JP5952117B2 - Biomass-containing resin composition - Google Patents

Description

  The present invention relates to a biomass-containing resin composition. More specifically, the present invention relates to a biomass-containing resin composition that has excellent mechanical properties and gives an environmentally friendly molded product when discarded. In the present invention, biomass means a biological resource.

Conventionally, polyolefin resins have been widely used in large quantities for various applications because of their light weight, high strength, and ease of molding.
However, due to the increased plastic waste as a result, environmental pollution is a problem. Examples of disposal methods for discarded plastics that have passed the useful life include incineration and landfilling. However, these disposal methods have the following problems. In other words, the incineration method has a high calorie burn and easily damages the incinerator, the incineration of carbon dioxide that causes global warming is inevitable, and the landfill method is stable in the soil. There are many problems, such as a shortage of landfills, because it remains without being biodegraded.
Therefore, as a measure for reducing substantial carbon dioxide emissions in the incineration method and promoting biodegradation in the landfill method, a resin composition containing polyolefin resin and biomass-derived powder (wood fiber, wood powder, etc.) (See, for example, Patent Documents 1, 2, and 3).

JP-A-8-269254 JP-A-9-286880 Japanese Patent Laid-Open No. 10-130437

However, in the case of the resin composition as described above, since the affinity between the polyolefin resin and the biomass-derived powder is insufficient, mechanical properties such as impact resistance of a molded product formed by molding the resin composition. There was a problem.
An object of the present invention is to provide a resin composition excellent in affinity comprising a polyolefin resin and a biomass-derived powder, and formed from the composition, excellent in mechanical properties, and has an environmental load even when discarded. It is to provide a small number of molded products.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention contains a polyolefin (a) having a number average molecular weight of 800 to 50,000, an unsaturated (poly) carboxylic acid (anhydride) (b), and an α-olefin (c) having 6 to 36 carbon atoms. A dispersant (A) obtained by copolymerizing a copolymer component not containing styrene or a styrene derivative in the presence of a radical initiator (d), a polyolefin resin (B), and a biomass-derived powder (C). This is a biomass-containing resin composition.

The biomass-containing resin composition of the present invention has the following effects.
(1) The affinity between the constituent polyolefin resin and biomass is good.
(2) The molded product obtained is excellent in mechanical properties such as impact resistance.
(3) The molded product is an environmentally harmonious type that has a low environmental impact upon disposal.

[Polyolefin (a)]
The polyolefin (a) in the present invention includes one or more (co) polymers of olefins, and a copolymer of one or more olefins and one or more other monomers. A polymer is included.
Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter abbreviated as C) such as ethylene, propylene, 1- and 2-butene, and isobutene, and C5-30 α-olefins (1-hexene, 1-hexene, Decene, 1-dodecene, etc.); other monomers include C4-30 unsaturated monomers that are copolymerizable with olefins, such as vinyl acetate.

Specific examples of (a) include ethylene unit-containing (propylene unit-free) (co) polymers 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.), copolymer with vinyl acetate, etc. [weight ratio is the moldability of the resin composition and in the molecule of (a) From the viewpoint of the number of double bonds, preferably 30/70 to 99/1, more preferably 50/50 to 95/5) and the like; propylene unit-containing (ethylene unit-free) (co) polymers such as polypropylene and propylene Copolymer with C4-30 unsaturated monomer (same as above) [weight ratio is preferably 30/70 from the viewpoint of the number of double bonds in the molecule of (a) and the moldability of the resin composition] ~ 99/1, more preferably 50/50 to 95/5]; ethylene / propylene copolymer [weight ratio is preferably 0.5 / 99.5 from the viewpoint of moldability of the resin composition and the number of double bonds in the molecule of (a). ~ 30/70, more preferably 2/98 ~ 20/80]; (co) polymers of C4 or higher olefins such as polybutene.
Among these, from the viewpoint of copolymerization with an unsaturated (poly) carboxylic acid (anhydride) (b) and C6-36 α-olefin (c) described later, polyethylene, polypropylene, ethylene / propylene copolymer are preferable. Polymers, propylene / C4-30 unsaturated monomer copolymers, more preferably ethylene / propylene copolymers.

