JP2022141595A - Resin composition, molding, and fluidity improver for polyolefin resin - Google Patents

Abstract

To provide a polyolefin resin composition which is excellent in moldability while maintaining mechanical strength of a polyolefin resin.SOLUTION: The resin composition contains a polyolefin resin (A) and a rosin acid (B). The weight average molecular weight of the rosin acid (B) is 280-340, and the content of the rosin acid (B) is 0.1-5 pts.mass based on 100 pts.mass of the polyolefin resin (A).SELECTED DRAWING: None

Description

The present invention relates to a resin composition, a molded article, and a fluidity improver for polyolefin resins.

Since polyolefin resins have excellent mechanical properties, they are processed into injection-molded articles, blow-molded articles, films, sheets, fibers, and the like, and are used for various purposes.

These polyolefin resins have excellent impact strength, but have poor fluidity when melted, and cause problems such as melt fracture when subjected to high-speed molding. For this reason, additives such as lubricants are usually added to polyolefin resins to lower the apparent flow viscosity when melted, thereby improving molding processability and increasing the throughput rate to improve productivity. (Patent Document 1).

However, when a conventional lubricant is used, there is a problem that the mechanical strength of the polyolefin resin is lowered while the melt fluidity is improved as the amount of the lubricant is increased.

JP 2012-009754 A

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyolefin resin composition that maintains the mechanical strength of polyolefin resins and is excellent in moldability.

Another object of the present invention is to provide a novel fluidity improver capable of improving moldability of a polyolefin resin while maintaining the mechanical strength of the polyolefin resin.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by a composition comprising a polyolefin resin and a specific amount of rosin acid. Moreover, the present inventors have found that the above problems can be solved by a fluidity improver containing a specific rosin acid. That is, the present invention relates to the following resin composition, molded article, and fluidity improver.

1. Containing polyolefin resin (A) and rosin acid (B),
The rosin acid (B) has a weight average molecular weight of 280 to 340,
The resin composition, wherein the content of the rosin acid (B) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin (A).

2. Item 2. The resin composition according to item 1, wherein component (A) is at least one selected from the group consisting of polyethylene and polypropylene.

3. 3. The resin composition according to item 1 or 2, wherein the component (B) has an acid value of 130 to 200 mgKOH/g.

4. 4. The resin composition according to any one of items 1 to 3, wherein component (B) is at least one selected from the group consisting of natural rosin, refined rosin, hydrogenated rosin and disproportionated rosin.

5. A molded article obtained from the resin composition according to any one of items 1 to 4 above.

6. A fluidity improver for polyolefin resins, comprising a rosin acid (B) having a weight average molecular weight of 280-340.

7. 7. The fluidity improver for a polyolefin resin according to Item 6, wherein the polyolefin resin is at least one selected from the group consisting of polyethylene and polypropylene.

8. 8. The fluidity improver for polyolefin resins according to Item 6 or 7 above, wherein the component (B) has an acid value of 130 to 200 mgKOH/g.

9. 10. The polyolefin resin composition according to any one of items 6 to 9 above, wherein the component (B) is at least one selected from the group consisting of natural rosin, refined rosin, hydrogenated rosin and disproportionated rosin. Flow improver.

INDUSTRIAL APPLICABILITY The resin composition of the present invention maintains the mechanical strength of the polyolefin resin and has excellent flowability when melted, so that it has excellent moldability. Further, when the fluidity improver of the present invention is used in a polyolefin resin, it maintains the mechanical strength of the polyolefin resin and improves the fluidity when melted, thereby improving the moldability.

[Resin composition]
The resin composition of the present invention contains a polyolefin resin (A) (hereinafter also referred to as component (A)) and rosin acid (B) (hereinafter also referred to as component (B)).

<Polyolefin resin (A)>
Component (A) is not particularly limited, and various known components can be used. Component (A) may be used alone or in combination of two or more.

