JP6306560B2 - Polyolefin resin modifier - Google Patents

Description

  The present invention relates to a modifier for polyolefin resins. More specifically, the present invention relates to a modifier for polyolefin resin containing an acid-modified polyolefin.

  Acid-modified polyolefins are widely used as polyolefin resin modifiers such as resin surface modifiers, dispersants, compatibilizers, and the like. As a method for producing acid-modified polyolefin, a method of adding an unsaturated carboxylic acid to a low molecular weight polyolefin is known (for example, Patent Documents 1 and 2).

JP 2005-194507 A JP-A-3-91547

However, the acid-modified polyolefins described in Patent Documents 1 and 2 have a problem that the modification effect of the polyolefin resin is insufficient.
The objective of this invention is providing the modifier for polyolefin resins which provides the modification effect excellent in polyolefin resin, without impairing mechanical strength.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises an acid-modified polyolefin (X) having a polyolefin (A) and an unsaturated (poly) carboxylic acid (anhydride) (B) as structural units, and the (X) is the following: A polyolefin resin modifier satisfying any of (1) to (4) , wherein the polyolefin (A) has an ethylene unit / propylene unit weight ratio [ethylene unit / propylene unit] of 1/99 to 10 / 90 modifier for polyolefin resin;
(1) Acid value is 1-60
(2) Number average molecular weight (Mn) is 1,000-40,000
(3) The melt viscosity at 160 ° C. is 10 to 50,000 mPa · s.
(4) The heat of fusion measured with a differential scanning calorimeter (DSC) is 1 to 80 J / g.
And a number average molecular weight obtained by thermally degrading a polyolefin (A0) polymerized using a metallocene catalyst is 800 to 20,000, and 1 to 20 terminal doubles per 1,000 carbon atoms. Polyolefin (A) which is an ethylene / propylene copolymer having a bond [(ethylene unit) / (propylene unit) = 1/99 to 10/90], and unsaturated (poly) carboxylic acid (anhydride) (B) Acid-modified polyolefin in which the weight ratio [(A) / (B)] of (A) and (B) is 90/10 to 99.5 / 0.5 in the absence of a radical initiator It is a manufacturing method of (X).

The polyolefin resin modifier (K) of the present invention has the following effects.
(1) The polyolefin resin is imparted with reforming characteristics such as adhesion to resins having different polarities and dispersibility of pigments / fillers while maintaining mechanical strength.
(2) Excellent solvent solubility.
(3) The molded article of the polyolefin resin composition is excellent in reforming characteristics and mechanical strength.

[Polyolefin (A)]
In the polyolefin (A) in the present invention, a polyolefin (A0) described later may be referred to as a thermal degradation method (hereinafter referred to as a thermal degradation method, for example, Japanese Patent Publication No. 43-9368, Japanese Patent Publication No. 44-29742), A thermal degradation product obtained by thermal degradation by the production method described in JP-B-6-70094 is preferred.

  The weight ratio [(ethylene unit) / (propylene unit)] of (ethylene unit) and (propylene unit) in (A) is the moldability of the polyolefin resin composition described below and the polyolefin resin modifier (K) described below. From the viewpoint of the reforming characteristics, the ratio is preferably 1/99 to 10/90, more preferably 2/98 to 8/92.

  The thermal degradation method includes a method in which the polyolefin (A0) is thermally degraded at 300 to 450 ° C. for 0.5 to 10 hours in the absence of an organic peroxide under nitrogen flow.

  The number average molecular weight (Mn) of (A) is preferably 800 to 20,000, more preferably 1, from the viewpoint of the mechanical strength of the molded product of the polyolefin resin composition and the productivity of the modifier (K). 000 to 18,000.

