JP7340421B2 - Polyolefin resin modifier - Google Patents

Description

The present invention relates to polyolefin resin modifiers.

Polyolefin resins are widely used as general plastics for various purposes. Among these, a resin composition containing a polyolefin resin and biomass-derived powder (wood fiber, wood flour, etc.) has been developed (for example, Patent Document 1).

Japanese Patent Application Publication No. 8-269254

Even with the technique disclosed in Patent Document 1, the molded product of the resin composition cannot be said to have fully satisfactory mechanical properties, and improvements have been sought.
An object of the present invention is to provide a polyolefin resin modifier that imparts excellent mechanical properties to molded articles of biomass-containing resin compositions.

The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides an acid-modified polyolefin (X ) and an ionic liquid (G).

The polyolefin resin modifier (K) of the present invention has the following effects.
(1) Provide excellent mechanical properties (tensile strength, bending strength, etc.) to molded products of the biomass-containing resin composition (J).

<Polyolefin (A)>
The polyolefin (A) in the present invention is a polyolefin having a double bond at the molecular end and/or in the molecular chain.
The polyolefin (A) is preferably obtained by converting the polyolefin (A0) described below by a thermal degradation method (hereinafter referred to as a thermal degradation method, for example, as described in Japanese Patent Publication No. 43-9368 and Japanese Patent Publication No. 44-29742). It is obtained by thermal degradation according to the production method described above.

Moreover, (A) has a double bond at the molecular end and/or in the molecular chain from the viewpoint of copolymerizability with the below-described unsaturated (poly)carboxylic acid (anhydride) (B).
The number of double bonds in the molecular terminal and/or molecular chain per 1,000 carbon atoms (also referred to as 1,000 carbon atoms) of (A) is 0.1 to 20, preferably 0.3 to 20. The number is 18, more preferably 0.5 to 15. If the number of double bonds is less than 0.1, the copolymerizability with (B) described below will be poor, and if it exceeds 20, the productivity of the acid-modified polyolefin (X) described below will be poor.

Here, the number of double bonds can be determined from the spectrum of ¹ H-NMR (nuclear magnetic resonance) spectroscopy of (A). That is, the peak in the spectrum is assigned, and from the integral value derived from the double bond at 4.5 to 6 ppm of (A) and the integral value derived from (A), the number of double bonds in (A) and the integral value derived from (A) are determined. The relative value of the number of carbon atoms in (A) is determined, and the number of double bonds in the molecular terminal and/or in the molecular chain per 1,000 carbon atoms in (A) is calculated. The number of double bonds in the Examples described below was determined according to this method.

The thermal degradation method includes a method in which polyolefin (A0) is thermally degraded under nitrogen gas flow, (1) in the absence of an organic peroxide, for example, at 300 to 450°C for 0.5 to 10 hours, and (2) ) A method of thermal degradation in the presence of an organic peroxide [e.g. 2,5-dimethyl-2,5-di(t-butylperoxy)hexane] at 180 to 300°C for 0.5 to 10 hours, etc. included.
Among these methods, method (1) is preferable from the viewpoint of copolymerizability between (A) and (B), since it is easy to obtain a product with a larger number of double bonds at the molecular terminal and/or in the molecular chain. be.
The above nitrogen aeration is expressed as a nitrogen flow rate per 1 kg of polyolefin (A0) [abbreviated as nitrogen flow rate, unit: L/min, only numerical values may be described below], and is preferably 1.0 to 55.0. , more preferably 5.0 to 45.0, particularly preferably 10.0 to 35.0.

The Mn of (A) is 800 to 70,000, preferably 1,000 to 60,000, more preferably 1,500 to 50,000, particularly preferably 2,000 to 40,000. If the Mn of (A) is less than 800, the mechanical strength (mechanical properties) of the molded product described below will be poor, and if it exceeds 70,000, the productivity of the resin modifier (K) described below will be poor.