Component (A) is, for example, a homopolymer of an α-olefin having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene; 1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, Binary or ternary (co)polymers with other α-olefins having about 2 to 18 carbon atoms, such as 1-octadecene, and vinyl acetate, etc. can be mentioned.

Component (A) is, for example, polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, Ethylene resins such as ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, ethylene-1-octene copolymer; polypropylene, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer Propylene-based resins such as coalescence, propylene-ethylene-4-methyl-1-pentene copolymer, propylene-ethylene-1-hexene copolymer; 1-butene homopolymer, 1-butene-ethylene copolymer, 1 - 1-butene resin such as butene-propylene copolymer; 4-methyl-1-pentene resin such as 4-methyl-1-pentene homopolymer, 4-methyl-1-pentene-ethylene copolymer, etc. is mentioned.

Component (A) is a homopolymer of an α-olefin having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, etc., from the viewpoint of excellent moldability; , 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene , 1-decene, 1-octadecene, and other α-olefins having about 2 to 18 carbon atoms are preferably binary or ternary (co)polymers, and from the same point of view, from the group consisting of polyethylene and polypropylene At least one selected is more preferable.

It should be noted that if the component (A) is a copolymer of the α-olefin and unsaturated carboxylic acid, or a salt of the copolymer, it is not preferable because the moldability is lowered. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and maleic anhydride.

<Rosin acid (B)>
Component (B) is not particularly limited as long as it is a rosin acid having a weight average molecular weight (Mw) of 280 to 340, and various known compounds can be used. Component (B) may be used singly or in combination of two or more.

By using the component (B), the resin composition of the present invention has improved fluidity when the resin composition is melted, and is excellent in moldability, and can maintain the mechanical strength of the component (A). . When using a rosin-based resin other than the component (B), such as rosin esters, which are reaction products of rosin acid and alcohol, and various metal salts of rosin acid, the resin composition may be added when the resin composition is melted. Since the fluidity in the liquid is not improved or deteriorated, the moldability is not improved.

Component (B) is, for example, Pinus massonia, Pinus elliottii, Pinus merkusii, Pinus caribaea, Pinus kesiya, Pinus taeda and Natural rosin (gum rosin, tall oil rosin, wood rosin) derived from Pinus palustris, etc., refined rosin (hereinafter, natural rosin and refined rosin are collectively referred to as unmodified rosin), hydrogenated rosin, disproportionation Examples include rosin and resin acids contained in these rosins.

The above purified rosin can be obtained using various known means. Specifically, for example, it can be obtained using various known purification means such as distillation, extraction, recrystallization, and adsorption. The distillation method includes, for example, a method of distilling the natural rosin at a temperature of about 200 to 300° C. under a reduced pressure of about 0.01 to 3 kPa. Examples of the extraction method include a method in which the natural rosin is made into an alkaline aqueous solution, insoluble and unsaponifiable substances are extracted with various organic solvents, and then the aqueous layer is neutralized. Examples of the recrystallization method include a method of dissolving the natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and then adding an organic solvent as a poor solvent. Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, chlorinated hydrocarbon solvents such as chloroform, lower alcohols, ketones such as acetone, and acetic esters such as ethyl acetate. Poor solvents include, for example, n-hexane, n-heptane, cyclohexane, isooctane and the like. The adsorption method includes, for example, a method of bringing the natural rosin in a molten state or the natural rosin in solution dissolved in an organic solvent into contact with a porous adsorbent. Porous adsorbents include, for example, activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and microporous porous clays.

As for the above-mentioned purified rosin, the obtained purified rosin may be further subjected to disproportionation described later and hydrogenation described later either singly or in combination of two or more.

The disproportionated rosin can be obtained using various known means. Specifically, for example, it can be obtained by a method (disproportionation) of heating the unmodified rosin in the presence of a disproportionation catalyst. As the disproportionation catalyst, supported catalysts such as palladium-carbon, rhodium-carbon and platinum-carbon; metal powders such as nickel and platinum; various known iodides such as iodine and iron iodide can be used. The amount of the catalyst used is usually about 0.01 to 5 parts by weight, preferably about 0.01 to 1 part by weight, per 100 parts by weight of the unmodified rosin. The reaction temperature is about 100 to 300°C, preferably about 150 to 290°C.