  Number average molecular weight of (a) [hereinafter abbreviated as Mn. The measurement is performed by a gel permeation chromatography (GPC) method described later] is 800 to 50,000, preferably 1,000 to 45,000. If Mn is less than 800, the mechanical properties of a molded article (hereinafter sometimes simply referred to as a molded article) described later deteriorate, and if it exceeds 50,000, the productivity of (A) decreases and the high viscosity of (A). The function of improving the dispersibility of the biomass-derived powder (C), which will be described later, into the polyolefin resin (B) (hereinafter sometimes abbreviated as dispersion performance) is deteriorated.

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

(A) is a compound in the molecular chain and / or at the molecular terminal from the viewpoint of copolymerization with an unsaturated (poly) carboxylic acid (anhydride) (b) described later and an α-olefin (c) of C6-36. It preferably has a double bond.
The number of double bonds per 1,000 carbon atoms in (a) is preferably from the viewpoint of the copolymerizability between (a), (b) and (c) and the productivity of (A). The number is 20, more preferably 0.3 to 18, and particularly preferably 0.5 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 from the integrated value derived from the double bond at 4.5 to 6 ppm of (a) and the integrated value derived from (a), the number of double bonds in (a) and (a) Is calculated, and the number of double bonds in the molecular end and / or molecular chain per 1,000 carbon atoms in (a) is calculated. The number of double bonds in the examples described later followed this method.

  Polyolefin (a) can be produced by polymerization methods (for example, those described in JP-A-59-206409) and degradation methods (thermal, chemical and mechanical degradation methods, etc.). Examples of the degradation method (hereinafter also referred to as the thermal degradation method) include those described in Japanese Patent Publication No. 43-9368, Japanese Patent Publication No. 44-29742, and Japanese Patent Publication No. 6-70094]. .

  The polymerization method includes a method of (co) polymerizing one or more of the olefins, and a method of copolymerizing one or more of the olefins and one or more of the other monomers. It is.

  In the degradation method, a polyolefin (a0) having a high molecular weight [preferably Mn of 30,000 to 400,000, more preferably 50,000 to 200,000] obtained by the polymerization method is thermally, chemically or A method of mechanical degradation is included.

In the thermal degradation method, the high molecular weight polyolefin (a0) is subjected to thermal degradation in the presence of nitrogen (1) in the absence of an organic peroxide, usually at 300 to 450 ° C. for 0.5 to 10 hours. And (2) a method of thermally degrading usually at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide.
Among these, the polyolefin (a) obtained from the viewpoint of copolymerizability with (b) and (c) is preferably one having a larger number of double bonds in the molecular chain and / or molecular terminal. This is the easy method (1).

  Among these production methods (a), those having a larger number of double bonds in the molecular chain and / or at the molecular end are easily obtained, and the copolymerization of (a), (b) and (c) From the viewpoint of ease, a degradation method is preferable, and a thermal degradation method is more preferable.

[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 anhydride.
Among these (b), as the 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 these, unsaturated dicarboxylic acid (anhydride) is preferable from the viewpoint of copolymerizability with C6-36 α-olefin (c) described later, more preferably unsaturated dicarboxylic acid anhydride, and particularly preferable. Maleic anhydride.

[C6-36 α-olefin (c)]
The α-olefin (c) in the present invention includes C6 to 36, preferably C8 to 30 linear α-olefins and branched α-olefins. When C of (c) is less than 6, the mechanical properties of the molded product described later deteriorate, and when it exceeds 36, (A) has the dispersibility of the biomass-derived powder (C) described later in the polyolefin resin (B). The improvement function [(A) dispersion performance] deteriorates.
Examples of the linear α-olefin in (c) include 1-hexene, 1-octene, 1-nonene, 1-decene, and a mixture of two or more thereof.
Examples of the α-olefin having a branched chain include propylene trimer, propylene tetramer, and a mixture of two or more thereof.
Of these, linear α-olefins are preferred from the viewpoint of copolymerizability with (a) and (b), and 1-decene is more preferred.