The measurement conditions of Mn by GPC in the present invention are as follows.
<Measurement conditions>
Apparatus: High-temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Made by Polymer Laboratories, Inc.]
Column temperature: 135 ° C

(A) preferably has a double bond at the molecular end from the viewpoint of reactivity with an unsaturated (poly) carboxylic acid (anhydride) (B) described later.
The number of double bonds at the molecular end per 1,000 carbons (also referred to as 1,000 carbon atoms) of (A) is the reactivity between (A) and (B) and the modifier (K). From the viewpoint of productivity, the number is preferably 1.0 to 20, more preferably 1.1 to 18, and particularly preferably 1.2 to 15.
Here, the number of double bonds can be determined from the spectrum of (A) ¹ H-NMR (nuclear magnetic resonance) spectroscopy.
That is, the peak in the spectrum is assigned, and the number of double bonds in (A) and (A) are calculated from the integral value derived from double bonds and the integral value derived from (A) at 4.5 to 6 ppm in (A). The relative value of the number of carbon atoms is determined, and the number of double bonds at the molecular end per 1,000 carbon atoms of (A) is calculated. The number of terminal double bonds in the examples described later was in accordance with this method.

[Polyolefin (A0)]
The polyolefin (A0) is preferably an ethylene / propylene copolymer polymerized using a metallocene catalyst. As in the case of (A), (A0) is the weight ratio of (ethylene unit) to (propylene unit) [(ethylene unit) / (propylene unit)], which is the moldability of the polyolefin resin composition described later. From the viewpoint of the modification property of the polyolefin resin modifier (K) described later, the ratio is preferably 1/99 to 10/90, more preferably 2/98 to 8/92.
The number average molecular weight of the polyolefin (A0) [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method described later. same as below. ] Is preferably from 30,000 to 400,000, more preferably from 50,000 to 200,000, from the productivity of the polyolefin (A) described later and from an industrial viewpoint.

[Unsaturated (poly) carboxylic acid (anhydride) (B)]
The unsaturated (poly) carboxylic acid (anhydride) (B) in the present invention is a (poly) carboxylic acid having 3 to 30 carbon atoms having one polymerizable unsaturated group [hereinafter sometimes abbreviated as C]. (Anhydride). In the present invention, the unsaturated (poly) carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic anhydride.
Among these (B), as unsaturated monocarboxylic acid, aliphatic (C3-24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic ring-containing (C6-24, For example, cyclohexene carboxylic acid); unsaturated poly (2-3 or more) carboxylic acid (anhydride) include unsaturated dicarboxylic acid (anhydride) [aliphatic dicarboxylic acid (anhydride) (C4-24, eg malee Acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), alicyclic dicarboxylic acids (anhydrides) (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptide) Tendenedicarboxylic acid, methyltetrahydrophthalic acid, and their anhydrides) and the like. (B) may be used alone or in combination of two or more.
Of the above (B), unsaturated dicarboxylic acid anhydride is preferred, and maleic anhydride is more preferred from the viewpoints of reactivity with polyolefin (A) and modifying properties of the modifying agent (K) described below. .

[Acid-modified polyolefin (X)]
The acid-modified polyolefin (X) in the present invention comprises the polyolefin (A) and the unsaturated (poly) carboxylic acid (anhydride) (B) as structural units. Preferably, the polyolefin (A) and the unsaturated (poly) carboxylic acid (anhydride) (B) are reacted in the absence of a radical initiator.

  The weight ratio [(A) / (B)] between (A) and (B) is preferably from the viewpoint of the affinity with the polyolefin resin (C) described later and the modifying properties of the modifier (K). The reaction is carried out at 90/10 to 99.5 / 0.5, more preferably 92/8 to 99/1.

  The acid-modified polyolefin (X) is preferably added to the polyolefin (A) and the unsaturated (poly) carboxylic acid (anhydride) (B), if necessary, in the absence of a radical initiator. -18, such as hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (di-, tri-, and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di- -T-butyl ketone, etc.) and ether (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)] are added and reacted.

  The reaction temperature is preferably 100 to 270 ° C., more preferably 120 to 250 ° C., particularly preferably 130 to 240 ° C. from the viewpoints of the reactivity and productivity of (A) and (B).