As for the disproportionated rosin, the obtained disproportionation rosin may be further subjected to the above refining, disproportionation, and hydrogenation described later, either singly or in combination of two or more.

The hydrogenated rosin can be obtained using various known means. Specifically, for example, it can be obtained by hydrogenating the unmodified rosin using known hydrogenation conditions. Hydrogenation conditions include, for example, a method of heating the unmodified rosin to about 100 to 300° C. under a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst. Further, it is preferable that the hydrogen pressure is about 5 to 20 MPa and the reaction temperature is about 150 to 300.degree. As the hydrogenation catalyst, various known catalysts such as supported catalysts and metal powders can be used. Supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, platinum-carbon and the like. Metal powders include nickel, platinum, and the like. Among these, palladium, rhodium, ruthenium, and platinum-based catalysts are preferred because they increase the hydrogenation rate of the unmodified rosin and shorten the hydrogenation time. The amount of the hydrogenation catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, per 100 parts by mass of the unmodified rosin.

The hydrogenation may be carried out with the unmodified rosin dissolved in a solvent, if necessary. The solvent to be used is not particularly limited as long as it is inert to the reaction and easily dissolves the starting material and the product. Specifically, for example, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane and the like can be used singly or in combination of two or more. The amount of the solvent used is not particularly limited, but it may be used so that the solid content is usually 10% by mass or more, preferably in the range of about 10 to 70% by mass, based on the unmodified rosin.

As for the hydrogenated rosin, the obtained hydrogenated rosin may be further subjected to the above refining, hydrogenation and disproportionation operations singly or in combination of two or more.

For the purpose of improving the color tone of the component (B), the refined rosin, hydrogenated rosin, and disproportionated rosin may be further subjected to dehydrogenation treatment. The dehydrogenation treatment is not particularly limited, and ordinary conditions can be adopted. In the dehydrogenation treatment, for example, the component (B) is treated in the presence of a dehydrogenation catalyst in a closed vessel under an initial hydrogen pressure of less than 10 kg/cm2, preferably less than 5 kg/cm2, at a reaction temperature of about 100 to 300°C, preferably The lower limit is 200°C and the upper limit is 280°C. As the dehydrogenation catalyst, various known catalysts can be used without any particular limitation, but palladium-based, rhodium-based, and platinum-based catalysts are preferred, and they are usually supported on carriers such as silica and carbon. The amount of the catalyst to be used is generally about 0.01 to 5% by weight, with a lower limit of 0.05% and an upper limit of 3% by weight based on the component (B).

The above resin acids include, for example, abietic acid, neoabietic acid, levopimaric acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, tetrahydropimaric acid, tetrahydroiso pimaric acid, communic acid, dihydroagathic acid and the like.

Component (B) is at least one selected from the group consisting of natural rosin, refined rosin, hydrogenated rosin and disproportionated rosin, from the viewpoint of excellent mechanical strength and moldability of the resin composition. preferable.

(Physical properties of rosin acid (B))
The weight average molecular weight (Mw) of component (B) is 280-340. In addition, in this specification, a weight average molecular weight (Mw) is a polystyrene conversion value by a gel permeation chromatography (GPC) method.

When the weight average molecular weight of component (B) is 280 or more, the mechanical strength of the resin composition is excellent. When the weight average molecular weight of component (B) is 340 or less, the resin composition is excellent in mechanical strength and moldability. The weight-average molecular weight of component (B) is preferably about 300 to 320 from the viewpoint of excellent mechanical strength and moldability of the resin composition.

