JP5555145B2 - Biodegradable resin composition - Google Patents

Description

  The present invention relates to a biodegradable resin composition. More specifically, the present invention relates to a biodegradable resin composition containing a biomass-derived resin, a polyolefin resin, and a compatibilizing agent. Here and below, the biomass-derived resin refers to a resin obtained from biomass (biologically derived material) as a raw material, and the resin is a fermented synthetic resin (obtained by polymerizing biomass in the body), natural Material-derived resins (those that utilize biomass itself as a polymer), chemically synthesized resins (those obtained by chemically polymerizing biomass-derived monomers), and the like are included, and specific examples include those described below.

In recent years, there has been a movement to use as a plastic raw material as much as possible a biomass-derived resin excellent in biodegradability from the viewpoint of protecting the global environment. However, when the biomass-derived resin is used in combination as various molded articles, it is compatible with other plastic raw materials (hereinafter sometimes referred to as dispersibility) and the impact resistance of plastics particularly required for various molded articles. There was a problem in terms of mechanical properties such as properties.
Therefore, improvement of mechanical properties such as impact resistance of biodegradable resins by blending biomass-derived resins and polyolefin resins has been actively studied. For example, a method of using a styrenic thermoplastic elastomer or modified polyolefin as a compatibilizing agent in the blending has been proposed (see, for example, Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 56-100900 JP-A-6-256417 JP 2007-177213 A

However, in the above prior art, when a resin composition is formed by blending a biomass-derived resin and a polyolefin resin, mechanical properties such as compatibility and impact resistance are not yet satisfactory and improvements are required.
The objective of this invention is providing the biodegradable resin composition which is excellent in compatibility of biomass origin resin and polyolefin resin, and gives the molded article excellent in mechanical physical properties, such as impact resistance.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a resin composition comprising a biomass-derived resin (A), a polyolefin resin (B) and a compatibilizer (C), wherein (C) is 0.1 to 20 in the molecule. A biodegradable resin composition comprising only a modified polyolefin (C1) having a hydroxyl group.

The biodegradable resin composition of the present invention has the following effects.
(1) An environmentally friendly molded product that can reduce carbon dioxide emissions is provided.
(2) A molded product having a high content of biomass-derived resin and excellent mechanical properties such as impact resistance is provided.

[Biomass-derived resin (A)]
Specifically, as the biomass-derived resin (A), polylactic acid (A1), polyhydroxybutyrate (A2), polytrimethylene terephthalate (A3), esterified starch (A4) and cellulose acetate (A5) and these The mixture of 2 or more types is mentioned.

  Of these, (A1), (A2) and (A3) are preferable from the viewpoint of dispersibility in the polyolefin resin (B) described later, and (A1) and (A2) are more preferable. .

The polylactic acid (A1) includes a polymer having a lactic acid component of 50% by weight or more, including a lactic acid homopolymer. As a specific example,
(1) Polylactic acid (2) Copolymer of lactic acid and other aliphatic oxycarboxylic acid (3) Copolymer of lactic acid, aliphatic polyhydric alcohol and aliphatic polybasic acid (4) (1) to (3) The mixture by any combination is mentioned.
Examples of lactic acid used in the present invention include L-, D- and DL-lactic acid, a mixture thereof, and lactide which is a cyclic dimer of lactic acid.

Specific examples of the production method (A1) include the following methods, but the production method is not particularly limited.
[1] A method of direct dehydration polycondensation using lactic acid or a mixture of lactic acid and aliphatic oxycarboxylic acid as a raw material (for example, a production method described in US Pat. No. 5,310,865)
[2] A ring-opening polymerization method in which a cyclic dimer (lactide) of lactic acid is melt-polymerized (for example, a production method described in US Pat. No. 2,758,987)
[3] A ring-opening polymerization method in which a cyclic dimer of lactic acid and an aliphatic oxycarboxylic acid, for example, lactide or glycolide and ε-caprolactone is melt-polymerized in the presence of a catalyst (for example, a production method described in US Pat. No. 4,057,537) )
[4] A method of directly dehydrating polycondensation of a mixture of lactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid (for example, a production method described in US Pat. No. 5,428,126)
[5] A method of condensing a polymer of polylactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid in the presence of an organic solvent (for example, a production method described in European Patent Publication No. 071880A2)
[6] A method of solid-phase polymerization in at least a part of the steps when producing a polyester polymer by dehydrating polycondensation reaction of lactic acid in the presence of a catalyst.