  The content of each component based on the total weight of (a), (b) and (c) is preferably 30 to 98% from the viewpoint of (a) productivity and (A) dispersion performance. More preferably 40 to 90%; (b) is preferably 0.03 to 40%, more preferably 0.5 to 35% from the viewpoint of the dispersion performance of (A) and the productivity of (A); (c) Is preferably 0.6 to 65%, more preferably 1 to 50% from the viewpoint of the productivity of (A) and the dispersion performance of (A).

[Radical initiator (d)]
(A), (b) and (c) in the present invention are copolymerized in the presence of the radical initiator (d).
Examples of (d) include azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobiscyclohexane-1-carbohydrate. Nitrile, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (N-cyclohexyl-2- Methylpropionamide)), peroxides [monofunctional (having one peroxide group in the molecule) (benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and many Functional (having two or more peroxide groups in the molecule) [2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t Butyl peroxyhexahydroterephthalate, diallyl peroxydicarbonate and the like]], and the like.

Of these, an azo compound is more preferable from the viewpoints of the copolymerizability of (a), (b) and (c) and the suppression of the crosslinking of (a) by the hydrogen abstraction reaction of (a) which is a side reaction. Of 1,1′-azobiscyclohexane-1-carbonitrile, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane) 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), particularly preferably 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis (N-butyl-2- Methylpropionamide).
When an azo compound is used as (d), the hydrogen abstraction reaction of (a) hardly occurs, the crosslinking of (a) is suppressed, and (A) of the crosslinked product is hardly generated. As a result, the affinity with the polyolefin resin (B) described later is increased, the dispersion performance of (A) is more effectively exhibited, and the mechanical properties of the molded product are further improved.

  The amount of (d) used is preferably 0.05 to 10%, more preferably 0.2 based on the total weight of (a), (b) and (c) from the viewpoint of reactivity and side reaction suppression. -5%, particularly preferably 0.5-3%.

[Dispersant (A)]
The dispersant (A) of the present invention comprises a polyolefin (a) having an Mn of 800 to 50,000, an unsaturated (poly) carboxylic acid (anhydride) (b), and C6 to 36 in the presence of the radical initiator (d). The α-olefin (c) is copolymerized with a copolymer component that does not contain styrene or a styrene derivative.

The copolymer component constituting the dispersant (A) does not contain styrene or styrene derivatives. When the copolymer component contains styrene or a styrene derivative, the dispersion performance of (A) is inferior.
The styrene derivatives include those having C9 to 15 such as α-methylstyrene, p-methoxystyrene, m-butylstyrene and the like.

The specific production method (A) includes the following methods [1] and [2].
[1] (a), (b) and (c) are mixed with a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (di- -, 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.) )], Or (d) [or a solution in which (d) is dissolved in an appropriate organic solvent (the same as above)] and, if necessary, a chain transfer agent (t) described below are added. Method of heating and stirring (solution method);
[2] A method (melting method) in which (a), (b), (c) and (d), and (t) as necessary are mixed in advance and kneaded using an extruder, a Banbury mixer, a kneader or the like.

  The reaction temperature in the solution method may be a temperature at which (a) is dissolved in an organic solvent, and is preferably 50 from the viewpoint of productivity of (A) and reaction control of (a), (b), and (c). It is -220 degreeC, More preferably, it is 110-210 degreeC, Most preferably, it is 120-180 degreeC.

  The reaction temperature in the melting method may be a temperature at which (a) melts, and is preferably 120 from the viewpoint of the copolymerizability of (a), (b) and (c) and the decomposition temperature of the reaction product. It is -260 degreeC, More preferably, it is 130-240 degreeC.

Examples of the chain transfer agent (t) include aromatic hydrocarbons (C6-24, such as (toluene, xylene, ethylbenzene, isopropylbenzene, etc.)); halogen hydrocarbons (C1-24, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane). ); Alcohol (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol, allyl alcohol); thiol (C1-24, such as ethylthiol, propylthiol, 1- and 2-butylthiol, 1-octylthiol) ); Ketones (C3-24, such as acetone, methyl ethyl ketone); aldehydes (C2-18, such as 2-methyl-2-propylaldehyde, 1- and 2-butyraldehyde, 1-pentylaldehyde); phenols (C6-36, For example, Feno , O-, m- and p-cresol); amines (C3-24, such as diethylmethylamine, triethylamine, diphenylamine); disulfides (C2-24, such as diethyldisulfide, di-1-propyldisulfide) and the like. .
The amount of (t) used is usually 30% or less based on the total weight of (a), (b) and (c), the productivity of (a), (b) and (c) and the molded product described later. From the viewpoint of mechanical properties, it is preferably 0.1 to 20%.