If the weight-average molecular weight of component (B) is more than 340, moldability and mechanical strength are lowered in the resin composition. Examples of such rosin acids include rosins modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride (unsaturated carboxylic acid-modified rosins), polymerized rosins, and the like. be done.

Component (B) is not particularly limited in physical properties other than the weight average molecular weight. The acid value of component (B) is preferably about 130 to 200 mgKOH/g from the viewpoint of excellent mechanical strength and moldability of the resin composition, and more preferably about 150 to 195 mgKOH/g from the same viewpoint. In the present invention, the acid value is a value measured according to JIS K0070 or a value measured according to the method described in Examples below.

The color tone of the component (B) is preferably 8 Gardner or less, more preferably about 10 to 400 Hazen, and particularly preferably about 10 to 200 Hazen, from the viewpoint of suppressing coloring in the resin composition. In this specification, the color tone is measured in accordance with JIS K 0071-1 in terms of Hazen units and in accordance with JIS K 0071-2 in terms of Gardner units.

Component (B) may optionally contain various known additives as long as they do not impair the effects of the present invention. Additives include, for example, dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, and the like. The above additives can be used singly or in combination of two or more.

(Additive)
The resin composition may contain additives, if necessary, as long as the effects of the present invention are not impaired. Additives include, for example, flame retardants (e.g., phosphorus-containing epoxy resins, red phosphorus, phosphazene compounds, phosphates, phosphate esters, etc.), silicone oils, wetting and dispersing agents, antifoaming agents, defoaming agents, natural waxes. synthetic waxes, straight-chain fatty acid metal salts, fatty acid amides, esters, paraffins and other release agents, crystalline silica, fused silica, calcium silicate, alumina, calcium carbonate, talc, inorganic pigments, organic pigments , a dehydrating agent, a crystal nucleating agent, a plasticizer, a fluidity improver other than component (B), a weathering agent, an antioxidant, an ultraviolet absorber, a heat stabilizer, a light stabilizer, and the like.

Examples of the inorganic pigment include cadmium red, cadmium lemon yellow, cadmium yellow orange, titanium dioxide, carbon black, black iron oxide, and black complex inorganic pigment.

Examples of the organic pigment include aniline black, perylene black, anthraquinone black, benzidine yellow pigment, phthalocyanine blue and phthalocyanine green.

(Content of each component)
The content of component (B) in the resin composition is 0.1 to 5 parts by mass per 100 parts by mass of component (A).

When the content of component (B) is 0.1 parts by mass or more per 100 parts by mass of component (A), the resin composition is excellent in moldability. When the content of component (B) is 5 parts by mass or less per 100 parts by mass of component (A), the resin composition is excellent in moldability and maintains its mechanical strength.

The content of the component (B) in the resin composition is 0.3 to 2 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of excellent mechanical strength and moldability of the resin composition. is preferred.

The content of the additive in the resin composition is not particularly limited, but usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0 01 parts by mass or more, and usually 100 parts by mass or less, preferably 50 parts by mass or less.

(Method for producing resin composition)
The method for producing the resin composition is not particularly limited, and various known methods can be employed. In the method for producing the resin composition, for example, the components (A), (B) and, if necessary, the additives are mixed in advance using various mixers such as a tumbler mixer and a Henschel mixer, followed by a Banbury mixer, A method of melt-kneading with a mixer such as a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader can be used. The melt-kneading temperature is not particularly limited, but is usually in the range of 170 to 300°C, preferably 180 to 250°C.

[Molded body]
The molded article of the present invention is obtained by molding the above resin composition by various known molding methods. The shape of the molded article is not particularly limited, and can be appropriately selected according to the application and purpose of the molded article. Circular, elliptical, polygonal, odd-shaped, hollow, frame-shaped, box-shaped, panel-shaped and the like can be mentioned.