  A small amount of trimethylolpropane (hereinafter abbreviated as TMP), aliphatic polybasic (3- to 4-valent) alcohols such as glycerin (hereinafter abbreviated as GR), and aliphatic polybasic acids such as butanetetracarboxylic acid (trivalent to Hexavalent or higher) and polyhydric alcohols such as polysaccharides (tetravalent to octavalent or higher) may be copolymerized, and a binder (polymer chain extender) such as a diisocyanate compound may be used. It may be used to increase the molecular weight, and may be crosslinked with a peroxide such as bis (t-butylperoxyisopropyl) benzene or dicumyl peroxide.

Number average molecular weight of (A1) [hereinafter abbreviated as Mn. The measurement is based on the gel permeation chromatography (GPC) method described later. ] Or molecular weight distribution is not particularly limited, but Mn is preferably 500 to 100,000, more preferably 1,000 to 80,000, and particularly preferably 2, from the viewpoint of compatibility with (B) and from an industrial viewpoint. 000 to 50,000.
The molecular weight can be adjusted by adjusting the conditions such as monomer concentration, other raw material concentrations, reaction temperature, etc., and it can also be adjusted by reducing the molecular weight by thermal decomposition, hydrolysis, transesterification, etc. of high molecular weight polylactic acid. is there.

The GPC measurement conditions are as follows. Thereafter, Mn is also measured under the same conditions.
<GPC measurement conditions>
[1] Apparatus: Waters 150-CV [manufactured by Waters Co., Ltd.]
[2] Column: PLgel 10 μm MIXED-B [Polymer Laboratories
Manufactured by]
[3] Eluent: o-dichlorobenzene [4] Reference material: polystyrene [5] Injection conditions: sample concentration 3 mg / ml, column temperature 135 ° C.

The polyhydroxybutyrate (A2) includes those obtained by a fermentation synthesis method and a chemical synthesis method. The polyhydroxybutyrate obtained by the fermentation method is poly [(R) -3-hydroxybutanoic acid] (homopolymer), and the one obtained by the chemical synthesis method is poly [(R) -3-hydroxybutanoic acid. ] And a poly [(S) -3-hydroxybutanoic acid] (racemic).
Here, (R) represents the four groups bonded to the asymmetric central carbon atom clockwise in the order of priority of the order law (hydroxyl group, CH ₂ COOH group, methyl group, H), S) represents counterclockwise rotation.

Specific examples of the production method (A2) include the following methods, but the production method is not particularly limited.
[1] A polyhydroxybutyrate can be produced by culturing a microorganism capable of producing polyhydroxybutyrate in a normal medium containing a carbon source, a nitrogen source, inorganic ions, and other organic components as required. And is extracted with an organic solvent such as chloroform (for example, a production method described in JP-A-9-131186).
[2] A method of culturing a microorganism transformed by introducing a recombinant DNA containing a polyhydroxybutyrate synthesis gene and collecting polyhydroxybutyrate produced in the microbial cell (for example, Japanese Patent Application Laid-Open No. 10-176070) Described manufacturing method).
[3] A method of directly dehydrating polycondensation using hydroxybutanoic acid as a raw material (for example, a production method described in US Pat. No. 5,310,865)
[4] Ring-opening polymerization method in which β-butyrolactone is melt-polymerized in the presence of a catalyst (for example, a production method described in JP-A-11-323115)

Mn and molecular weight distribution of (A2) are not particularly limited, but Mn is preferably 500 to 2,000,000, more preferably 1,000 to 1,000, from the viewpoint of compatibility with (B) and an industrial viewpoint. 1,000, particularly preferably 2,000 to 500,000.
The molecular weight can be adjusted by adjusting the monomer concentration, other raw material concentrations, reaction temperature, and other conditions, and it can also be adjusted by reducing the molecular weight by thermal decomposition, hydrolysis, transesterification, etc. of high molecular weight polyhydroxybutyrate. Is possible.

