JP6748441B2 - Method for producing acid-modified polyolefin - Google Patents

Description

The present invention relates to a method for producing an acid-modified polyolefin. More specifically, it relates to a method for producing an acid-modified polyolefin having an excellent modifying effect.

Acid-modified polyolefins are widely used as modifiers for polyolefin resins such as resin surface modifiers, dispersants, and compatibilizers. Further, as the production method thereof, a low molecular weight polyolefin obtained by polymerization of an olefin monomer, or a low molecular weight polyolefin obtained by thermally degrading a high molecular weight polyolefin obtained by polymerization of an olefin monomer, in the presence of a radical initiator, Method of graft-polymerizing unsaturated carboxylic acid (for example, refer to Patent Document 1), unsaturated carboxylic acid is added to high molecular weight polyolefin in the presence of a radical initiator, thermal degradation of high molecular weight polyolefin and polyolefin of unsaturated carboxylic acid There is known a method of simultaneously performing graft polymerization on (see, for example, Patent Document 2).

JP, 2005-194507, A JP-A-6-287401

However, with the method for producing an acid-modified polyolefin described in Patent Documents 1 and 2, it is difficult to obtain an acid-modified polyolefin that can impart a sufficiently excellent modifying effect without impairing the mechanical strength.
An object of the present invention is to provide a method for producing an acid-modified polyolefin capable of imparting an excellent modifying effect without impairing the mechanical strength of the polyolefin resin composition, and a resin modifier containing the acid-modified polyolefin. It is to provide a manufacturing method of.

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention relates to a polyolefin (A1) having a weight average molecular weight of 3,000 to 20,000, a polyolefin (A2) having a weight average molecular weight of 30,000 to 100,000, and an unsaturated (poly)carboxylic acid ( Anhydride) (B) is reacted in the presence of a radical generator (C), a method for producing an acid-modified polyolefin (X); a resin modifier containing the (X) ( K) is a manufacturing method.

The method for producing an acid-modified polyolefin of the present invention and the method for producing a resin modifier containing the acid-modified polyolefin obtained by the production method have the following effects.
(1) The resin modifier containing the acid-modified polyolefin obtained by the production method imparts an excellent modifying effect to the polyolefin resin without impairing the mechanical strength.

[Polyolefin (A0)]
The polyolefin (A0) in the present invention includes one or more (co)polymers of olefins, and one or more of olefins and one or more of other monomers. A polymer is included.
The above olefins include alkenes having 2 to 30 carbon atoms (hereinafter, may be abbreviated as C), such as ethylene, propylene, 1- and 2-butene, and isobutene, and C5-30 α-olefins (1- (Hexene, 1-decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

Specific examples of (A0) include (co)polymers containing ethylene units (not containing propylene units), such as high-, medium- and low-density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1- Butene, etc.), C5-30 α-olefin (1-hexene, 1-dodecene, etc.), vinyl acetate, etc.] (the weight ratio is the moldability of the polyolefin resin composition and the molecular end of (A) and From the viewpoint of the amount of double bonds in the molecular chain, preferably 30/70 to 99/1, more preferably 50/50 to 95/5) and the like; propylene unit-containing (ethylene unit-free) (co)polymer For example, polypropylene, a copolymer of propylene and a C4-30 unsaturated monomer (the same as the above) (the weight ratio is the same as the above); an ethylene/propylene copolymer (the weight ratio is a molding of a polyolefin resin composition). From the standpoint of the properties and the amount of double bonds in the molecular ends of (A1) and (A2) and/or in the molecular chain, it is preferably 0.5/99.5 to 30/70, more preferably 2/98 to 20/. 80); Included are (co)polymers of C4 or higher olefins such as polybutene.
Among these, polyethylene, polypropylene, ethylene/propylene copolymers, propylene/C4-30 unsaturated monomer copolymers are preferable from the industrial viewpoint, and more preferable are polyethylene and ethylene/propylene copolymers. , A propylene/C4-30 unsaturated monomer copolymer. In addition, (A0) may be used alone or in combination of two or more.