The polyolefin (A0) includes one or more (co)polymers of olefins, and copolymers of one or more olefins and one or more other monomers. is included.
The above olefins include alkenes having 2 to 30 carbon atoms (sometimes abbreviated as C in the present invention), such as ethylene, propylene, 1- and 2-butene, and isobutene, and α-olefins having 5 to 30 carbon atoms ( (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 (but not 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.] (weight ratio is determined by the moldability of the polyolefin resin composition and the molecular terminal and /or from the viewpoint of the amount of double bonds in the molecular chain, preferably from 30/70 to 99/1, more preferably from 50/50 to 95/5); propylene unit-containing (ethylene unit-free) (co)polymer For example, polypropylene, a copolymer of propylene and a C4-30 unsaturated monomer (the same as above); ethylene/propylene copolymer (the weight ratio is the same as above); from the viewpoint of the molecular terminal and/or the amount of double bonds in the molecular chain of (A), preferably 0.5/99.5 to 30/70, more preferably 2/98 to 20/80); C4 Included are (co)polymers of the above olefins, such as polybutene.
Among these, polyethylene, polypropylene, ethylene/propylene copolymer, propylene/ C4-30 unsaturated monomer copolymers, more preferred are ethylene/propylene copolymers and propylene/C4-30 unsaturated monomer copolymers.

Number average molecular weight of (A0) [hereinafter abbreviated as Mn]. The measurement is based on the gel permeation chromatography (GPC) method described below. same as below. ] is 30,000 to 400,000, preferably 50,000 to 200,000. If the Mn is less than 30,000, the mechanical strength of the molded product described below will be poor, and if the Mn exceeds 400,000, the productivity of the polyolefin (A) described below will be poor.

The conditions for measuring Mn by GPC in the present invention are as follows.
Equipment: High temperature gel permeation chromatograph
[“Alliance GPC V2000”,
Manufactured by Waters Co., Ltd.]
Detection device: Refractive index detector Solvent: Orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3mg/ml
Column stationary phase: PLgel 10μm, MIXED-B 2 bottles in series
[Manufactured by Polymer Laboratories Co., Ltd.]

<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, the unsaturated (poly)carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid, and/or an unsaturated polycarboxylic acid anhydride.

Among the unsaturated monocarboxylic acids (B), aliphatic (C3-24, such as acrylic acid, methacrylic acid, α-ethyl acrylic acid, crotonic acid, isocrotonic acid), alicyclic-containing (C6-24, For example, cyclohexenecarboxylic acid); unsaturated poly(2-3 or more) carboxylic acids (anhydrides) include unsaturated dicarboxylic acids (anhydrides) [aliphatic dicarboxylic acids (anhydrides) (C4-24, e.g. maleic acids, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), alicyclic-containing dicarboxylic acids (anhydrides) (C8-24, e.g. cyclohexenedicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptene dicarboxylic acid, dicarboxylic acid, methyltetrahydrophthalic acid, anhydrides thereof, etc.). (B) may be used alone or in combination of two types.
Among these, unsaturated dicarboxylic acid anhydride is preferred from the viewpoint of polymerizability with polyolefin (A) and modification effect of modifier (K), and maleic anhydride is more preferred.

<Acid-modified polyolefin (X)>
The acid-modified polyolefin (X) in the present invention contains the polyolefin (A) and the unsaturated (poly)carboxylic acid (anhydride) (B) as constituent units (constituent monomers).

The weight ratio of (A) and (B) in (X) [weight of (A)/weight of (B)] is preferably 80/20 to 99/2 from the viewpoint of mechanical strength and wettability of the molded product. 1, more preferably 85/15 to 98/2, particularly preferably 90/10 to 97/3.

Further, the forms of the acid-modified polyolefin (X) include the following.
[1] A graft copolymer having (A) as a trunk and (B) as branches.
[2] Random copolymer of (A) and (B).
In the form [1] above, (A) and (B) are heated and melted in the presence of a radical polymerization initiator (D), preferably a peroxide, or suspended or dissolved in an appropriate organic solvent, and then It can be formed by adding the above chain transfer agent (t) and polymerization inhibitor (f) and heating and stirring.
In the form of [2] above, (A) and (B) are heated and melted in the presence of a radical polymerization initiator (D), preferably an azo compound, or suspended or dissolved in an appropriate organic solvent, and if necessary, as described below. It can be formed by adding a chain transfer agent (t) and a polymerization inhibitor (f) and heating and stirring.
Among the forms [1] and [2], form [1] is preferable from the viewpoint of modification properties and mechanical strength of the molded article.