  The Mn of the dispersant (A) is preferably 1,500 to 70,000, more preferably 2,000 to 60,000, particularly preferably from the viewpoint of the mechanical properties of the molded product and the moldability of the resin composition described later. 2,500 to 50,000.

The acid value of (A) is preferably 0.5 to 200 mg KOH / g (only numerical values are shown below), more preferably 1 to 180, from the viewpoint of the dispersion performance of (A) and the productivity of (A). 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 (A) is dissolved in 100 g of xylene adjusted to 100 ° C.
(Ii) Titration is performed with a 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.
(Iii) The amount of potassium hydroxide required for titration is converted to mg, and the acid value (unit: mgKOH / g) is calculated.

[Polyolefin resin (B)]
The polyolefin resin (B) in the present invention is obtained by the polymerization method exemplified as the production method of the above (a), or a high molecular weight (preferably Mn 80,000 to 400,000) polyolefin degradation (thermally, Chemical and mechanical degradation), and (B) includes the above-mentioned ethylene unit-containing (propylene unit-free) (co) polymer, propylene unit-containing (ethylene-unit-free) ) (Co) polymers, ethylene / propylene copolymers and (co) polymers of C4 or higher olefins.

  As a combination of (A) and (B) in the present invention, there are cases where the structural unit of (B) and the structural unit of the polyolefin (a) constituting (A) are the same or similar (A) and (B ) From the viewpoint of compatibility. For example, when (B) is a propylene unit-containing (ethylene unit-free) (co) polymer, (a) constituting (A) is also a propylene unit-containing (ethylene unit-free) (co) polymer. Some cases are preferred.

  Mn in (B) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, from the viewpoint of the mechanical properties of the molded product described later and miscibility with (A).

[Powder derived from biomass (C)]
Biomass includes plant biomass (wood, bamboo, rice, rice straw, straw, rice husk, bagasse, coconut fiber, straw, straw, kenaf, cotton linter, wood pulp, banana fiber, sugarcane fiber, etc.) and animal biomass ( Crustacean exoskeleton, chitosan, chitin, etc.).
Among these, from the viewpoint of the productivity of (C), preferred is plant biomass, and more preferred is wood.
(C) is obtained by pulverizing biomass and pulverizing it.
The volume average particle diameter of (C) is preferably 1 μm to 3 mm, more preferably 20 μm to 1 mm, particularly preferably 50 μm to 500 μm from the viewpoint of the productivity of (C) and the mechanical properties of the molded product. The volume average particle diameter is determined by a laser diffraction scattering method, and examples of the measuring apparatus include a particle size distribution measuring instrument [trade name “Microtrack MT3000II particle size analyzer”, manufactured by Nikkiso Co., Ltd.].

[Resin composition]
The resin composition of the present invention comprises a dispersant (A), a polyolefin resin (B), and a biomass-derived powder (C).
In the resin composition, the ratio of each component based on the total weight of (A), (B), and (C) is as follows: (A) is dispersibility of (C) in (B) and mechanical properties of the molded product Is preferably 0.5 to 15%, more preferably 0.7 to 12%, particularly preferably 1 to 10%; (B) is preferably 5 from the viewpoint of mechanical properties and biodegradability of the molded product. -90%, more preferably 10-85%, particularly preferably 15-80%; (C) is preferably 5-85%, more preferably 10-80, from the viewpoint of biodegradability and mechanical properties of the molded article. %, Particularly preferably 15 to 75%.
The weight ratio [(B) / (C)] of (B) to (C) in the resin composition is preferably 10/90 to 90/10, more preferably from the viewpoint of mechanical properties and biodegradability of the molded product. 20/80 to 80/20, particularly preferably 30/70 to 70/30.