A method for molding the molded article is not particularly limited, and conventionally known molding methods can be employed. Specifically, for example, injection molding method, injection compression molding method, extrusion molding method, stretched film molding, inflation molding, profile extrusion method, transfer molding method, blow molding method, gas-assisted blow molding method, blow molding method, extrusion Blow molding, IMC (in-mold coating molding) molding method, press molding method, rotational molding method, multi-layer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method, pressure molding method, etc. mentioned. Among them, molding is preferably performed by injection molding. Examples of the injection molding machine include known injection molding machines such as ultra-high speed injection molding machines and injection compression molding machines.

The molded article has a wide range of applications ranging from household goods to industrial goods, for example, automotive materials such as automotive interior materials, outer panels and bumpers, electrical and electronic equipment, home appliance parts, OA equipment, information terminal equipment, machine parts, packaging materials. , building materials, civil engineering materials, fisheries materials, various containers, lighting equipment, films, sheets, fibers, and other industrial materials.

The electrical and electronic devices include, for example, car navigation systems, personal computers, game machines, televisions, display devices such as electronic paper, printers, copiers, facsimiles, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, and DVDs. display devices such as mobile phones, tablet-type mobile devices, touch panel-type mobile devices, and the like.

[Fluidity improver]
The fluidity improver of the present invention contains the above component (B). When used in a polyolefin resin, the fluidity improver of the present invention maintains the mechanical strength of the polyolefin resin, improves the fluidity of the polyolefin resin when melted, and improves moldability. When the fluidity improver contains a rosin-based resin other than the component (B), such as rosin esters, which are reaction products of rosin acid and alcohol, and various metal salts of rosin acid, the polyolefin resin is melted. Since the fluidity in the resin cannot be improved or deteriorated, the moldability cannot be improved. The fluidity improver of the present invention is different from the above resin composition.

The fluidity improver can be used for various known polyolefin resins. Examples of the polyolefin resin include the above-described component (A). The polyolefin resin may be used alone or in combination of two or more.

Polyolefin resins for which the fluidity improver is used include homopolymers of α-olefins having about 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene, from the viewpoint of excellent moldability; ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, Binary or ternary (co)polymers with other α-olefins having about 2 to 18 carbon atoms such as 1-heptene, 1-octene, 1-decene and 1-octadecene are preferred. At least one selected from the group consisting of polyethylene and polypropylene is more preferred.

Component (B) in the fluidity improver is at least one selected from the group consisting of natural rosin, refined rosin, hydrogenated rosin and disproportionated rosin from the viewpoint of excellent mechanical strength and moldability of polyolefin resin. Seeds are preferred.

The weight average molecular weight (Mw) of component (B) in the fluidity improver is 280-340. In addition, in this specification, a weight average molecular weight (Mw) is a polystyrene conversion value by a gel permeation chromatography (GPC) method.

When the weight average molecular weight of component (B) is 280 or more, the mechanical strength of the polyolefin resin is maintained. When the weight average molecular weight of component (B) is 340 or less, the moldability is improved while maintaining the mechanical strength of the polyolefin resin. The weight average molecular weight of component (B) is preferably about 300 to 320 from the viewpoint of excellent mechanical strength and moldability of the polyolefin resin.

If the weight-average molecular weight of component (B) is more than 340, the polyolefin resin has poor moldability and mechanical strength. Examples of such rosin acids include rosins modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride (unsaturated carboxylic acid-modified rosins), polymerized rosins, and the like. be done.

The physical properties of the component (B) in the fluidity improver are not particularly limited except for the weight average molecular weight. The acid value of component (B) is preferably about 130 to 200 mgKOH/g from the viewpoint of excellent mechanical strength and moldability of the polyolefin resin, and more preferably about 150 to 195 mgKOH/g from the same viewpoint. In the present invention, the acid value is a value measured according to JIS K0070 or a value measured according to the method described in Examples below.

The color tone of the component (B) in the fluidity improver is preferably 8 Gardner or less, more preferably about 10 to 400 Hazen, and particularly preferably about 10 to 200 Hazen, from the viewpoint of suppressing coloring of the polyolefin resin. In this specification, the color tone is measured in accordance with JIS K 0071-1 in terms of Hazen units and in accordance with JIS K 0071-2 in terms of Gardner units.