  The acid value of (X) is 1 to 60 mgKOH / g (only numerical values are shown below), preferably 3 to 50, from the viewpoint of the modifying properties of the modifier (K). The acid value here is a value measured according to JIS K0070. When the acid value is less than 1, the reforming property of the modifier (K) is inferior, and when it exceeds 60, the productivity of (X) is inferior.

  Mn of (X) is 1,000 to 40,000, preferably 1,500 to 35,000, and more preferably 2,000 to 30,000. When Mn is less than 1,000, the mechanical strength of the molded product is inferior, and when it exceeds 40,000, the reforming property of (K) is inferior.

  The melt viscosity at 160 ° C. of (X) is 10 to 50,000 mPa · s (only numerical values are shown below), preferably 50 to 45,000, and more preferably 100 to 40,000. When the melt viscosity is less than 10, the productivity of (X) is inferior, and when it exceeds 50,000, the reforming property of (K) is inferior.

  The heat of fusion measured with a differential scanning calorimeter (DSC) of (X) is 1 to 80 J / g (only numerical values are shown below), preferably 3 to 75, more preferably 5 to 70. When the heat of fusion is less than 1, the productivity is inferior, and when it exceeds 80, the reforming characteristics and the solvent solubility are inferior.

[Modifier for polyolefin resin (K)]
The polyolefin resin modifier (K) of the present invention comprises the acid-modified polyolefin (X). The modifier (K) is used as a modifier for the polyolefin resin (C) described later.
The modifier (K) can impart to the polyolefin resin (C) modification properties such as adhesion to resins having different polarities and dispersibility of pigments / fillers while maintaining mechanical strength.
Moreover, the primer for plastic molded articles of the present invention comprises the polyolefin resin modifier (K). The primer is obtained by adding a solvent to the modifier (K) or the modifier (K) and the polyolefin as necessary.

[Polyolefin resin composition]
The polyolefin resin composition of the present invention comprises the polyolefin resin modifier (K) and the polyolefin resin (C).
(C) includes, for example, ethylene unit-containing (propylene unit-free) (co) polymer, propylene unit-containing (ethylene unit-free) (co) polymer, ethylene / propylene copolymer, and C4 or more olefins. (Co) polymers are included.

  As a combination of (C) and (K), the case where the structural unit of (C) and the structural unit of the polyolefin (A) constituting (K) are the same or similar are the cases of (C) and (K) From the viewpoint of compatibility, (C) is preferably a propylene unit-containing (co) polymer, and particularly preferably an ethylene / propylene copolymer.

  Mn of (C) is preferably 10,000 to 500,000, more preferably 20 from the viewpoint of the mechanical strength of the molded article of the present invention described later and the compatibility with the polyolefin resin modifier (K). , 400,000 to 400,000.

  The polyolefin resin composition of the present invention may further include a colorant (D1), a filler (D2), a matting agent (D3), an antistatic agent (D4), a dispersant (as long as necessary). One or more additives selected from the group consisting of D5), flame retardant (D6), foaming agent (D7), antioxidant (D8), ultraviolet absorber (D9) and plasticizer (D10) ( D) can be included.

  The total amount of (D) used in the polyolefin resin composition of the present invention is usually 30% or less based on the total weight of the polyolefin resin composition. 20%.

  The amount of each additive (D) used based on the total weight of the polyolefin resin composition is such that (D1) is usually 10% or less, preferably 1 to 5%; (D2) is usually 25% or less, preferably 3 to 20 (D3) is usually 20% or less, preferably 1-10%; (D4) is usually 10% or less, preferably 1-5%; (D5) is usually 20% or less, preferably 0-15%, Particularly preferably 0 to 10%; (D6) is usually 15% or less, preferably 3 to 10%; (D7) is usually 1 to 20% or less, preferably 5 to 15%; (D8) is usually 3% or less. , Preferably 0.01-1%; (D9) is usually 3% or less, preferably 0.01-1%; (D10) is usually 20% or less, preferably 5-15%.

  When the additive is the same and overlaps between (D1) to (D10), the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive. Considering that the effect as an additive can be obtained at the same time, the amount used is adjusted according to the purpose of use.