The resin composition of the present invention can further contain various additives (D) as necessary within the range not inhibiting the effects of the present invention.
(D) includes colorant (D1), flame retardant (D2), filler (D3), lubricant (D4), antistatic agent (D5), antioxidant (D6) and ultraviolet absorber (D7). 1 type (s) or 2 or more types selected from the group which consists of.

Examples of the colorant (D1) include pigments and dyes.
Examples of pigments include inorganic pigments (alumina white, graphite, etc.), organic pigments (azo lakes, etc.), and examples of dyes include azos, anthraquinones, and the like.

  Examples of the flame retardant (D2) include organic flame retardants [nitrogen-containing compounds [salts such as urea compounds and guanidine compounds], sulfur-containing compounds [sulfuric esters, sulfamic acids and their salts, esters, amides, etc.], silicon-containing compounds Compound [polyorganosiloxane etc.], phosphorus-containing [phosphate ester etc.]]; inorganic flame retardant [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, etc.] and the like.

  Fillers (D3) include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, etc.), sulfites (calcium sulfite, etc.), metal sulfides (such as molybdenum disulfide), silicates (aluminum silicate) Etc.), diatomaceous earth, silica powder, talc, silica, zeolite, and mixtures thereof.

  Examples of the lubricant (D4) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

  Antistatic agents (D5) include low molecular weight antistatic agents (nonionic, cationic, anionic and amphoteric interfaces described in US Pat. Nos. 3,929,678 and 4,331,447). Activators and the like), and polymer type permanent antistatic agents (such as block copolymers of polyolefin and polyoxyalkylene glycol, block copolymers of polyamide and polyoxyalkylene glycol, etc.).

  Antioxidants (D6) include hindered phenol compounds [pt-amylphenol-formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-tert-butyl-4-methylphenol (BHT). ), 2-t-butyl-4-methylphenol (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B) and the like]; Compound [N, N′-diphenylthiourea, dimyristylthiodipropionate, etc.]; Phosphorus compound [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p- Nonylphenyl) phosphite, dioctadecyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate, etc.].

  Examples of the ultraviolet absorber (D7) include salicylate compounds [phenyl salicylate and the like]; benzophenone compounds [2,4-dihydroxyzenzophenone and the like]; benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl). ) -Benzotriazole and the like].

The total content of (D) in the resin composition is usually 20% or less based on the total weight of the composition, preferably 0.05 to 10% from the viewpoint of the functional expression of each (D) and the industrial viewpoint. More preferably, it is 0.1 to 5%.
The amount of each additive used based on the total weight of the composition is as follows: (D1) is usually 5% or less, preferably 0.1 to 3%; (D2) is usually 8% or less, preferably 1 to 3%; (D3) is usually 5% or less, preferably 0.1 to 1%; (D4) is usually 8% or less, preferably 1 to 5%; (D5) is usually 25% or less, preferably 1 to 20%; (D6) is usually 2% or less, preferably 0.05 to 0.5%; (D7) is usually 2% or less, preferably 0.05 to 0.5%.

  When the additive is the same and overlaps between (D1) to (D7), the additive is not used regardless of the effect as the other additive in an amount in which each additive exhibits the corresponding effect, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

As a method for producing the resin composition of the present invention, (1) a method in which (A), (B), (C) and, if necessary, an additive (D) are mixed together to form a resin composition (collective method) ;
(2) A master batch polyolefin resin composition containing a high concentration of (A) is prepared by mixing a part of (B), the total amount of (A), and if necessary, a part or all of (D). Then, the remaining (B), (C) and, if necessary, the remaining (D) are added and mixed to obtain a resin composition (masterbatch method).
The method (2) is preferable from the viewpoint of the mixing efficiency of (A).