Mn of the acid-modified polyolefin (X) is preferably 1,000 to 70,000, more preferably 1,500 from the viewpoint of mechanical strength and moldability of the molded product (hereinafter sometimes simply referred to as molded product) described below. 60,000, particularly preferably 2,000 to 50,000.

From the viewpoint of the mechanical strength of the molded product, the lower limit of the acid value of (X) is preferably 5 mgKOH/g (only numerical values are shown below), more preferably 10, particularly preferably 15, most preferably 20, From the viewpoint of compatibility between (X) and the polyolefin resin (E) described below, the upper limit is preferably 150, more preferably 100, particularly preferably 80, and most preferably 60.
The acid value herein is a value obtained by measuring according to the following procedures (i) to (iii) in accordance with JIS K0070.
(i) Dissolve 1 g of (X) in 100 g of xylene whose temperature is adjusted to 100°C.
(ii) Titration 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) Calculate the acid value (unit: mgKOH/g) by converting the amount of potassium hydroxide required for titration into mg.
In addition, in the above measurement, a result is obtained in which one acid anhydride group is equivalent to one carboxyl group. The acid values in the Examples described below were determined according to this method.

<Ionic liquid (G)>
The ionic liquid (G) in the present invention is a salt composed of an anion component (Ga) and a cation component (Gb). The ionic liquid (G) preferably has a melting point of 150° C. or lower from the viewpoint of productivity of the polyolefin resin modifier (K) described below.

<Anion component (Ga)>
The anion component (Ga) constituting the ionic liquid (G) includes halogen ions (F ^- , Cl ^- , Br ^- and I ^-, etc.), carboxylate anions {mono- or dicarboxylic acids having 1 to 7 carbon atoms (formic acid, Ions such as acetic acid, propionic acid, oxalic acid, and succinic acid (-COO ^- )}, sulfonic acid ions {sulfonic acids having 1 to 20 carbon atoms (methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid) and ions such as p-toluenesulfonic acid (-SO ₃ ^- )}, phosphate ions {phosphoric acid or ions of phosphoric acid group-containing compounds having 1 to 10 carbon atoms (-OPO ₃ ^2- )}, thiocyanate ions, Perchlorate ion, sulfate ion, nitrate ion, BF ₄ ^- , PF ₆ ^- , SbF ₆ -, AsF ₆ ^- , TlF ₆ ^- , BF ₃ Cl ^- , PF ₅ Cl ^- , SbF ₅ Cl ^- , AsF ₅ ^{Cl -} , TIF ₅ Cl ⁻ , BF ₃ Br ⁻ , PF ₅ Br ⁻ , SbF ₅ Br − , AsF ₅ Br ⁻ , TIF ₅ Br ⁻ , BF ₃ I ⁻ , PF _{5 I − , SbF 5} ^I ₋ ^{, AsF} ₅ I ⁻ and TIF ₅ I ^- ; and other anions such as OH ^- , ClO ₄ ^- and the like.
Among the anion components (Ga), preferred are halogen ions and sulfonic acid ions from the viewpoint of mechanical strength of the molded product.

<Cation component (Gb)>
Examples of the anion component (Gb) constituting the ionic liquid (G) include ammonium cations, amidinium cations, pyridinium cations, and the like.
Among the anion components (Gb), preferred is amidinium cation, and more preferred is 1-ethyl-3-methyl-imidazolium.

Examples of ammonium cations include the following.
[1] Aliphatic quaternary ammonium having an alkyl and/or alkenyl group having 4 to 30 or more carbon atoms Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, trimethylethylammonium, tetraethylammonium, trimethyl Propylammonium, dimethyldipropylammonium, ethylmethyldipropylammonium, butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium, tetrahexylammonium, trimethyldecylammonium, dimethyldidecylammonium, etc.;
[2] Aromatic quaternary ammonium having 6 to 30 carbon atoms or more; trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium, etc.;
[3] Alicyclic quaternary ammonium having 3 to 30 or more carbon atoms N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N,N-diethylpyrrolidinium, N,N -dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N,N-diethylmorpholinium, N,N-dimethylpiperidinium, N,N-diethylpiperidinium, etc.;