As a production method of the polyolefin resin composition of the present invention,
(1) A method (collective method) in which (C), (K) and, if necessary, (D) are mixed together to obtain a polyolefin resin composition (collective method);
(2) A masterbatch polyolefin resin composition containing a high concentration of (K) is prepared by mixing a part of (C), the whole amount of (K), and if necessary, a part or all of (D). Then, the method (masterbatch method) including adding the remaining (C) and, if necessary, the remaining (D) and mixing to obtain a polyolefin resin composition is included.
The method (2) is preferable from the viewpoint of the mixing efficiency of (K).

  The weight ratio [(K) / (C)] of (K) and (C) in the polyolefin resin composition of the present invention is preferably from the viewpoint of the reforming characteristics and mechanical strength of the molded product described later. It is 1 / 99.9-50 / 50, More preferably, it is 1 / 99-40 / 60.

As a specific mixing method in the manufacturing method of the polyolefin resin composition,
(I) Each component to be mixed is, for example, a powder mixer [“Hensiel mixer” [trade name “Hensiel mixer FM150L / B”, Mitsui Mining Co., Ltd., manufactured by Nippon Coke Industries, Ltd.] , “Nautamixer” [trade name “Nautamixer DBX3000RX”, manufactured by Hosokawa Micron Co., Ltd.], “Banbury Mixer” [trade name “MIXTRON BB-16MIXER”, manufactured by Kobe Steel Co., Ltd.], etc.] A method of kneading usually at 120 to 220 ° C. for 2 to 30 minutes using a [batch kneader, continuous kneader (single screw kneader, biaxial kneader, etc.), etc .;
(Ii) A method of directly kneading the components to be mixed under the same conditions using the same melt-kneading apparatus as described above without mixing powders in advance.
Among these methods, the method (i) is preferable from the viewpoint of mixing efficiency.

[Molded products, molded articles]
The molded product of the present invention is a molded product of the polyolefin resin composition. That is, the polyolefin resin composition is molded.
Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding, foam molding and the like can be performed by any method that incorporates means. Examples of the form of the molded product include a plate shape, a sheet shape, a film, and a fiber (including a nonwoven fabric).
Since the molded article of the present invention contains the modifier for polyolefin resin (K) having a carboxyl group or the like, it is excellent in affinity with paints, inks and the like having relatively high polarity.

The molded article of the present invention has excellent mechanical strength and good paintability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, acrylic urethane resin paint, and these so-called relatively high-polarity paints, Further, paints with low polarity (such as olefins) can also be used.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

Further, as a method for further printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing, Examples include printing, screen printing, pad printing, dry offset printing, and offset printing.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.

[Polyolefin (A)]
Production Example 1
A reaction vessel was charged with 100 parts of polyolefin (A0-1) [trade name “Versify 3000”, manufactured by Dow Chemical Co., Ltd., Mn: 120,000] using a metallocene catalyst having propylene and ethylene as structural units. While ventilating industrial nitrogen (purity 99.999%) in the phase portion, the mixture was heated and melted with a mantle heater and subjected to thermal degradation at 360 ° C. for 70 minutes with stirring to obtain polyolefin (A-1). In (A-1), the number of double bonds at the molecular end per 1,000 carbon atoms was 7.2, and Mn was 3,000.

Production Examples 2-5, Comparative Production Examples 1-3
In Production Example 1, except that thermal degradation was performed according to Table 1, it was carried out in the same manner as in Production Example 1, and polyolefins (A-2) to (A-5) and (RA-1) to (RA-3) Obtained. The results are shown in Table 1.

[Modifier for polyolefin resin]
Example 1
A reaction vessel was charged with 100 parts of (A-1) and 5 parts of maleic anhydride (B-1), heated to 200 ° C. under aeration of industrial nitrogen (purity 99.999%), and stirred for 10 hours. It was. Thereafter, unreacted maleic anhydride is distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter), and a modifier for polyolefin resin (K-1) containing acid-modified polyolefin (X-1). Got. (X-1) had an acid value of 26, Mn of 3,200, a melt viscosity of 420, and a heat of fusion of 48.