As a specific mixing method in the manufacturing method of the resin composition,
(I) For each component to be mixed, for example, a powder mixer [“Henschel Mixer” [trade name “Henschel Mixer FM150L / B”, manufactured by Mitsui Mining Co., Ltd.], “Nauter Mixer” [trade name “Nauter Mixer” DBX3000RX ", manufactured by Hosokawa Micron Co., Ltd.]," Banbury mixer "[trade name" MIXTRON BB-16MIXER ", manufactured by Kobe Steel Co., Ltd.], etc.] and then mixed with a melt kneader [batch kneader, continuous kneader (Single-screw kneader, twin-screw kneader, etc.)] and kneading at 120 to 220 ° C. for 0.5 to 30 minutes;
(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.

[Molding]
The molded product of the present invention is formed by molding the resin composition.
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 block shape, a plate shape, a sheet shape, and a film.

The molded article of the present invention has excellent mechanical properties 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, and acrylic urethane resin paint.
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”. In the following, Example 4 is referred to as Reference Example 1.

Production Example 1
Polyolefin (a0-1) [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mn 100,000; 100 parts were charged in a nitrogen atmosphere, heated and melted with a mantle heater while nitrogen was passed through the gas phase, 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 per 1,000 carbon atoms was 7.2, and Mn was 3,000.

Production Example 2
In Production Example 1, a polyolefin (a-2) was obtained in the same manner as in Production Example 1 except that the heat degradation time was changed from 70 minutes to 100 minutes. In (a-2), the number of double bonds per 1,000 carbon atoms was 18, and Mn was 1,200.

Production Example 3
In Production Example 1, a polyolefin (a-3) was obtained in the same manner as in Production Example 1 except that the heat degradation time was changed from 70 minutes to 20 minutes. In (a-3), the number of double bonds per 1,000 carbon atoms was 0.3, and Mn was 45,000.

Production Example 4
In Production Example 1, instead of 100 parts of polyolefin (a0-1), polyolefin (a0-2) having 80 mol% of propylene and 20 mol% of 1-butene as structural units [trade name “Tuffmer XM-7080”, Mitsui Chemical Co., Ltd., Mn 90,000, and so on. ] Except having used 100 parts, it carried out similarly to manufacture example 1 and obtained polyolefin (a-4). In (a-4), the number of double bonds per 1,000 carbon atoms was 7.2, and Mn was 3,000.

Comparative production example 1
In Production Example 1, a polyolefin (ratio a-1) was obtained in the same manner as in Production Example 1 except that the heat degradation time was changed from 70 minutes to 120 minutes. In (ratio a-1), the number of double bonds per 1,000 carbon atoms was 36, and Mn was 600.

Comparative production example 2
In Production Example 1, a polyolefin (ratio a-2) was obtained in the same manner as in Production Example 1 except that the heat degradation time was changed from 70 minutes to 10 minutes. In (ratio a-2), the number of double bonds per 1,000 carbon atoms was 0.04, and Mn was 65,000.

Production Example 5
A reaction vessel was charged with 100 parts of (a-1), 24 parts of maleic anhydride (b-1), 18.5 parts of 1-decene (c-1), and 100 parts of xylene. The mixture was heated to 120 ° C. and dissolved uniformly. Here, a solution prepared by dissolving 0.5 part of 1,1′-azobiscyclohexane-1-carbonitrile [trade name “V-40”, manufactured by Wako Pure Chemical Industries, Ltd.] in 10 parts of xylene was added for 10 minutes. After dropwise addition, stirring was continued for 3 hours under reflux of xylene. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain a dispersant (A-1). (A-1) had an acid value of 95 and Mn of 4,500.

Production Example 6
In Production Example 5, instead of (a-1) 100 parts, (b-1) 24 parts, (c-1) 18.5 parts, (a-2) 100 parts, (b-1) 100 parts, (C-1) Except having used 85.7 parts, it carried out similarly to manufacture example 5, and obtained the dispersing agent (A-2). (A-2) had an acid value of 200 and Mn of 3,500.

Production Example 7
In Production Example 5, instead of (a-1) 100 parts, (b-1) 24 parts, (c-1) 18.5 parts, (a-3) 100 parts, (b-1) 1 part, (C-1) Except having used 2 parts, it carried out similarly to manufacture example 5, and obtained the dispersing agent (A-3). (A-3) had an acid value of 6 and Mn of 45,000.