Examples of the amidinium cation include the following.
[1] Imidazolinium cation C5-15, such as 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3 , 4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3 -Triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethylimidazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl -1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolinium, 3-methylcarboxymethyl -1,2-dimethylimidazolinium, 4-methoxy-1,2,3-trimethylimidazolinium, 3-methoxymethyl-1,2-dimethylimidazolinium, 4-formyl-1,2,3-trimethyl Imidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium, 4-hydroxymethyl-1,2,3-trimethylimidazolinium, 2- Hydroxyethyl-1,3-dimethylimidazolinium;

[2] Imidazolium cation C5-15, such as 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2 , 3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl- 3-ethyl-imidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzyl Imidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3- Dimethyl-imidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolium, 3 -Methylcarboxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2,3 -Trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, 2-hydroxyethyl -1,3-dimethylimidazolium;

[3] Tetrahydropyrimidinium cation C6-15, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyri Midinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium , 1,8-diazabicyclo[5,4,0]-7-undecenium, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium, 1,5-diazabicyclo[4,3,0 ]-5-nonenium, 5-methyl-1,5-diazabicyclo[4,3,0]-5-nonenium, 4-cyano-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidium 3-cyanomethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4- Acetyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methyl Carboxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methylcarboxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium , 4-methoxy-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 3 -Hydroxyethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2 -hydroxyethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium;

[4] Dihydropyrimidinium cation C6-20, such as 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium, [these are 1,3-dimethyl-1,4(6)- It is written as dihydropyrimidinium, and the same notation will be used below. ]1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4(6)-dihydropyrimidinium, 1,2,3, 5-tetramethyl-1,4(6)-dihydropyrimidinium, 8-methyl-1,8-diazabicyclo[5,4,0]-7,9(10)-undecadienium, 5-methyl- 1,5-diazabicyclo[4,3,0]-5,7(8)-nonadienium, 4-cyano-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 3-cyanomethyl- 1,2-dimethyl-1,4(6)-dihydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4(6)-dihydropyrimidinium, 4-acetyl-1,2,3- Trimethyl-1,4(6)-dihydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 4-methylcarboxymethyl-1,2,3- Trimethyl-1,4(6)-dihydropyrimidinium, 3-methylcarboxymethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl -1,4(6)-dihydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-1, 4(6)-dihydropyrimidinium, 3-formylmethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4(6) -dihydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 2-hydroxyethyl-1,3-dimethyl-1,4(6)-hydro Pyrimidinium.

Examples of pyridinium cations include C6-20, such as 3-methyl-1-propylpyridinium, 1-propyl-3-methylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl- Examples include 3,4-dimethylpyridinium and 1-butyl-3,5-dimethylpyridinium.

<Polyolefin resin modifier (K)>
The polyolefin resin modifier (K) of the present invention contains the acid-modified polyolefin (X) and an ionic liquid (G).

The weight ratio [(X)/(G)] of the above (X) and (G) is preferably 50/50 to 95/5, more preferably 75/25 to 95/5, from the viewpoint of modification properties and mechanical strength. It's 90/10.
The polyolefin resin modifier (K) is useful as a variety of modifiers, but it is preferably used as a resin modifier for the biomass-containing resin composition (J) described below, especially as a modifier for biomass-derived fillers. It will be done. That is, it is thought to function as a dispersant for dispersing the biomass-derived filler (H) in the polyolefin resin (E).

The method for producing the polyolefin resin modifier (K) of the present invention includes:
(1) A method of mixing the above (X), (G) and an organic solvent to form a polyolefin resin modifier (K) (solvent method);
(2) A method of mixing the above (X) and (G) without a solvent to form a polyolefin resin modifier (K) (solvent-free method);
Preferred method from the viewpoint of productivity of (K) is method (2).

<Polyolefin resin (E)>
The polyolefin resin (E) in the present invention can be produced by the polymerization method exemplified as the production method for (A0) above, or by the degradation (thermal, chemical and mechanical methods) of high molecular weight polyolefin (preferably Mn 80,000 to 400,000). For example, the above-mentioned ethylene unit-containing (propylene unit-free) (co)polymers, propylene unit-containing (ethylene unit-free) (co)polymers, ethylene/ Included are propylene copolymers and (co)polymers of C4 or higher olefins.