  Polytrimethylene terephthalate (A3) includes those obtained from 1,3-propanediol and terephthalic acid. Here, 1,3-propanediol is produced by plant fermentation. Although it does not specifically limit as a manufacturing method of 1, 3- propanediol, For example, the method of fermenting plants, such as corn, manufacturing glucose, and converting into 1, 3- propanediol etc. is mentioned ( The method described in Japanese Patent Publication No. 2006-50412).

  The reaction of 1,3-propanediol and terephthalic acid is carried out by the above-mentioned known method (for example, the production method described in US Pat. No. 5,428,126).

Mn and molecular weight distribution of (A3) are not particularly limited, but Mn is preferably 500 to 100,000, more preferably 1,000 to 80,000, particularly from the viewpoint of compatibility with (B) and an industrial viewpoint. Preferably it is 2,000-50,000.
The molecular weight can be adjusted by adjusting the conditions such as monomer concentration, other raw material concentrations, reaction temperature, etc., and can also be adjusted by reducing the molecular weight by thermal decomposition, hydrolysis, transesterification, etc. of high molecular weight polytrimethylene terephthalate. Is possible.

  Examples of the esterified starch (A4) include those described in JP-A No. 2006-299271, that is, starch having 2 to 22 carbon atoms (hereinafter abbreviated as C), such as starch acetate, starch propionate, And at least one starch ester selected from the group consisting of starch butyrate, starch pentanoate and starch hexanoate.

  Examples of the cellulose acetate (A5) include those described in JP-A-2008-56768, such as cellulose triacetate and other cellulose acetates having different degrees of acetylation.

  The Mn and molecular weight distribution of (A4) and (A5) are not particularly limited, but Mn is preferably 500 to 100,000, more preferably 1 from the viewpoint of compatibility with the polyolefin resin (B) described below and an industrial viewpoint. 1,000 to 80,000, particularly preferably 2,000 to 50,000.

[Polyolefin resin (B)]
Examples of the polyolefin resin (B) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate Copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40 ] Etc. are mentioned.
Among these, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

  The melt flow rate (hereinafter abbreviated as MFR) of (B) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the mechanical properties of the molded product described later. The MFR is measured according to JIS K 6758 (in the case of polypropylene: 230 ° C., load 2.16 kgf, in the case of polyethylene: 190 ° C., load 2.16 kgf).

  The compatibilizing agent (C) in the present invention is composed only of a hydroxyl group-modified polyolefin (C1) having 0.1 to 20 hydroxyl groups in the molecule, and (C1) is obtained by modifying the polyolefin (C0). It is obtained by having a hydroxyl group.

[Polyolefin (C0)]
Examples of the polyolefin (C0) include one or more (co) polymers of olefins, copolymers of one or more olefins and one or more other monomers, and (co) polymers of these (co) polymers. Examples include degradation products obtained by degradation (thermal, chemical or mechanical degradation) of high molecular weight substances.
The olefins include C2-30 (preferably 2-12, more preferably 2-4) alkenes such as ethylene, propylene, and C4-30 alpha-olefins (1-, 2- and isobutene, 1-hexene). , 4-methylpentene-1,1-decene, 1-dodecene, etc.); and other monomers include C3-36 unsaturated monomers copolymerizable with olefins such as styrene, vinyl acetate, (meth) acrylic Acids and their alkyl (C1-30) esters are included.
Of the above (C0), 80 to 100 (more preferably 90 to 100, particularly preferably 95 to 100) mol% is preferable from the viewpoint of compatibility between the compatibilizer (C) and the polyolefin resin (B). (Co) polymerized polyolefin containing propylene as a structural unit.
(C0) can further add ethylene and C4-12 (preferably 4-8) alpha-olefin to a structural unit if necessary.
The content of ethylene in (C0) is usually 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% from the viewpoint of compatibility between the compatibilizer (C) and the polyolefin resin (B). It is as follows.
Further, the content of α-olefin in (C0) is usually 25 mol% or less, preferably 20 mol% or less, more preferably 20 mol% or less from the viewpoint of compatibility between the compatibilizer (C) and the polyolefin resin (B). Is 15 mol% or less.