Production Example 8
In Production Example 5, a dispersant (A-4) was obtained in the same manner as in Production Example 5 except that 100 parts of (a-4) was used instead of 100 parts of (a-1). (A-4) had an acid value of 95 and Mn of 4,500.

Production Example 9
Manufacturing Example 5 except that (b-1) 24 parts were used instead of itaconic acid (b-2) [trade name “Itaconic acid”, manufactured by Fuso Chemical Industry Co., Ltd.] 31.8 parts. In the same manner as in Example 5, a dispersant (A-5) was obtained. (A-5) had an acid value of 180 and Mn of 4,500.

Production Example 10
In Production Example 5, in place of 18.5 parts of (c-1), except that 3.8 parts of 1-hexene (c-2) was used, the same procedure as in Production Example 5 was carried out. ) (A-6) had an acid value of 108 and Mn of 4,300.

Production Example 11
In Production Example 5, instead of 24 parts of (b-1) and 18.5 parts of (c-1), 33 parts of (b-1), 1-hexatriacontene (C36 α-olefin) (c-3) ) Except having used 200 parts, it carried out similarly to manufacture example 5, and obtained the dispersing agent (A-7). (A-7) had an acid value of 57 and Mn of 6,500.

Production Example 12
In Production Example 5, instead of 0.5 part of 1,1′-azobiscyclohexane-1-carbonitrile, 0.5 part of dicumyl peroxide [trade name “Park Mill D”, manufactured by NOF Corporation] was added. Except having used, it carried out similarly to manufacture example 5 and obtained the dispersing agent (A-8). (A-8) had an acid value of 95 and Mn of 5,000.

Production Example 13
In Production Example 5, instead of (a-1) 100 parts, (b-1) 24 parts, (c-1) 18.5 parts, (a-2) 100 parts, acrylic acid (b-3) 15 Part, (c-2) Except having used 8.7 parts, it carried out similarly to manufacture example 5, and obtained the dispersing agent (A-9). (A-9) had an acid value of 95 and Mn of 4,500.

Comparative production example 3
In Production Example 5, instead of 24 parts (b-1) and 18.5 parts (c-1), 11 parts (b-1) were used, except that (c-1) was not used. In the same manner as in Production Example 5, a dispersant (ratio A-1) was obtained. (Ratio A-1) had an acid value of 50 and Mn of 3,500.

Comparative production example 4
In Production Example 5, instead of (a-1) 100 parts, (b-1) 24 parts, (c-1) 18.5 parts, (ratio a-1) 100 parts, (b-1) 40 parts (C-1) Except having used 60 parts, it carried out similarly to manufacture example 5 and obtained the dispersing agent (ratio A-2). (Ratio A-2) had an acid value of 114 and Mn of 1,000.

Comparative Production Example 5
In Production Example 5, instead of (a-1) 100 parts, (b-1) 24 parts, (c-1) 18.5 parts, (ratio a-2) 100 parts, (b-1) 5. 5 parts and (c-1) Except having used 5.5 parts, it carried out similarly to manufacture example 5 and obtained the dispersing agent (ratio A-3). (Ratio A-3) had an acid value of 28 and Mn of 67,000.

Comparative Production Example 6
In Production Example 5, instead of 24 parts (b-1) and 18.5 parts (c-1), 27 parts (b-1) and 7 parts 1-butene (c-4) were used. This was carried out in the same manner as in Production Example 5 to obtain a dispersant (Ratio A-4). (Ratio A-4) had an acid value of 115 and Mn of 3,500.

Comparative Production Example 7
In Production Example 5, the same procedure as in Production Example 5 was performed except that 120 parts of 1-pentacontene (C50 α-olefin) (c-5) was used instead of 18.5 parts of (c-1). A dispersant (ratio A-5) was obtained. (Ratio A-5) had an acid value of 57 and Mn of 3,000.

Examples 1-14, Comparative Examples 1-10
After blending the obtained dispersant and the following raw materials [polyolefin resin (B), biomass-derived powder (C)] for 3 minutes with a Henschel mixer, respectively, according to the composition (parts) in Table 1, vent The biomass-containing resin composition was obtained by melt kneading with a twin screw extruder at 180 ° C., 100 rpm, and a residence time of 5 minutes. Each resin composition was molded at a cylinder temperature of 190 ° 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 1.

