weather resistance improving effect is suitably used.

The ultraviolet absorber may be used singly or in combination of two or more.

In the polyolefin resin composition of the present invention, the content of the ultraviolet absorber is preferably 0.01 parts by mass or more, and more preferably 0.02 parts by mass or more, based on 100 parts by mass of the polyolefin resin. More preferably, it is 0.05 mass part or more. In addition, the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less based on 100 parts by mass of the polyolefin resin. In particular, the content of the ultraviolet absorber is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the polyolefin resin. If the content of the ultraviolet absorber is 5 parts by mass or less, it is economical because an effect corresponding to the amount of use can be obtained. In addition, when the content of the ultraviolet absorber is 0.01 parts by mass or more, the weather resistance of the polyolefin resin composition can be further improved.

In addition, when the total mass of the polyolefin resin, the aliphatic polycarbonate resin, and the acid-modified polypropylene is 100 parts by mass, the ultraviolet absorber is preferably contained in an amount of 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass.

The method for producing the polyolefin-based resin composition of the present invention is not particularly limited, and examples thereof include a polyolefin resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber in an arbitrary order. , through Henschel mixer, screw stirrer (ribbon blender), a stirrer or the like to mix and form a homogeneous mixture, and then melt-kneading the mixture; and a polyolefin resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber A method of removing the solvent, etc. after dissolving in a solvent or the like, and the like. Among such a production method, a polyolefin resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and the like are suitably used from the viewpoint that the production of the composition is easy and a uniform composition can be obtained. A method in which a UV absorber is melt-kneaded.

The method of melt-kneading a polyolefin-based resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber is not particularly limited, and a vent-type twin-screw extruder (vent-type) is used. Twin-screw extruder), Bamburi mixer, kneading machine, mixing roll, etc.

The shape of the polyolefin-based resin composition of the present invention is not limited, and any shape such as a strand-shaped shape, a sheet shape, a flat shape, or a strand cut into a pellet of an appropriate length may be used. In particular, in order to apply injection molding which is easy to form, it is preferable to form a pellet having a length of 2 to 50 mm.

In the polyolefin-based resin composition of the present invention, other additives such as a metal deactivator, a heat stabilizer, a neutralizing agent, and a foam inhibitor may be used without departing from the effects of the present invention. ), flame retardant, flame retardant, dispersant, antistatic agent, lubricant, anti-blocking agent such as antimony oxide, colorant such as dye or pigment, glue, plasticizer, etc. Glass shards, mica, glass powder, glass beads, talc, A plate-like, powder-like inorganic compound or whisker such as clay, alumina, carbon black, or ash. The amount of addition of the polyolefin resin composition is, for example, preferably 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the polyolefin resin composition.

The molding system of the present invention is a molded article formed from the polyolefin resin composition of the present invention.

Examples of the method for obtaining the molded body of the present invention include an injection molding method, a compression molding method, an injection compression molding method, a gas injection injection molding method, and a foam injection molding method. An inflation method, a T-die method, a calendaring method, a blow molding method, a vacuum forming method, a pressure forming method, and the like. In the case of the film or sheet of the molding system of the present invention, at least one layer of a multilayer structure of different resins is formed by a blow molding method, a T-die method, or a calendering method, or an extrusion layering method or heat is used. Layering, dry lamination, etc. to form a film, thereby enabling multilayering. Further, the obtained film or sheet can be uniaxially or biaxially stretched by a roll drawing method, a tenter stretching method, a tubular stretching method, or the like. And use. In the molded body of the present invention, for example, surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment or the like can be applied.

The molded article of the present invention can be used as, for example, an electric/electronic component, a building component, an automobile component, a mechanical component, a commodity, an industrial material, or the like. Specifically, as an electric/electronic component, for example, a photocopying machine, a personal computer, a printer, an electronic musical instrument, a home game machine, and carrying a casing or an internal component of a game machine or the like; as a building component, for example, a curtain member, a louver member, a roof panel, a heat insulating wall, a regulator, a plastic short column, a ceiling spreader, etc.; For example: fenders, overfenders, grille guards, cowl louver, wheel caps, side protectors, sides Side molding, side lower skirt, front grill, roof rail, rear spoiler, bumper, lower dashboard ( Lower instrument panel), trim, etc.; as mechanical parts, for example, gears, screws, springs, bearings, levers, cams, ratchets, rolls, etc.; as daily necessities, for example, various tablewares, various cosmetics Parts, cartons, packaging film, Cling film, Portable laminated paper bag, prepaid card, saw blade for household cling film, food tray, garbage bag, laminate bag , bags, labels, thermoforms (thermoforming), packaging tape, fabric (clothing/interior decoration), carpet, sanitary material, packaging film, box, food cup, etc.; as industrial materials, for example, fiber binder, paper coating, and then Agents, agricultural films, machine-spun yarns, slit yarns, ropes, meshes, filters, fabrics (industrial materials), biopost bags, waterproof sheets, soil bags, and the like.