Examples of C4-12 α-olefins include linear α-olefins (1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, etc.), branched α-olefins ( 4-methyl-1-pentene, 2-ethylhexene, etc.).
Among these, C4-8 α-olefins (1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene are preferable from the viewpoint of compatibility with the polyolefin resin (B). Octene and the like), more preferred are C4-6 α-olefins (such as 1-butene, 1-pentene and 4-methyl-1-pentene), and particularly preferred is 1-butene.
When the number of the monomers constituting the polyolefin (C0) is two or more, the bonding type may be random and / or block.

The number of double bonds per 1,000 carbon atoms in the molecular end and / or in the molecule of the polyolefin (C0) is preferably 0.2 to 10 from the viewpoint of ease of modification and industrial point of view described later. Preferably it is 0.3-6, Especially preferably, it is 0.5-5. Further, the number of double bonds can be calculated from a peak derived from a double bond between 4.5 and 6.0 ppm in a spectrum obtained from ¹ H-NMR (nuclear magnetic resonance) spectroscopy.

  Polyolefin (C0) production methods include polymerization methods (for example, those described in JP-A-59-206409, JP-A-55-135102, etc.) and degradation methods (thermal, chemical and mechanical). Among them, thermal degradation methods (sometimes referred to as thermal degradation methods) include, for example, Japanese Patent Publication No. 43-9368, Japanese Patent Publication No. 44-29742, Japanese Patent Publication No. And those described in Japanese Patent No. 70094. Among these, from the viewpoint of dispersibility of the biomass-derived resin (A) to the polyolefin resin (B) and from an industrial viewpoint, the degrading method is preferred, and the thermal degrading method is more preferred.

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.
Specific examples of polyolefins produced by the polymerization method include propylene polymers such as polypropylene, ethylene / propylene copolymers, propylene / C4-12 α-olefin copolymers, propylene and C3-36 unsaturated monomers ( Copolymers with the other monomers) are included.

  The polyolefin obtained by the degradation method is a polymer obtained by the above polymerization method, and more preferably has a lower limit of Mn from the viewpoint of ease of modification of high molecular weight [(C0), more preferably 1,000, and particularly preferably. The upper limit of Mn, which is preferable from an industrial viewpoint, is 100,000, more preferably 80,000, particularly preferably 50,000], which is a thermally, chemically or mechanically degraded polyolefin. included.

  Among these degradation methods, the thermal degradation method easily yields a low molecular weight polyolefin having an average terminal double bond amount of 1.5 to 2 per molecule [Katsuhide Murata, Tadahiko Makino, Journal of Chemical Society of Japan. 192 (1975)] from the viewpoint of the ease of modification of the polyolefin (C0), and therefore the compatibility of the compatibilizer (C) with the biomass-derived resin (A) and the polyolefin resin (B). Is a thermal degradation method.

In the thermal degradation method, the above-described high molecular weight polyolefin is continuously subjected to thermal degradation in the presence of nitrogen (1) in the absence of organic peroxide, usually at 300 to 450 ° C. for 0.5 to 10 hours. And (2) a method of continuously thermally degrading at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide.
Of these, the ease of introducing double bonds to the molecular ends of the polyolefin, the ease of modification of the resulting heat-degraded polyolefin, and therefore the compatibilizer (C), the biomass-derived resin (A), and the polyolefin The method (1) is preferable from the viewpoint of compatibility with the resin (B).

  Mn of the polyolefin (C0) is preferably 100 to 40,000, more preferably 500 to 30,000, and particularly preferably 1,000 to 20,000 from the viewpoint of ease of modification described later.