Weight average molecular weight of (A0) [hereinafter abbreviated as Mw. The measurement is based on the gel permeation chromatography (GPC) method described later. same as below. ] Is preferably 100,000 to 2,000,000, more preferably 150,000 to 1,500, from the viewpoint of the mechanical strength of the molded article and the productivity of the polyolefins (A1) and (A2) described below. 000, particularly preferably 200,000 to 1,000,000.

The measurement conditions of Mw and number average molecular weight (Mn) by GPC in the present invention are as follows.
Equipment: High temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Co., Ltd.]
Detector: Refractive index detector Solvent: Orthodichlorobenzene standard substance: Polystyrene Sample concentration: 3 mg/ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Polymer Laboratories Co., Ltd.]
Column temperature: 135℃

[Polyolefin (A1)]
The polyolefin (A1) in the present invention is preferably a thermal degradation method (hereinafter sometimes referred to as a thermal degradation method, for example, the polyolefin (A0) described in JP-B-43-9368 and JP-B-44-29742. It is obtained by thermal degradation according to the manufacturing method described in Japanese Patent Publication No. 6-70094).

In the thermal degradation method, the polyolefin (A0) is subjected to (1) thermal degradation at 300 to 450° C. for 0.5 to 10 hours in the absence of organic peroxide, and (2) organic peroxide. In the presence of a product [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], heat degradation is usually performed at 180 to 300° C. for 0.5 to 10 hours.
Among these, the method of (1) is preferable from the viewpoint of the modifying properties of the resulting modifier (K), since it is easy to obtain one having a larger number of double bonds in the molecular end and/or the molecular chain.

It is preferable that (A1) has a double bond at the molecular end and/or in the molecular chain from the viewpoint of reactivity with the unsaturated (poly)carboxylic acid (anhydride) (B) described later.
The number of double bonds of the molecule per 1,000 carbons (also referred to as 1,000 carbons) of (A1) is from the viewpoint of reactivity with (B) and productivity of the modifier (K). , Preferably 3.0 to 20, more preferably 3.2 to 18, particularly preferably 3.5 to 15.
Here, the number of double bonds can be determined from the spectrum of ¹ H-NMR (nuclear magnetic resonance) spectroscopy of (A1).
That is, the peak in the spectrum is assigned, and from the integrated value derived from the double bond at 4.5 to 6 ppm of (A1) and the integrated value derived from (A1), the number of double bonds of (A1) and (A1) The relative value of the number of carbon atoms of is calculated, and the number of double bonds of the molecule per 1,000 carbons of (A1) is calculated. The number of double bonds in the examples described below was according to the method. The number of double bonds in the molecule is the same as in (A1) for the polyolefin (A2) described later.

The weight average molecular weight of (A1) (hereinafter sometimes abbreviated as Mw) is 3,000 to 20,000, preferably 4,000 to 18,000. If the Mw is less than 3,000, the mechanical strength of the molded product of the polyolefin resin composition described below is poor, and if the Mw is more than 20,000, the resin modifier (K) modification properties described below are poor.

[Polyolefin (A2)]
The polyolefin (A2) in the present invention is preferably obtained by thermally degrading the above polyolefin (A0) by a thermal degradation method.

The number of double bonds of the molecule per 1,000 carbons of (A2) is preferably 0.2 from the viewpoint of the mechanical strength of the molded product of the polyolefin resin composition and the productivity of the modifier (K). To 3.0, more preferably 0.3 to 2.8, and particularly preferably 0.5 to 2.5.

The weight average molecular weight (Mw) of (A2) is 30,000 to 100,000, preferably 40,000 to 90,000. When Mw is less than 30,000, the mechanical strength of the molded product of the polyolefin resin composition is poor, and when Mw is more than 100,000, the productivity of the modifier (K) is poor.