According to the present invention, the mechanism for obtaining a polyolefin-based resin composition excellent in weather resistance is not clear, and although a restrictive explanation is not desired, it is presumed as follows. It is considered that the crystal form of the polyolefin resin is not affected by its crystallinity, crystal form (size of spherulites), and the aliphatic polycarbonate resin is permeable to acid. The modified polypropylene is dispersed in the amorphous portion of the polyolefin resin. In addition, the ultraviolet absorber is not only present in the polyolefin resin but also in the aliphatic polycarbonate resin which is present in the polyolefin resin in a dispersed state. As a result, the bleed out does not occur, and the weather resistance of the polyolefin-based resin is maintained because it is gradually released from the aliphatic polycarbonate resin into the polyolefin-based resin over time.

Example

Hereinafter, the present invention will be specifically described by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited to the Examples.

[Evaluation]

The weight average molecular weight of the aliphatic polycarbonate resin obtained by the production example was measured by the following method, and the tensile test and accelerated weather resistance test of the polyolefin resin composition obtained from the examples and the comparative examples. .

(1) Determination of weight average molecular weight (Mw)

A chloroform solution having a concentration of the measurement target resin of 0.5% by mass was prepared and measured by high performance liquid chromatography. The molecular weight was calculated by comparison with polystyrene having a known weight average molecular weight measured under the same conditions. Further, in the same manner, the number average molecular weight (Mn) was determined, and the molecular weight distribution (Mw/Mn) was calculated. Furthermore, the measurement conditions are as follows.

Measuring machine: HLC-8020 (made by Tosoh Co., Ltd.)

Column: GPC column

(Tokyo Co., Ltd. trade name TSK GEL Multipore H _XL -M)

Column temperature: 40 ° C

Effervescent solution: chloroform

Flow rate: 1mL/min

(2) Tensile test

According to JIS K 7161:1994, the following test pieces and measuring devices were used to measure the fracture stress and the strain at break. Further, the larger the fracture stress, the stronger the strength of the material. Further, the larger the strain at break, the more excellent the stretchability, and it can be said that the material has high toughness.

Test piece: dumbbell shape 4

Measuring machine: tensile testing machine manufactured by Shimadzu Corporation, AUTOGRAPH AGS-J

Stretching speed: 50mm/min

Measuring temperature: 25 ° C

(3) Accelerated weather resistance test

According to JIS A 1415:1999 "accelerated exposure testing method", an accelerated weathering test was carried out using the following test piece and measuring device.

Test piece: dumbbell type (neck size: length 10 mm, width 4 mm, thickness 0.2 mm)

Measuring machine: Sunshine Super long life weather meter

(WEL-SUN-HC type) Suga Test Instruments Co., Ltd.

Measurement conditions: Sunshine carbon arc, light cycle (120 minutes, rainfall 18 minutes)

Black panel temperature: 45 ° C

[Production Example 1] (Production of Organic Zinc Catalyst)

In a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux cooling tube in a volume of 300 mL, 8.1 g (100 mmol) of zinc oxide, 12.7 g of glutaric acid (96 mmol), and 0.1 g of acetic acid were charged. (2 mmol) and toluene 130 g (150 mL). Next, after replacing the inside of the reaction system with a nitrogen gas atmosphere, the temperature was raised to 55 ° C, and the reaction was carried out by stirring at the same temperature for 4 hours. Thereafter, the temperature was raised to 110 ° C, and further stirred at the same temperature for 4 hours to cause azeotropic dehydration. After only removing water, the mixture was cooled to room temperature to obtain a reaction liquid containing an organic zinc catalyst.

A part of the reaction liquid was separated, and the result of IR was measured for the organic zinc catalyst obtained by filtration using a device manufactured by Thermo Nicolet Japan Co., Ltd. (trade name: AVATAR360), and a peak based on a carboxylic acid group was not observed.

[Production Example 2] (Production of Polypropylene Carbonate)

In the system in which the autoclave having a capacity of 1 L of a stirrer, a gas introduction tube, and a thermometer was replaced with a nitrogen gas atmosphere, a reaction liquid containing the organic zinc catalyst obtained in Production Example 1 was charged in an amount of 8.0 mL (containing a zinc-touch). Medium 1.0 g), hexane 131 g (200 mL) and propylene oxide 46.5 g (0.80 mol). Next, carbon dioxide was added under stirring, and the reaction system was replaced with a carbon dioxide gas atmosphere, and carbon dioxide was filled until the reaction system became 1.5 MPa. Thereafter, the temperature was raised to 60 ° C, and the polymerization reaction was carried out for 6 hours while replenishing the carbon dioxide consumed by the reaction.