[Hydroxyl-modified polyolefin (C1)]
The hydroxyl group-modified polyolefin (C1) in the present invention has 0.1 to 20, preferably 0.5 to 15, and more preferably 1 to 10 hydroxyl groups in the molecule. If the number of hydroxyl groups is less than 0.1, the compatibility between the compatibilizer (C) and the biomass-derived resin (A) is poor, and if it exceeds 20, the compatibility between the (C) and the polyolefin resin (B) is poor. . The number of hydroxyl groups in the (C1) molecule can be determined by calculation from the Mn of (C1) and the hydroxyl value (unit: mgKOH / g; hereinafter, only numerical values are shown).
Mn of (C1) can be measured by the above method, and the hydroxyl value can be measured according to JIS K0070 after dissolving (C1) in an organic solvent such as xylene to obtain a homogeneous solution. . Therefore, the number of hydroxyl groups in the molecule (C1) can be determined from the following formula.

(C1) Number of hydroxyl groups in the molecule =
[Mn of (C1)] × [hydroxyl value of (C1)] / 56100

  The hydroxyl group-modified polyolefin (C1) can be obtained by modifying the polyolefin (C0) by the following method.

(1) Polyolefin (C0) and an ethylenically unsaturated monomer (x) having preferably 1 to 2 acid anhydride groups are reacted in the presence or absence of the radical initiator (d) to perform acid anhydride After obtaining the product-modified polyolefin (C0a), the (C0a), preferably 1 to 4 hydroxyl groups (more preferably 1 to 2) and preferably 1 to 3 amino acids (more preferably 1 to 1). 2) A method of reacting the compound (e) having two. What is obtained by this method is hereinafter referred to as a hydroxyl group-modified polyolefin (C11).
(2) Polyolefin (C0) and an ethylenically unsaturated monomer (y) having preferably 1 to 4 (more preferably 1 to 2) hydroxyl groups in the presence or absence of the radical initiator (d) How to react with. What is obtained by this method is hereinafter referred to as a hydroxyl group-modified polyolefin (C12).
Among these methods, the method (1) is preferable from the industrial viewpoint.

Examples of the ethylenically unsaturated monomer (x) having 1 to 2 acid anhydride groups include C4-10 unsaturated poly (n = 2 to 3 or more, preferably 2) carboxylic acid anhydrides such as anhydrous Mention may be made of maleic acid, itaconic anhydride, citraconic anhydride, cyclohexenedicarboxylic anhydride, aconitic acid and mixtures of two or more thereof.
Among these (x), the compatibility of the compatibilizing agent (C) with the biomass-derived resin (A) and the polyolefin resin (B) and preferred from the industrial viewpoint are unsaturated dicarboxylic acid anhydrides, More preferred is maleic anhydride.

  The weight ratio of (C0) and (x) when modified by reacting polyolefin (C0) with (x) is the compatibility between (C) and polyolefin resin (B) and (C) and biomass-derived resin (A From the viewpoint of compatibility with (A), it is preferably 80/20 to 99/1, more preferably 83/17 to 98/2, and particularly preferably 85/15 to 95/3.

  (C0) and (x) can be reacted in the presence or absence of the radical initiator (d). From the viewpoint of the reactivity between (C0) and (x), (d) It is preferable to react in presence of this.

Examples of (d) include azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.) and peroxides [monofunctional (having one peroxide group in the molecule)] [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-butylperoxy (Cyclohexyl) propane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate, t-butylperoxyallylcarbonate, etc. ]].
Among these, from the viewpoint of the reactivity between (C0) and (x), a peroxide is preferable, a monofunctional peroxide is more preferable, and di-t-butyl peroxide and lauroyl peroxide are particularly preferable. And dicumyl peroxide.

  The amount of (d) used is usually 30% or less based on the weight of (x), preferably 0.001 to 20%, more preferably from the viewpoint of the reactivity between (C0) and (x) and from an industrial viewpoint. 0.01 to 10%, particularly preferably 0.1 to 5%.