[Unsaturated (poly)carboxylic acid (anhydride) (B)]
The unsaturated (poly)carboxylic acid (anhydride) (B) in the present invention is a C3-30 (poly)carboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, unsaturated (poly)carboxylic acid (anhydride) means unsaturated monocarboxylic acid, unsaturated polycarboxylic acid and/or unsaturated polycarboxylic acid anhydride.
Among the (B), as the unsaturated monocarboxylic acid, aliphatic (C3-24, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic containing (C6-24, For example, cyclohexenecarboxylic acid); unsaturated poly(2 to 3 or more) carboxylic acid (anhydride) as unsaturated dicarboxylic acid (anhydride) [aliphatic dicarboxylic acid (anhydride) (C4 to 24, for example maleic acid Acids, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), alicyclic dicarboxylic acids (anhydrides) (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptyl And the like] and the like] and the like. (B) may be used alone or in combination of two.
Of these, unsaturated dicarboxylic acid anhydrides are preferable, and maleic anhydride is more preferable, from the viewpoint of the polymerizability with the polyolefins (A1) and (A2) and the modifying effect of the resin modifier (K) described later. It is an acid.

[Radical initiator (C)]
The acid-modified polyolefin (X) in the present invention can be obtained by reacting the above (A1), (A2) and (B) in the presence of a radical initiator (C).
Examples of (C) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile), etc.], peroxides [monofunctional (in the molecule (Having one peroxide group) (benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and polyfunctional (having two or more peroxide groups in the molecule) [2. 2-bis(4,4-di-t-butylperoxycyclohexyl)propane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate and the like]] and the like.
Of these, from the viewpoint of the reactivity of (A1), (A2) and (B), a peroxide is preferable, a monofunctional peroxide is more preferable, and di-t-butyl peroxide is particularly preferable. These are lauroyl peroxide and dicumyl peroxide.

The amount of (C) used is preferably 0.05 to 10%, more preferably 0.2, based on the total weight of (A1), (A2) and (B) from the viewpoint of reactivity and suppression of side reactions. ˜5%, particularly preferably 0.3 to 3%.

[Method for producing acid-modified polyolefin (X)]
Specific methods for producing the acid-modified polyophine (X) of the present invention include the following methods [1] and [2].
[1] (A1), (A2) and (B) are combined with a suitable organic solvent [C3-18, such as hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (diene). -, tri-, and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane) Etc.)], and then (C) [or a solution of (C) dissolved in a suitable organic solvent (the same as above)], and if necessary, a chain transfer agent (t) described below, polymerization Method of adding the inhibitor (f) and heating and stirring (solution method);
[2] A method in which (A1), (A2), (B), (C), and optionally (t) and (f) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like ( Melting method).

The reaction temperature in the solution method may be a temperature at which (A1) and (A2) are dissolved in an organic solvent, and preferably 50 to 220° C. from the viewpoint of the reactivity of (A1), (A2) and (B). , More preferably 110 to 210°C, and particularly preferably 120 to 180°C.

Further, the reaction temperature in the melting method may be a temperature at which (A1) and (A2) melt, and from the viewpoint of the reactivity of (A1), (A2) and (B) and the decomposition temperature of the reaction product. It is preferably 120 to 260°C, more preferably 130 to 240°C.

Examples of the chain transfer agent (t) include alcohol (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol, allyl alcohol); thiol (C1-24, such as ethylthiol, propiothiol, 1- And 2-butylthiol, 1-octylthiol); aldehydes (C2-18, such as 2-methyl-2-propylaldehyde, 1- and 2-butyraldehyde, 1-pentylaldehyde); phenols (C6-36, such as phenol). , O-, m- and p-cresol); amines (C3-24 such as diethylmethylamine, triethylamine, diphenylamine); disulfides (C2-24 such as diethyldisulfide, di-1-propyldisulfide).
The amount of (t) used is usually 30% or less based on the total weight of (A1), (A2) and (B), and preferably 0 from the viewpoint of reactivity of (A1), (A2) and (B). 1 to 20%.