<Raw materials>
Polyolefin resin (B)
(B-1): Commercially available polypropylene [trade name “Sun Allomer PL500A”, manufactured by Sun Allomer, Mn 300,000]
(B-2): Commercially available polyethylene [trade name “NOVATEC HJ490”, manufactured by Nippon Polyethylene Co., Ltd., Mn300,000]
(B-3): Commercially available ethylene / propylene copolymer [trade name “Sun Allomer PB222A”, manufactured by Sun Allomer Co., Ltd., Mn 350,000]

Powder derived from biomass (C)
(C-1): Wood flour [trade name “Sel Yunt”, manufactured by Shimada Shokai Co., Ltd., volume average particle size 80 μm]
(C-2): Wood flour [trade name “Super Feeder # 100”, manufactured by Sankyo Seiko Co., Ltd., volume average particle diameter 150 μm]
(C-3): Chitosan powder [trade name “SK-10”, manufactured by Koyo Chemical Co., Ltd., flaky, and the same hereinafter. ] Is pulverized using a high-speed impact pulverizer with a soundproof case [trade name “MIKRO-PULVERIZER”, model number “AP-BL”, manufactured by Hosokawa Micron Co., Ltd., hereinafter abbreviated as high-speed hammer mill]. Adjusted to 500 μm.
(C-4): A chitosan powder pulverized using a high-speed hammer mill and adjusted to a volume average particle size of 60 μm.

<Evaluation method>
(1) Impact resistance (unit: kJ / m ² )
The Charpy impact value was measured according to ASTM D6110.
(2) Affinity of polyolefin resin (B) and biomass-derived powder (C) The fracture surface of the test piece after the test of (1) above was observed, and the affinity of (B) and (C) was determined as follows. It was evaluated with.
◎ No interfacial delamination between (B) / (C) ○ Interfacial delamination between (B) / (C) but very small △ Interfacial delamination is slightly between (B) / (C) × (B) / (C) Interfacial delamination is large (3) Flexural modulus (unit: MPa)
Measured according to ASTM D790.

  From the results in Table 1, the biomass-containing resin composition of the present invention has better affinity between the polyolefin (B) and the biomass-derived powder (C) than the comparative one, and the composition is molded. It can be seen that the resulting molded product is superior in mechanical properties (impact resistance, flexural elasticity) compared to the comparative product.

  The biomass-containing resin composition of the present invention has good compatibility with the constituent components and excellent moldability, and the resulting molded product has excellent mechanical properties and is environmentally friendly with little environmental impact during disposal. The present invention can be applied to a wide range of fields such as electronic devices, conveyance materials, daily life materials, and building materials, and is extremely useful.

Claims (6)

Ethylene / propylene copolymer having a number average molecular weight of 800 to 50,000 having a weight average molecular weight of 800 to 50,000 having a weight average molecular weight of 800 to 50,000 per 1,000 carbon atoms in the molecular chain and at the molecular terminal 99.5-20 / 80] , an unsaturated (poly) carboxylic acid (anhydride) (b), and an α-olefin (c) having 6 to 36 carbon atoms, and styrene or a styrene derivative A biomass-containing resin comprising a dispersant (A) obtained by copolymerizing a copolymer component not containing a radical initiator (d), a polyolefin resin (B), and a biomass-derived powder (C) A method for producing the composition . The proportions based on the total weight of (a), (b) and (c) are: (a) 30-98%, (b) 0.03-40%, (c) 0.6-65% A method for producing a resin composition according to claim 1 . (A), (B), the ratio based on the total weight of (C), (A) is 0.5 to 15% (B) 5 to 90% according to a is 5 to 85% (C) Item 3. A method for producing a resin composition according to Item 1 or 2 . The weight ratio of (B) and (C) is 10/90 to 90/10, The manufacturing method of the resin composition in any one of Claims 1-3 . The manufacturing method of the molded article formed by shape | molding the resin composition in any one of Claims 1-4 . A method for producing a molded article obtained by coating and / or printing the molded article according to claim 5 .