Although the amount of the fluidity improver used is not particularly limited, it is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

When the amount of the fluidity improver used is 0.1 parts by mass or more with respect to 100 parts by mass of the polyolefin resin, the moldability of the polyolefin resin is more excellent. When the amount of the fluidity improver used is 5 parts by mass or less with respect to 100 parts by mass of the polyolefin resin, the polyolefin resin has better moldability and maintains its mechanical strength.

The amount of the fluidity improver to be used is more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the polyolefin resin, from the viewpoint of excellent mechanical strength and moldability of the polyolefin resin.

The fluidity improver of the present invention may optionally contain various known additives as long as the effects of the present invention are not impaired. Additives include, for example, dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, and the like. The above additives can be used singly or in combination of two or more. Although the content of the additive is not particularly limited, it is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the fluidity improver.

The method of using the fluidity improver of the present invention is not particularly limited. The method of using the fluidity improver includes, for example, a method of adding the fluidity improver together with the polyolefin resin to a mixer and melt-kneading them in the mixer. Examples of the mixer include Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail by showing examples of the present invention, but the present invention is not limited to these examples. "Parts" and "%" in the examples represent "mass parts" and "mass%", respectively.

(Production of rosin acid (B))
Production example 1
A reaction vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 1000 parts of gum rosin (acid value 172 mgKOH/g, softening point 75°C) and 5% palladium carbon (water content 50) as a disproportionation catalyst. %) is added, and under a nitrogen blanket, the disproportionation reaction is carried out by stirring at 280 ° C. for 4 hours, and the acid value is 160 mg KOH / g, the weight average molecular weight is 320, and the color tone is 6 Gardner's disproportionation rosin (hereinafter referred to as (B1) component) was obtained.

Production example 2
A 3-liter autoclave was charged with 1000 parts of gum rosin (acid value 171 mgKOH/g, softening point 76°C, color Gardner 6) and 2 parts of 5% palladium carbon (water content 50%) as a hydrogenation catalyst to remove oxygen from the system. After that, the inside of the system was pressurized with hydrogen to 100 kg/cm ² , the temperature was raised to 260° C. with stirring, and a hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydrogenated rosin. Next, the hydrogenated rosin was distilled under a reduced pressure of 3 mmHg under a nitrogen blanket to obtain a purified hydrogenated rosin. Then, 200 parts of the purified hydrogenated rosin and 0.1 part of 5% palladium carbon (water content of 50%) were charged into a 1-liter shaking autoclave, and after nitrogen substitution to remove oxygen in the system, the system was evacuated. The temperature was raised to 250° C., and dehydrogenation was carried out at the same temperature for 3 hours to obtain a hydrogenated rosin having an acid value of 172.6 mgKOH/g, a weight average molecular weight of 300, and a color tone of 80 Hazen (hereinafter referred to as component (B2)). Obtained.

(acid number)
The acid values of components (B1) to (B2) and components (b1) to (b3) were measured according to JIS K 0070. Results are shown in Tables 1 and 2.

The acid value of component (b4) was measured by the following method. Results are shown in Tables 1 and 2.

A solution was prepared by adding 25 ml of 0.1 mol/L potassium hydroxide aqueous solution to an acetone solution of 0.3 g of component (b4) dissolved in 50 ml of acetone. Next, the solution was allowed to stand for 10 minutes, and after adding a few drops of phenolphthalein as an indicator, it was titrated with 0.1 mol/L hydrochloric acid. The acid value of the component (b4) was calculated by the following formula from the hydrochloric acid titer and the weight of the component (b4).

Acid value (mgKOH/g) = {25-hydrochloric acid titer (ml)} x 5.611/(b4) component weight (g)

(color tone)
The color tones of components (B1) and (B2) were measured according to JIS K 0071-1 for Hazen units and according to JIS K 0071-2 for Gardner units.