As the polymerization inhibitor (f), catechol (C6 to 36, such as 2-methyl-2-propylcatechol), quinone (C6 to 24, such as p-benzoquinone), hydrazine (C2 to 36, such as 1,3,3). 5-triphenylhydrazine), nitro compounds (C3-24, such as nitrobenzene), stabilizing radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6. -Tetramethyl-1-piperidinyl oxide (TEMPO)].
The amount of (f) used is usually 5% or less based on the total weight of (A1), (A2) and (B), and from the viewpoint of stability and polymerizability of (A1), (A2) and (B). It is preferably 0.01 to 0.5%.

[Acid-modified polyolefin (X)]
The acid-modified polyolefin (X) in the present invention is obtained by the method for producing the acid-modified polyolefin (X).

The weight ratio [(A1)/(A2)] of (A1) and (A2) in (X) is preferably 1/99 to 30/70, from the viewpoint of mechanical strength and reforming property of the molded product, More preferably, it is 2/98 to 25/75.

The weight ratio [{(A1)+(A2)}/(B)] of the total of (A1) and (A2) in (X) and (B) is the mechanical strength of the molded product and From the viewpoint of the modifying characteristics of the resin modifier (K), it is preferably 80/20 to 99.5/0.5, and more preferably 85/15 to 99/1.

The acid value of (X) is preferably 10 to 60 mgKOH/g (only numerical values are shown below), and more preferably 12 from the viewpoint of the modification characteristics of the resin modifier (K) described later and the mechanical strength of the molded product. -50, particularly preferably 15-45.
The acid value here is a value obtained by measurement according to the following procedures (i) to (iii) according to JIS K0070.
(I) 1 g of (X) is dissolved in 100 g of xylene whose temperature is adjusted to 100°C.
(Ii) Titrated with 0.1 mol/L potassium hydroxide ethanol solution [trade name "0.1 mol/L ethanolic potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator at the same temperature. I do.
(Iii) The acid value (unit: mgKOH/g) is calculated by converting the amount of potassium hydroxide required for titration into mg.
In the above measurement, one acid anhydride group is equivalent to one carboxyl group. The acid value in the examples described below was according to the method.

The Mw of (X) is preferably 20,000 to 120,000, more preferably 30,000 to 110,000, from the viewpoint of the mechanical strength of the molded product and the modifying properties of the resin modifier (K). More preferably, it is 40,000-100,000.

The product of the acid value and the weight average molecular weight of (X) [(acid value) x (weight average molecular weight)] is the property of modification and the mechanical strength of the molded product, and the productivity of the resin modifier (K). From the viewpoint, it is preferably 800,000 to 4,000,000, and more preferably 1,000,000 to 3,500,000.

[Method for producing resin modifier (K)]
The method for producing the resin modifier (K) of the present invention is a method for producing the resin modifier (K) containing the acid-modified polyolefin (X).
The resin modifier (K) in the present invention contains the acid-modified polyolefin (X).
The resin modifier (K) is preferably used as a resin modifier for the polyolefin resin (D) described later.

[Polyolefin resin (D)]
The polyolefin resin (D) in the present invention includes the polyolefin resins exemplified as the above (A0) or the degradation (thermal, chemical and mechanical) of the high molecular weight polyolefin (preferably Mw 150,000 to 3,000,000). Degradation) method, for example, ethylene unit-containing (propylene unit-free) (co)polymer, propylene unit-containing (ethylene unit-free) (co)polymer, and ethylene/propylene as exemplified above. Copolymers and (co)polymers of C4 or higher olefins are included.

The Mw of (D) is preferably 100,000 to 3,000,000, and more preferably 200 from the viewpoint of the mechanical strength of the molded article in the present invention described later and the compatibility with the resin modifier (K). 1,000 to 2,000,000.