In a specific method for producing the acid anhydride-modified polyolefin (C0a),
[1] Polyolefin (C0) and an ethylenically unsaturated monomer (x) having an acid anhydride group are heated and melted, or an appropriate organic solvent [C3-18, such as hydrocarbon (for example, hexane, toluene and xylene), halogenated Suspended or dissolved in hydrocarbons (eg di-, tri- and tetrachloroethane and dichlorobutane), ketones (eg acetone and methyl ethyl ketone) and ethers (eg ethyl-n-propyl ether, di-i-propyl ether and dioxane)] If necessary, the radical initiator (d) [or a solution in which (d) is dissolved in an appropriate organic solvent (the same as above)], a chain transfer agent (t) described later, and a polymerization inhibitor (u) And heating and stirring (melting method, suspension method and solution method);
[2] A method (melt kneading method) in which (C0), (x) and, if necessary, (d), (t), (u) are mixed in advance and melt kneaded using an extruder, a Banbury mixer or a kneader, etc. Is included.
Among these, the method [1] is preferable from the viewpoint of the reactivity between (C0) and (x), and the melting method and the solution method are more preferable.

  The melting temperature in the melting method may be a temperature at which (C0) melts, and preferably 120 to 260 ° C. from the viewpoint of the reactivity between (C0) and (x) and the decomposition temperature of (C0a) obtained. More preferably, it is 130-240 degreeC.

  The solution temperature in the solution method may be any temperature at which (C0) is dissolved in a solvent, and is preferable from the viewpoint of the reactivity between (C0) and (x), the decomposition temperature of (C0a) to be obtained, and an industrial viewpoint. Is 50 to 220 ° C, more preferably 110 to 210 ° C, and particularly preferably 120 to 180 ° C.

Examples of the chain transfer agent (t) include hydrocarbons [C6-24, such as aromatic hydrocarbons (such as toluene, xylene, ethylbenzene and isopropylbenzene) and unsaturated aliphatic hydrocarbons (such as 1- and 2-butene, 1- and 2-hexene, 1-dodecene and 1-tetradecene)]; halogenated hydrocarbons (C1-24, such as dichloromethane, chloroform, carbon tetrachloride and benzyl chloride); alcohols (C1-24, such as methanol, ethanol, 1-propanol and allyl alcohol); thiols (C1-24, such as ethylthiol, propylthiol and 1-dodecylthiol); ketones (C3-24, such as acetone, methylethylketone and ethylbutylketone); aldehydes (C2-18, such as -Methyl-2-propylaldehyde and 1-octylaldehyde); phenol (C6-36, eg phenol, m-, p- and o-cresol); quinone (C6-24, eg hydroquinone); amine (C3-24, For example, diethyl methylamine, triethylamine and diphenylamine); and disulfides (C2-24, such as diethyl disulfide, di-1-propyl disulfide and di-1-octyl disulfide).
Among these, from the viewpoint of compatibility between the polyolefin (C0) and the chain transfer agent (t), preferred are hydrocarbons, halogenated hydrocarbons, more preferred are hydrocarbons, and particularly preferred are unsaturated aliphatic hydrocarbons. is there.
The amount of (t) used is usually 40% or less based on the weight of (x), preferably 0 from the viewpoint of the reactivity between (C0) and (x) and the compatibility between (C0) and (t). 0.05 to 20%.

Examples of the polymerization inhibitor (u) include inorganic compounds [for example, oxygen, sulfur and metal salts (for example, ferric chloride)] and organic compounds [catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone ( C6-24, such as p-benzoquinone and duroquinone), hydrazine (C2-36, such as 1,1-diphenyl-2-picrylhydrazine), ferrazine (C5-36, such as 1,3,5-triphenylferrazine) Nitro compounds (C3-24, such as nitrobenzene) and stable radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6-tetramethyl-1-pi Peridinyloxy (TEMPO) and 1,3,5-triphenylfeldazyl]].
The amount of (u) used is preferably 5% or less based on the weight of (x), preferably 0 from the viewpoint of the reactivity between (C0) and (x) and the compatibility between (C0) and (x). 0.01 to 0.5%.

  Examples of the compound (e) having 1 to 4 hydroxyl groups and 1 to 3 amino groups include the following, and one or a mixture of two or more thereof can be used.