Examples 2-4, Comparative Examples 1-3
In Example 1, according to Table 2, except having used each use raw material, it carried out similarly to Example 1, the modifier for polyolefin resins (K-2)-(K-5), (RK-1)- (RK-3) was obtained. The results are shown in Table 2.

[Primers for plastic molded products]
Examples 6 to 15 and Comparative Examples 4 to 9
According to the blending composition (part) in Table 3, the polyolefin resin modifiers (K-1) to (K-5), (RK-1) to (RK-3) and the polyolefin (A0-1) were mixed with a Henschel mixer. [Brand name “Hensiel Mixer FM150L / B”, Mitsui Mining Co., Ltd., after changing the company name, manufactured by Nihon Coke Kogyo Co., Ltd.] for 3 minutes, 180 ° C., 100 rpm with a vented twin screw extruder Then, after melt-kneading under the condition of a residence time of 5 minutes, a primer solution (solid content concentration 20%) dissolved in xylene at 80 ° C. with stirring was prepared. The primer solution was evaluated for solvent solubility by the following evaluation method.

<Evaluation method>
1. Solvent solubility The properties of the prepared primer solution were observed for 1 day in an oven at 80 ° C. The results are shown in Table 3.
Evaluation criteria:
◎: Solution is transparent ○: Solution is slightly hazy △: Solution is hazy and precipitates X: Almost not dissolved

Next, the primer solution is sprayed onto the surface of a polyolefin resin substrate [trade name “PP1300”, polypropylene, manufactured by Takin Co., Ltd.] using a spray machine [trade name “EBG-115EXB”, manufactured by Anest Iwata Co., Ltd.]. It was applied and dried at 80 ° C. for 10 minutes (film thickness after drying 80 μm).
Then, a polyurethane paint [trade name “Yukot UX-150” manufactured by Sanyo Kasei Kogyo Co., Ltd.] was spray-coated using the same spray machine and dried at 80 ° C. for 10 minutes (after drying, the urethane paint film thickness was 100 μm). The coated surface was subjected to an adhesion test (cross cut test) by a cross cut tape method in accordance with JIS K5400.
The number of portions where the coating film did not peel is represented by 0 to 100 in the grid number 100, and the larger the value, the better the adhesion between the substrate and the coating film. The results are shown in Table 3.

[Polyolefin resin composition, molded product]
Examples 16-23, Comparative Examples 10-16
The modifiers (K-1) to (K-5), (RK-1) to (RK-3), commercially available polypropylene (C-1) [trade name “Novatech PP MA3”, Nippon Polypro Co., Ltd. Manufactured], commercially available polyethylene (C-2) [trade name “Novatech HD HJ580N”, manufactured by Nippon Polyethylene Co., Ltd.] and commercially available ethylene / propylene copolymer (C-3) [trade name “Novatech PP BC3H”, Nippon Polypro Co., Ltd.], commercially available talc (D2-1) [trade name “LMS-100”, manufactured by Fuji Talc Co., Ltd., volume average particle size 6 μm], commercially available magnesium hydroxide (D2-2) [ The product name “Sukima 5A”, manufactured by Kyowa Chemical Industry Co., Ltd., volume average particle size 1 μm], according to the blending composition (parts) in Table 4, respectively, Hensiel mixer [trade name “Hensiel mixer FM150L / B”, Mitsui mine After changing the company name, Nippon Coke Kogyo Co., Ltd.], blended for 3 minutes, and then melt-kneaded in a twin-screw extruder with a vent at 180 ° C., 100 rpm, residence time 5 minutes for polyolefin resin composition I got a thing.
Each resin composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was prepared. Evaluation was made according to the method. The results are shown in Table 4.