[Method for producing polyolefin resin composition]
The method for producing a polyolefin resin composition of the present invention is a method for producing a polyolefin resin composition containing the resin modifier (K) and the polyolefin resin (D).
The polyolefin resin composition in the present invention contains the resin modifier (K) and the polyolefin resin (D).
As a combination of (D) and (K), when the structural unit of (D) and the structural units of the polyolefins (A1) and (A2) constituting (K) are the same or similar, (D) and ( It is preferable from the viewpoint of compatibility with K). For example, when (D) is a propylene unit-containing (ethylene unit-free) (co)polymer, (A1) and (A2) constituting (K) are also propylene unit-containing (ethylene unit-free) (co). ) It is preferably a polymer.

The polyolefin resin composition of the present invention may further contain a colorant (E1), a reinforcing agent (E2), a matting agent (E3), an antistatic agent (E4), and a dispersant as long as the effects of the present invention are not impaired. (E5), flame retardant (E6), foaming agent (E7), antioxidant (E8), ultraviolet absorber (E9), and one or more additives selected from the group consisting of plasticizers (E10). (E) can be contained.

The total amount of (E) 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, and preferably 1 to 1 from the viewpoint of expression of the function of (E) and industrial. 10%.
The amount of each additive (E) used based on the total weight of the polyolefin resin composition is such that (E1) is usually 10% or less, preferably 1 to 5%; (E2) is usually 30% or less, preferably 3 to 20. %; (E3) is usually 20% or less, preferably 1 to 10%; (E4) is usually 25% or less, preferably 1 to 20%, more preferably 2 to 10%; (E5) is usually 20% or less. , Preferably 0 to 15%, particularly preferably 0 to 10%; (E6) is usually 15% or less, preferably 3 to 10%; (E7) is usually 1 to 20% or less, preferably 5 to 15%; (E8) is usually 3% or less, preferably 0.01 to 1%; (E9) is usually 3% or less, preferably 0.01 to 1%; (E10) is usually 20% or less, preferably 5 to 15 %.
In the case where the additives are the same and overlap between (E1) to (E10), the amount of each additive exhibiting the corresponding addition effect is not used regardless of the effect as other additives, and Considering that the effect as the additive of (1) is obtained at the same time, the amount used is adjusted according to the purpose of use.

The method for producing the polyolefin resin composition of the present invention,
(1) A method of collectively mixing (D), (K) and (E) if necessary to form a polyolefin resin composition (collective method);
(2) A masterbatch polyolefin resin composition containing a high concentration of (K) is once prepared by mixing a part of (D), the whole amount of (K), and optionally a part or the whole amount of (E). Then, a method (masterbatch method) of adding the rest of (D) and optionally the rest of (E) and mixing them to obtain a polyolefin resin composition is included.
The method (2) is preferred from the viewpoint of the mixing efficiency of (K).

The weight ratio [(K)/(D)] of (K) and (D) in the polyolefin resin composition in the present invention is preferably 0.1 from the viewpoint of the reforming property and mechanical strength of the molded article described later. /99.9 to 40/60, and more preferably 1/99 to 35/65.

As a specific mixing method in the method for producing 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., after changing the company name, manufactured by Nippon Coke Industry Co., Ltd.]. , "Nauter Mixer" [trade name "Nauter Mixer DBX3000RX" manufactured by Hosokawa Micron Co., Ltd.], "Banbury Mixer" [trade name "MIXTRON BB-16 MIXER" manufactured by Kobe Steel Ltd., etc.] A method of kneading for 2 to 30 minutes at 120 to 220° C. using a melt kneading device [batch kneader, continuous kneader (single screw kneader, twin screw kneader, etc.)].
(Ii) A method of directly kneading the respective components to be mixed under the same conditions using the same melt-kneading device as described above without previously mixing the powders.
Of these methods, the method (i) is preferable from the viewpoint of mixing efficiency.