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

<Biomass-derived filler (H)>
Biomass includes plant biomass (wood, pulp, bamboo, rice, rice bran, rice straw, wheat straw, rice husk, bagasse, coconut husk fiber, bamboo, reed, kenaf, cotton linter, banana fiber, sugarcane fiber, flour, wheat bran, Contains soybeans, soybean hulls, soybean oil cake, rapeseed, rapeseed oil cake, sesame, sesame oil cake, corn flour, corn husk, corn endosperm, corn starch, etc.), and animal biomass (crustacean exoskeleton, chitosan, chitin, etc.) .
Among these, from the viewpoint of productivity of (H), plant biomass is preferred, and wood is more preferred.
Examples of (H) include those obtained by pulverizing and pulverizing biomass (powder form) and those obtained by pulverizing and disintegrating biomass (fibrous form).
When (H) is in powder form, its volume average particle diameter is preferably 0.01 μm to 3 mm, more preferably 0.1 μm to 1 mm, and particularly preferably 1 μm to 500 μm from the viewpoint of mechanical properties of (H). . The volume average particle diameter is determined by a laser diffraction scattering method, and examples of the measuring device include a particle size distribution analyzer [trade name "Microtrac MT3000II Particle Size Analyzer", manufactured by Nikkiso Co., Ltd.].
When (H) is fibrous, the fiber diameter is preferably 0.1 μm to 1 mm, more preferably 1 to 500 μm, from the viewpoint of mechanical strength and moldability of the molded product. Further, the fiber length of (E) is preferably 1 μm to 10 mm, more preferably 10 μm to 1 mm, from the viewpoint of mechanical strength and moldability of the molded product. The fiber diameter and fiber length are determined by image analysis of electron microscope images.

<Biomass-containing resin composition (J)>
The biomass-containing resin composition (J) of the present invention contains the polyolefin resin modifier (K), the polyolefin resin (E), and the biomass-derived filler (H).

In addition, based on the total weight of (K), (E), and (H), from the viewpoint of modification properties and mechanical properties, (K) is preferably 1 to 20% by weight, and (E) is preferably 30 to 30% by weight. (H) is 5 to 60 weight %, more preferably (K) is 3 to 15 weight %, (E) is 30 to 90 weight %, and (H) is 7 to 60 weight %.

The combination of (E) and (K) is when the constitutional units of (E) and the constitutional units of polyolefin (A) constituting (K) are the same or similar. Preferable from the viewpoint of compatibility. For example, if (E) is a (co)polymer containing propylene units (no ethylene units), then (A) constituting (K) is also a (co)polymer containing propylene units (no ethylene units). It is preferable if there is.

The biomass-containing resin composition (J) of the present invention may further contain a colorant (F1), a reinforcing agent (F2), a matting agent (F3), an antistatic agent (F4), if necessary, within a range that does not impede the effects of the present invention. ), dispersant (F5), flame retardant (F6), foaming agent (F7), antioxidant (F8), ultraviolet absorber (F9), and plasticizer (F10). The above additives (F) can be included.

The total amount of (F) used in the biomass-containing resin composition (J) of the present invention is, for example, 30% or less based on the total weight of the biomass-containing resin composition (J), and the functional expression of (F) and the industrial From the above point of view, it is preferably 1 to 10%.

The usage amount of each additive (F) based on the total weight of the biomass-containing resin composition (J) is, (F1) is, for example, 10% or less, preferably 1 to 5%; (F2) is, for example, 15% or less, preferably is 3 to 10%; (F3) is, for example, 20% or less, preferably 1 to 10%; (F4) is, for example, 10% or less, preferably 1 to 5%; (F5) is, for example, 20% or less, preferably 0 -15%, particularly preferably 0-10%; (F6) is, for example, 15% or less, preferably 3-10%; (F7) is, for example, 1-20% or less, preferably 5-15%; (F8) is For example, 3% or less, preferably 0.01 to 1%; (F9), for example, 3% or less, preferably 0.01 to 1%; (F10), for example, 20% or less, preferably 5 to 15%.

If the additives (F1) to (F10) are the same and overlap, do not use the amount of each additive that produces the corresponding additive effect regardless of the effect of the other additives. The amount used shall be adjusted depending on the purpose of use, taking into consideration that the effect as an additive can be obtained at the same time.