(Measurement of weight average molecular weight (Mw))
The weight average molecular weights (Mw) of components (B1) to (B2) and components (b1) to (b4) are calculated from standard polystyrene calibration curves by gel permeation chromatography (GPC), as polystyrene conversion values. Calculated. In addition, the GPC method was measured under the following conditions. Results are shown in Tables 1 and 2.
Analyzer: HLC-8320 (manufactured by Tosoh Corporation)
Column: TSK guard column HXL-L, TSK-GEL G2000HXL, and TSK-GEL G1000HXL are connected Eluent: Tetrahydrofuran Injection sample concentration: 3 mg/mL
Sample side flow rate: 1.0 mL/min
Reference side flow rate: 0.5 mL/min
Injection volume: 40 μL
Column temperature: 40°C
Detector: RI, UV (254 nm)

[Preparation of resin composition]
Example 1
Polypropylene (manufactured by Japan Polypropylene Co., Ltd., trade name "Novatec PP MA3") (hereinafter referred to as PP) is added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name "Laboplastomill Model 10C100"). 100 parts of component (B1) and 1 part of component (B1) were added and kneaded at a roller speed of 40 rpm and a temperature of 190° C. for 5 minutes. After that, the obtained kneaded product is taken out from the kneading device, hot-pressed at 200 ° C., molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm × 5 mm with a cutting machine to form pellets (resin composition ).

Example 2
A resin composition was obtained in the same manner as in Example 1, except that 1 part of component (B2) was used instead of component (B1).

Example 3
A resin composition was obtained in the same manner as in Example 1, except that 0.3 part of component (B1) was used.

Comparative example 1
100 parts of PP was added to a roller mixer kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Laboplastomill Model 10C100) and kneaded at a roller rotation speed of 40 rpm and a temperature of 190° C. for 5 minutes. After that, the obtained kneaded product is taken out from the kneading device, hot-pressed at 200 ° C., molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm × 5 mm with a cutting machine to form pellets (resin composition ).

Comparative example 2
In Example 1, hydrogenated rosin ester (manufactured by Arakawa Chemical Industries, Ltd., trade name "KE-311", weight average molecular weight 780, acid value 6 mgKOH/g) (hereinafter referred to as (b1)) was used instead of the component (B1). A pellet (resin composition) was obtained in the same manner as in Example 1, except that 1 part of the resin composition was used.

Comparative example 3
In Example 1, a hydride of acrylic acid-modified rosin (manufactured by Arakawa Chemical Industries, Ltd., trade name "KE-604", weight average molecular weight 380, acid value 240 mgKOH/g) (hereinafter referred to as A pellet (resin composition) was obtained in the same manner as in Example 1, except that 1 part of component (b2) was used.

Comparative example 4
In Example 1, polymerized rosin (manufactured by Arakawa Chemical Industries, Ltd., trade name "R-140", weight average molecular weight 520, acid value 145 mgKOH/g) (hereinafter referred to as component (b3)) was used instead of component (B1). ) was used to obtain pellets (resin composition) in the same manner as in Example 1.

Comparative example 5
In Example 1, instead of the (B1) component, a maleic acid-modified rosin ester (manufactured by Arakawa Chemical Industries, Ltd., trade name "Malquedo No. 32", weight average molecular weight 1,740, acid value 180 mgKOH / g) (hereinafter , (b4) component) was used in the same manner as in Example 1 to obtain pellets (resin composition).

Example 4
100 parts of polyethylene (Rombic Co., Ltd., product name "LLDPE RLL1BF") (hereinafter referred to as PE) is added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Laboplastomill Model 10C100"). and 1 part of component (B1) were added and kneaded at a roller speed of 40 rpm and a temperature of 210° C. for 5 minutes. After that, the obtained resin (composition) is taken out from the kneading device, hot-pressed at 180 ° C., molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm × 5 mm with a cutter to obtain pellets. Obtained.