[Molded article, method for manufacturing molded article]
The method for producing a molded article of the present invention is a method for producing a molded article obtained by molding the polyolefin resin composition.
The molded product according to the present invention is obtained by molding the polyolefin resin composition.
Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), and a single layer depending on the purpose. It can be molded by any method including means such as molding, multi-layer molding or foam molding. Examples of the form of the molded product include a plate shape, a sheet shape, a film, a fiber (including a non-woven fabric) and the like.
Since the molded product of the present invention contains the resin modifier (K) having a carboxyl group or the like, it has excellent affinity with paints, inks and the like having a relatively high polarity.

The method for producing a molded article according to the present invention is a method for producing a molded article obtained by coating and/or printing the above-mentioned molded article.
The molded article according to the present invention has excellent mechanical strength and good paintability and printability, and a molded article can be obtained by painting 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, dip coating, roller coating, and brush coating.
Examples of paints include polyester melamine resin paints, epoxy melamine resin paints, acrylic melamine resin paints, paints generally used for coating plastics such as acrylic urethane resin paints, and even these so-called relatively high paints, Further, it is possible to use a paint having a low polarity (such as olefin).
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 printing the molded product or for applying a coating to the molded product, any printing method generally used for printing plastics 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, flexo ink, screen ink, pad ink, dry offset ink and offset ink can be used.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples represent parts by weight, and% other than mol% represents% by weight.

[Polyolefin (A1), (A2)]
Production example 1
Polyolefin (A0-1) [commercial name "Sun Allomer PZA20A", manufactured by Sun Allomer Co., Ltd., Mw 200,000, the same applies hereinafter, in a reaction vessel containing 98 mol% propylene and 2 mol% ethylene as constituent units. ] 100 parts were charged, the gas phase was aerated with nitrogen while ventilating with a mantle heater, and heat-degraded at 360° C. for 70 minutes while stirring to obtain a polyolefin (A1-1). (A1-1) had a Mw of 8,000 and the number of double bonds in the molecular end and/or the molecular chain per 1,000 carbons was 7.4.

Production Examples 2-11, Comparative Production Examples 1-2
Polyolefin (A1-2) to (A1-6), (A2-1) to (A2-5), the same as in Production Example 1 except that thermal degradation was performed according to Table 1 in Production Example 1. (RA-1) to (RA-2) were obtained. The results are shown in Table 1.

[Production of acid-modified polyolefin (X), resin modifier (K)]
Example 1
Charge 15 parts (A1-1) and 85 parts (A2-1) and 4 parts maleic anhydride (B-1) to a reaction vessel, replace with nitrogen, and heat up to 180°C under nitrogen aeration to evenly heat. Dissolved.
A solution prepared by dissolving 1 part of dicumyl peroxide [trade name "Park Mill D", manufactured by NOF CORPORATION) (C-1) in 10 parts of xylene was added dropwise over 10 minutes, and then refluxed with xylene for 3 hours. Stirring was continued. Then, unreacted maleic anhydride is distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain a resin modifier (K-1) containing the acid-modified polyolefin (X-1). It was (X-1) had an acid value of 21 and Mw of 55,000.

Examples 2-11, Comparative Examples 1-4
In Example 1, according to Table 2, the same procedure as in Example 1 was performed except that each raw material used was used, and resin modifiers (K-2) to (K-11) and (RK-1) to (RK). -4) was obtained. The results are shown in Table 2.

[Resin composition, molded product]
Examples 12-25, Comparative Examples 5-12
The resin modifiers (K-1) to (K-11), (RK-1) to (RK-4), commercially available polypropylene (D-1) [trade name "Sun Allomer PL500A", manufactured by Sun Allomer Co., Ltd. ], commercially available polyethylene (D-2) [trade name "Novatech HJ490", manufactured by Nippon Polyethylene Co., Ltd.] and commercially available ethylene/propylene copolymer (D-3) [trade name "Sun Allomer PB222A", Sun Allomer (stock) )), mica (E2-1) [trade name “B-82”, manufactured by Yamaguchi Mica Co., Ltd., average particle size 180 μm], wollastonite (E2-2) [trade name “KGP-H45”, Kansai Matec Co., Ltd., average particle diameter 4.6 μm] according to the composition (part) of Table 3, according to the composition of Hensiel mixer [trade name "Hensiel mixer FM150L/B", Mitsui Mining Co., Ltd. Was manufactured by Nippon Coke Industry Co., Ltd.] for 3 minutes, and then melt-kneaded with a vented twin-screw extruder under the conditions of 180° C., 100 rpm and residence time of 5 minutes to obtain a polyolefin resin composition.
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.] to prepare a predetermined test piece, and the evaluation described below. It evaluated according to the method. The results are shown in Table 3.