After the completion of the reaction, the autoclave was cooled, depressurized, and filtered, and then dried under reduced pressure to obtain 80.8 g of poly propylene carbonate. The obtained polypropylene carbonate The weight average molecular weight was 336,000 (Mw/Mn = 9.02).

Examples 1 to 4 and Comparative Examples 1 to 6

According to the formulation of Table 1, an ethylene-propylene block copolymer (PP-based copolymer) (manufactured by Sumitomo Chemical Co., Ltd., trade name Noblen AZ564, MFR = 30 g/10 min), horse Acid-modified polypropylene (acid-modified PP) (manufactured by Mitsui Chemicals, Inc., trade name: Admer QE800, MFR = 9.1 g/10 min), polypropylene acrylate obtained in Production Example 1. Ester (PPC) and UV absorber (benzoate UV absorber) (manufactured by Ciba Japan Co., Ltd., trade name TINUVIN 120), using a mixer (Toyo Seiki Co., Ltd.) The company (Toyo Seiki Seisakusho Co., Ltd.) Labo Plasto Mill roll mixer R60 type) was kneaded at a set temperature of 180 ° C and a number of revolutions of 40 rpm for 5 minutes to obtain a molten mixture.

Weighing about 5g of the molten mixture to an aluminum template (10cm × 10cm) with a thickness of 0.6mm, using a PET sheet (pet sheet), further sandwiched by a stainless steel plate, and putting it into a stamping device heated to above Tg (glass transfer point) to Pressing the pressure of 5.0~10.0Mpa for about 2 minutes. After the press, in order to remove the residual heat, a press device cooled to room temperature or lower was placed, and the sample for tensile test (test piece) was obtained by pressing at a pressure of 0.1 to 1.0 MPa for about 1 minute.

The period (500 hours) prescribed for the accelerated weather resistance test was carried out using the obtained test piece. The tensile test was carried out using the test piece after the accelerated test, and the fracture stress and the fracture strain were measured. The results are shown in Table 1.

Comparative Example 7~12

A test piece was produced and evaluated in the same manner as in Comparative Examples 1 to 6, except that a benzoate-based ultraviolet absorber was used, and a hindered amine-based antioxidant (manufactured by Ciba Japan Co., Ltd., trade name: CHIMASSORB 944 FDL) was used.

Comparative Example 13~18

A test piece was produced and evaluated in the same manner as in Comparative Examples 1 to 6, except that a benzoate-based ultraviolet absorber was used, and a hindered phenol-based antioxidant (manufactured by Sumitomo Chemical Co., Ltd., trade name SUMIILIR BHT) was used.

Further, the hindered amine-based antioxidant and the hindered phenol-based antioxidant are a resin additive (light stabilizer) used for improving the weather resistance (especially, stability against light) of the resin in parallel with the ultraviolet absorber. Therefore, in the case of Table 1, these are collectively described as "light stabilizers".

【Table 1】

As is apparent from Examples 1 to 4 and Comparative Examples 1 to 18 shown in Table 1, it was apparent that the polyolefin resin composition of the present invention was subjected to a tensile test machine even after the weather resistance test. The strength is maintained, so the weather resistance is significantly improved.

Claims (10)

A polyolefin resin composition comprising a polyolefin resin, an aliphatic polycarbonate resin, an acid-modified polypropylene, and an ultraviolet absorber. The polyolefin-based resin composition of claim 1, which comprises 0.05 to 75 parts by mass of an aliphatic polycarbonate resin and 0.01 to 20 parts by mass of an acid-modified polypropylene, and a UV absorber, based on 100 parts by mass of the polyolefin resin. 0.01 to 5 parts by mass. The polyolefin resin composition according to claim 1 or 2, wherein the polyolefin resin is a polypropylene resin. The polyolefin resin composition according to claim 3, wherein the polypropylene resin is at least one selected from the group consisting of polypropylene and a copolymer of propylene and another olefin. The polyolefin-based resin composition of claim 4, wherein the copolymer of propylene and another olefin is a propylene-ethylene copolymer. The polyolefin-based resin composition according to any one of claims 1 to 5, wherein the aliphatic polycarbonate resin is obtained by polymerizing carbon dioxide and an alkylene oxide in the presence of a metal catalyst. The polyolefin-based resin composition according to any one of claims 1 to 6, wherein the aliphatic polycarbonate resin is a polypropylene carbonate. The polyolefin-based resin composition according to any one of claims 1 to 7, wherein the acid-modified polypropylene is a maleic acid-modified polypropylene or a maleic anhydride-modified polypropylene. The polyolefin resin composition according to any one of claims 1 to 8, wherein the purple The external absorbent is a benzoate-based ultraviolet absorber. A molded article formed by the polyolefin-based resin composition according to any one of claims 1 to 9.