Example 5
A resin composition was obtained in the same manner as in Example 4, except that 1 part of component (B2) was used instead of component (B1).

Example 6
A resin composition was obtained in the same manner as in Example 4, except that 0.3 part of component (B1) was used.

Comparative example 6
100 parts of PE was added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Laboplastomill Model 10C100) and kneaded at a roller rotation speed of 40 rpm and a temperature of 210° C. for 5 minutes. After that, the obtained kneaded product is taken out from the kneading device, hot-pressed at 180 ° C., molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm × 5 mm with a cutting machine to form pellets (resin composition ).

Comparative example 7
Pellets (resin composition) were obtained in the same manner as in Example 4, except that 1 part of component (b1) was used instead of component (B1).

Comparative example 8
In Example 4, preparation was carried out in the same manner as in Example 4 except that 1 part of component (b2) was used instead of component (B1) to obtain pellets (resin composition).

Comparative example 9
In Example 4, preparation was carried out in the same manner as in Example 4 except that 0.3 part of component (b4) was used instead of component (B1) to obtain pellets (resin composition).

(Evaluation of moldability)
In accordance with JIS K 7210, the pellets of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared under the conditions of a temperature of 230 ° C. and a load of 21.2 N (2.16 kg), Examples 4 to 6 and Comparative Example 6. The MFR of each pellet was measured under conditions of a temperature of 190° C. and a load of 21.2 N (2.16 kg). Results are shown in Tables 1 and 2.

(Evaluation of mechanical strength)
The pellets (resin composition) obtained above are placed in a mold of 100 mm × 100 mm × 1.0 mm, and the pellets of Examples 1 to 3 and Comparative Examples 1 to 5 are at a temperature of 200 ° C., Examples 4 to 6 and The pellets of Comparative Examples 6 to 9 were press-molded at a temperature of 180° C. to obtain resin sheets (molded bodies) having a thickness of 1.0 mm. The resulting resin sheet was punched out with a JIS K7139-A23 punching blade to obtain a dumbbell test piece for mechanical strength measurement. This test piece was subjected to a tensile test using a "universal testing machine AGX-V" manufactured by Shimadzu Corporation to measure the nominal strain at break (%). Results are shown in Tables 1 and 2.

The blending amounts in Tables 1 and 2 are values in parts by mass. Abbreviations in Tables 1 and 2 are as follows.
(Abbreviation and details of compound)
PP: polypropylene, trade name "Novatec PP MA3", manufactured by Japan Polypropylene Corporation PE: polyethylene, trade name "LLDPE RLL1BF", manufactured by Rhombic Co., Ltd.

Claims (9)

Containing polyolefin resin (A) and rosin acid (B),
The rosin acid (B) has a weight average molecular weight of 280 to 340,
The resin composition, wherein the content of the rosin acid (B) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin (A). 2. The resin composition according to claim 1, wherein component (A) is at least one selected from the group consisting of polyethylene and polypropylene. 3. The resin composition according to claim 1, wherein component (B) has an acid value of 130 to 200 mgKOH/g. The resin composition according to any one of claims 1 to 3, wherein component (B) is at least one selected from the group consisting of natural rosin, refined rosin, hydrogenated rosin and disproportionated rosin. A molded article obtained from the resin composition according to any one of claims 1 to 4. A fluidity improver for polyolefin resins, comprising a rosin acid (B) having a weight average molecular weight of 280-340. 7. The fluidity improver for polyolefin resin according to claim 6, wherein said polyolefin resin is at least one selected from the group consisting of polyethylene and polypropylene. 8. The fluidity improver for polyolefin resins according to claim 6, wherein component (B) has an acid value of 130 to 200 mgKOH/g. Component (B) is at least one selected from the group consisting of natural rosin, refined rosin, hydrogenated rosin and disproportionated rosin, for polyolefin resin according to any one of claims 6 to 8. Flow improver.