<Evaluation method>
1. Impact resistance (Unit: J / m)
Izod impact values were measured according to ASTM D256.
2. Affinity of polyolefin resin (C) and filler (D2) [dispersibility of (D2)]
The fracture surface of the test piece after the test 1 was observed with an electron microscope, and the affinity between (C) and (D2) was evaluated according to the following criteria.
◎: No interfacial delamination between (C) / (D2) ○: Interfacial delamination between (C) / (D2) but very small △: Interfacial delamination slightly between (C) / (D2) × : Almost no interfacial delamination between (C) / (D2) Flexural modulus (unit: MPa)
Measured according to ASTM D790.
4). Deflection temperature under load (unit: ° C)
The deflection temperature under load was measured according to JIS K7191-2.

From the results of Table 3, the polyolefin resin modifier of the present invention is superior in solvent solubility compared to the comparative one, and the primer for the plastic molded product containing the modifier is different between plastics having different polarities. It can be seen that the adhesion between the polyolefin resin and the polyurethane resin is excellent.
From the results of Table 4, it can be seen that the modifier for polyolefin resin of the present invention is superior in the reforming properties with respect to the dispersibility of the filler while maintaining the mechanical strength as compared with the comparative one.
Moreover, it is clear that the molded article of the polyolefin resin composition of the present invention is excellent in the reforming characteristics and mechanical strength as compared with the comparative product.

The modifier for polyolefin resin (K) of the present invention is excellent in solvent solubility, adhesion to other resins having different polarities, pigments and fillers without reducing the mechanical strength of the molded product. A molded product obtained by molding a polyolefin resin composition containing the modifying agent (K) is excellent in imparting modifying properties such as dispersibility, and is excellent in balance between the modifying properties and mechanical strength.
Therefore, the modifier (K) is a molded article or molded article obtained by molding a polyolefin resin composition containing the modifier (K) as a modifier for polyolefin resin, a primer for plastic molded article, or the like. As an article, it can be suitably applied to a wide range of fields such as for electric / electronic devices, for packaging materials, for conveying materials, for household materials, and for building materials.

Claims (9)

It comprises an acid-modified polyolefin (X) having a polyolefin (A) and an unsaturated (poly) carboxylic acid (anhydride) (B) as structural units, and (X) is represented by the following (1) to (4) ), A polyolefin resin having a weight ratio [ethylene unit / propylene unit] of ethylene unit to propylene unit of the polyolefin (A) of 1/99 to 10/90 Modifier .
(1) Acid value is 1-60
(2) Number average molecular weight (Mn) is 1,000-40,000
(3) The melt viscosity at 160 ° C. is 10 to 50,000 mPa · s.
(4) The heat of fusion measured with a differential scanning calorimeter (DSC) is 1 to 80 J / g. Polyolefin (A) is a number average molecular weight modifier for the polyolefin resin according to claim 1, wherein the 800 to 20,000. The polyolefin resin modifier according to claim 1 or 2 , wherein the polyolefin (A) has 1 to 20 terminal double bonds per 1,000 carbon atoms. A primer for a plastic molded article comprising the polyolefin resin modifier (K) according to any one of claims 1 to 3 . A polyolefin resin composition comprising the polyolefin resin modifier (K) according to any one of claims 1 to 3 and a polyolefin resin (C). The polyolefin resin composition according to claim 5 , wherein the weight ratio [(K) / (C)] of (K) and (C) is 0.1 / 99.9 to 50/50 . A molded article which is a molded article of the polyolefin resin composition according to claim 5 or 6 . A molded article obtained by coating and / or printing the molded article according to claim 7 .   The number average molecular weight obtained by thermally degrading a polyolefin (A0) polymerized using a metallocene catalyst is 800 to 20,000, and 1 to 20 terminal double bonds per 1,000 carbon atoms. A polyolefin (A) which is an ethylene / propylene copolymer [(ethylene unit) / (propylene unit) = 1/99 to 10/90] and an unsaturated (poly) carboxylic acid (anhydride) (B) In the absence of a radical initiator, the acid-modified polyolefin (X) is reacted at a weight ratio [(A) / (B)] of 90/10 to 99.5 / 0.5 between (A) and (B). ) Manufacturing method.