<Evaluation method>
1. Impact resistance (Unit: J/m)
The Izod impact value was measured according to ASTM D256.
2. Affinity between polyolefin resin (D) and filler (E2) [Dispersibility of (E2)]
The fracture surface of the test piece after the above test 1 was observed with an electron microscope, and the affinity between (D) and (E2) was evaluated according to the following criteria.
⊚: No interfacial peeling between (D)/(E2) ◯: There is interfacial peeling between (D)/(E2), but only a part Δ: Interfacial peeling between (D)/(E2) is slightly high × : Almost no interfacial peeling between (D)/(E2). Flexural modulus (Unit: MPa)
It was 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 shown in Table 3, the resin modifier containing the acid-modified polyolefin obtained by the production method of the present invention is more excellent in dispersibility of the filler than the comparative resin modifier while maintaining mechanical strength. It can be seen that the modification characteristics are excellent.
Further, it is apparent that the molded product of the polyolefin resin composition is superior in the modifying property and the mechanical strength to the comparative product.

The resin modifier (K) containing the acid-modified polyolefin (X) obtained by the production method of the present invention can disperse a pigment and a filler in a molded product without lowering the mechanical strength of the molded product. And the like, and a molded product obtained by molding a polyolefin resin composition containing the modifier (K) has an excellent balance between the modifying property and the mechanical strength.
From this, the modifier (K) is used as a resin modifier for a polyolefin resin, a molded product or a molded article obtained by molding a polyolefin resin composition containing the resin modifier (K), -It can be suitably applied to a wide range of fields such as electronic devices, packaging materials, conveying materials, daily life materials and building materials.

Claims (9)

Polyolefin (A1) having 3 to 20 double bonds per 1,000 carbon atoms and having a weight average molecular weight of 4,000 to 18,000 , and 0.2 to 3 carbon atoms per 1,000 carbon atoms. A polyolefin (A2) having a double bond of 40,000 to 90,000 and a weight average molecular weight of 40,000 and 90 , and an unsaturated (poly)carboxylic acid (anhydride) (B). A method for producing a resin modifier (K) comprising an acid-modified polyolefin (X) , which comprises reacting in the presence of the acid-modified polyolefin (X) . The method for producing a resin modifier (K) according to claim 1, wherein (A1) and (A2) are thermal degradation products of polyolefin (A0) . The method for producing a resin modifier (K) according to claim 1 or 2, wherein a weight ratio [(A1)/(A2)] of (A1) and (A2) is 1/99 to 30/70 . The resin modifier (K) according to any one of claims 1 to 3, wherein the acid-modified polyolefin has an acid value (unit: mgKOH/g) of 10 to 60 and a weight average molecular weight of 20,000 to 120,000. Method. The resin modification according to any one of claims 1 to 4, wherein the product of the acid value and the weight average molecular weight of the acid-modified polyolefin [(acid value) x (weight average molecular weight)] is 800,000 to 4,000,000. Method for producing agent (K). A method for producing a polyolefin resin composition comprising the resin modifier (K) obtained by the method according to claim 1 and a polyolefin resin (D). The method for producing a polyolefin resin composition according to claim 6, wherein the weight ratio [(K)/(D)] of (K) and (D) is 0.1/99.9 to 40/60. A method for producing a molded article obtained by molding the polyolefin resin composition according to claim 6 . A method for producing a molded article, which comprises coating and/or printing the molded article according to claim 8 .