The method for producing the biomass-containing resin composition (J) of the present invention includes:
(1) A method of preparing a biomass-containing fat composition (J) by simultaneously mixing the above (E), (K), (H), and if necessary (F) (batch method);
(2) Masterbatch biomass-containing resin composition containing a high concentration of (K) by mixing part of (E), all of (K), (H), and if necessary part or all of (F) The method includes a method (masterbatch method) in which product (J) is once prepared, and then the remaining (E) and, if necessary, the remainder of (F) are added and mixed to obtain a biomass-containing resin composition (J).
Method (2) is preferred from the viewpoint of mixing efficiency of (J).

The specific mixing method in the method for producing the biomass-containing resin composition (J) is as follows:
(i) Each component to be mixed is mixed using, for example, a powder mixer [“Hensiel Mixer” [trade name “Hensiel Mixer FM150L/B”, manufactured by Mitsui Mining Co., Ltd., after the company name change is made by Nippon Coke Industry Co., Ltd.] , "Nauta Mixer" [trade name "Nauta Mixer DBX3000RX", manufactured by Hosokawa Micron Co., Ltd.], "Banbury Mixer" [trade name "MIXTRON BB-16MIXER", manufactured by Kobe Steel Corporation], etc.], then melt-kneading equipment. A method of kneading for 2 to 30 minutes at 120 to 220° C. using a [batch kneader, continuous kneader (single screw kneader, twin screw kneader, etc.)];
(ii) A method in which the components to be mixed are directly kneaded under the same conditions using the same melt-kneading apparatus as above without pre-mixing the powders may be mentioned.
Among these methods, method (i) is preferred from the viewpoint of mixing efficiency.

<Molded products, molded articles>
The molded article of the present invention is obtained by molding the biomass-containing resin composition (J).
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.), and depending on the purpose, single-layer It can be molded by any method including molding, multilayer molding, foam molding, or the like. Examples of the form of the molded product include a plate, a sheet, a film, and fibers (including nonwoven fabrics, etc.).
Since the molded article of the present invention contains a resin modifier (K) containing the acid-modified polyolefin (X) having carboxyl groups, etc. and an ionic liquid (G), the molded article has a relatively high polarity. It also has excellent compatibility with inks, etc.

The molded article of 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 methods for coating the molded article 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 paints commonly used for coating plastics, such as polyester melamine resin paints, epoxy melamine resin paints, acrylic melamine resin paints, and acrylic urethane resin paints. Even with these so-called relatively highly polar paints, It is also possible to use paints with low polarity (olefin-based, etc.).
The coating film thickness (dry film thickness) can be appropriately selected depending on the purpose, and is, for example, 10 to 50 μm.

In addition, as a method for further printing after coating the molded product or molded product, any printing method generally used for printing plastics can be used, such as gravure printing, flexography, etc. Examples include printing, screen printing, pad printing, dry offset printing, and offset printing.
As the printing ink, known inks used for printing plastics can be used, such as gravure ink, flexo ink, screen ink, pad ink, dry offset ink, and offset ink.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight, and percentages other than mol% represent weight%.

<Manufacture example 1>
In a reaction vessel, a polyolefin (A0-1) containing 98 mol% of propylene and 2 mol% of ethylene as constituent units [trade name "Sun Allomer PZA20A", manufactured by Sun Allomer Co., Ltd., Mn 100,000, the same applies hereinafter. ] 100 parts were charged in a nitrogen atmosphere, heated and melted with a mantle heater while bubbling nitrogen into the gas phase (nitrogen flow rate: 15.0), and thermally degraded at 360°C for 70 minutes with stirring to obtain a polyolefin. (A-1) was obtained. In (A-1), the number of double bonds in the molecular terminal and/or molecular chain per 1,000 carbon atoms was 7.2, and the Mn was 3,000.

<Production Examples 2 to 8>
In Production Example 1, each polyolefin (A) was obtained in the same manner as in Production Example 1, except that thermal degradation was performed according to Table 1. The results are shown in Table 1.

Production of acid-modified polyolefin (X) <Production Example 11>
100 parts of (A-1) was placed in a reaction vessel, and after purging with nitrogen, the mixture was heated to 180° C. under nitrogen gas flow to uniformly melt the mixture. After charging and dissolving 8 parts of maleic anhydride (B-1), 2 parts of dicumyl peroxide [trade name "Percumil D", manufactured by NOF Corporation] (D-1) was added to 4 parts of xylene. The dissolved solution was added dropwise over 10 minutes, and stirring was continued at 180°C for 3 hours. Thereafter, xylene was distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain acid-modified polyolefin (X-1). (X-1) had an acid value of 41 and an Mn of 4,000.

<Production Examples 12 to 21>
In Production Example 11, each acid-modified polyolefin (X) was obtained in the same manner as in Production Example 11, except that each raw material was used according to Table 2. The results are shown in Table 2.

<Example 1>
A reaction vessel was charged with 5 parts of (X-1) and 5 parts of xylene, and after purging with nitrogen, the mixture was heated to 140° C. under nitrogen gas flow to uniformly melt the mixture. One part of the ionic liquid (G-1) was added thereto, and stirring was continued at 140°C for 1 hour. Thereafter, xylene was distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain a polyolefin resin modifier (K-1).

<Examples 2 to 14, Comparative Example 1>
In Example 1, each polyolefin resin modifier (K) was obtained in the same manner as in Example 1 except that each raw material was used according to Table 3. The results are shown in Table 3.

<Examples 21-42, Comparative Examples 11-12>
The obtained polyolefin resin modifier and the raw materials used below [polyolefin resin (E), biomass-derived filler (H)] were blended for 3 minutes in a Henschel mixer according to the composition (parts) in Table 4. Each biomass-containing resin composition (J) was obtained by melt-kneading in a vented twin-screw extruder under the conditions of 180° C., 100 rpm, and residence time of 5 minutes.
Each resin composition (J) was molded using an injection molding machine [trade name "PS40E5ASE", Nissei Jushi Kogyo Co., Ltd.] at a cylinder temperature of 190°C and a mold temperature of 60°C to create a prescribed test piece. Evaluation was made according to the evaluation method described below. The results are shown in Table 4.

<Evaluation method>
(1) Tensile strength (unit: MPa)
Measured according to ASTM D638.
(2) Bending strength (unit: MPa)
Measured according to ASTM D790.

From the results in Tables 1 to 4, it can be seen that the polyolefin resin modifier (K) of the present invention provides superior mechanical properties to molded articles of biomass-containing resin compositions compared to the comparative ones.

Molded products obtained from the biomass-containing resin composition (J) of the present invention have excellent mechanical properties and are environmentally friendly with less environmental impact when disposed of, so they can be used for electrical and electronic equipment, transportation materials, and household materials. It can be suitably applied to a wide range of fields such as construction materials and construction materials, and is extremely useful.

Claims (6)

An acid-modified polyolefin (X) containing a polyolefin (A) having a double bond at the molecular end and/or in the molecular chain and an unsaturated (poly)carboxylic acid (anhydride) (B) as constituent units, and an ionic liquid ( G), the acid value (unit: mgKOH/g) of the acid-modified polyolefin (X) is 5 to 150, and the number average molecular weight (Mn) of the acid-modified polyolefin (X) is 1,000 to 70, 000, the ionic liquid (G) is composed of an anion component (Ga) and a cation component (Gb), and the cation component (Gb) is selected from the group consisting of amidinium cation, pyridinium cation and ammonium cation. A polyolefin resin modifier (K), wherein the anion component (Ga) is at least one selected from the group consisting of halogen ions and sulfonic acid ions. The polyolefin resin modifier according to claim 1, wherein the weight ratio [(X)/(G)] of the acid-modified polyolefin (X) and the ionic liquid (G) is from 50/50 to 95/5. A biomass-containing resin composition (J) comprising the polyolefin resin modifier (K) according to claim 1 or 2 , a polyolefin resin (E), and a biomass-derived filler (H). Based on the total weight of (K), (E) and (H), (K) is 1 to 20% by weight, (E) is 30 to 90% by weight, and (H) is 5 to 60% by weight. The biomass-containing resin composition according to claim 3 . A molded article obtained by molding the biomass-containing resin composition (J) according to claim 3 or 4 . A molded article obtained by applying painting and/or printing to the molded article according to claim 5 .