(E) includes hydroxylamine, alkanolamine [C2-12 mono- and dialkanolamine (monoethanolamine, monoisopropanolamine, monobutanolamine, diethanolamine, dipropanolamine, etc.), and dimethyl sulfate or benzyl thereof. Quaternized products by quaternizing agents such as chloride, etc.] Primary-secondary monoamine hydroxyalkylated (C2-4), and primary-secondary monoamines and their alkylation (C1-4) Adducts [mono-, di- and tri (hydroxy) alkylamines (mono-, di- and triethanolamine, dimethylethanolamine, diethylethanolamine, N-hydroxyethylmorpholine) As well as ethylami , AO adduct) and tertiary amino group-containing diols such as morpholine.
The number of hydroxyl groups possessed by (e) is preferably 1 to 4, more preferably 1 to 2 from the viewpoint of compatibility of (C) with (A) and (B). The number of amino groups possessed is preferably 1 to 3 and more preferably 1 to 2 from an industrial viewpoint.
Of these, monoethanolamine is preferable from the viewpoint of compatibility between (A) and (B) and from an industrial viewpoint.

In the method for producing a hydroxyl group-modified polyolefin (C11) by a reaction between an acid anhydride-modified polyolefin (C0a) and (e),
[1] A method in which (C0a) and (e) are heated and melted, or suspended or dissolved in an appropriate organic solvent (the same as described above) and heated and stirred (melting method, suspension method and solution method);
[2] A method (melt kneading method) in which (C0a) and (e) are mixed in advance and melt kneaded using an extruder, a Banbury mixer, a kneader or the like is included.
Among these, the method [1] is preferable from the viewpoint of the reactivity between (C0a) and (e), and the melting method and the solution method are more preferable.

  The melting temperature in the melting method may be a temperature at which (C0a) melts, and is preferably 120 to 260 ° C, more preferably 130 to 240 ° C from the viewpoint of the reactivity between (C0a) and (e). .

  The solution temperature in the solution method may be a temperature at which (C0a) is dissolved in the solvent, and is preferably 50 to 220 ° C., more preferably 110 from the viewpoint of the reactivity between (C0a) and (e) and from an industrial viewpoint. It is -210 degreeC, Most preferably, it is 120-180 degreeC.

Examples of the unsaturated monomer (y) having 1 to 4 hydroxyl groups in the production method (2) of the hydroxyl group-modified polyolefin include the following (1) to (6).
(1) Hydroxyl group-containing (meth) acrylate (1-1) (meth) acrylate represented by the following general formula (1)

^{_{CH 2 = C (R 1)}} -COO- (A-O) m -H (1)

[Wherein, R ¹ is H or a methyl group, A is a C2-4 alkylene group, and m is a number of 1 to 20 (preferably 1 to 10, more preferably 1). ]

  For example, hydroxyalkyl (C2-4) (meth) acrylate such as 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA), 2- and 3-hydroxypropyl (meth) acrylate, etc. And hydroxyalkoxy (C2-4) alkyl (C2-4) (meth) acrylates such as 2-hydroxyethoxyethyl (meth) acrylate;

(1-2) (Meth) acrylates of polyhydric alcohols containing 3 to 8 hydroxyl groups Examples of polyhydric alcohols include C3-12 alkane polyols, intramolecular or intermolecular dehydrates, and sugars [for example, glycerin. , Trimethylolpropane, pentaerythritol, sorbitol (hereinafter abbreviated as GR, TMP, PE, SO), sorbitan, diGR, sucrose, methyl glucoside, etc.], and their (meth) acrylates include GR mono- And di- (meth) acrylate, TMP mono- and di- (meth) acrylate, and sucrose (meth) acrylate, etc .;
(2) C2-12 alkenol vinyl alcohol (formed by hydrolysis of vinyl acetate), and C3-12 alkenol [(meth) allyl alcohol, (iso) propenyl alcohol, crotyl alcohol, 1-butene-3 -Ol, 1-buten-4-ol, 1-octenol, 1-undecenol, 1-dodecenol and the like]
(3) C4-12 alkenediol 2-butene-1,4-diol, etc. (4) C3-12 hydroxyl group-containing alkenyl ether having an alkenyl group, for example, hydroxyalkyl (C1-6) alkenyl ether [for example, 2-hydroxy Ethyl propenyl ether, and alkenyl (C3-12) ether of polyhydric alcohol mentioned in (1-2) [TMP mono- and di- (meth) allyl ether, sucrose (meth) allyl ether, etc.]]
(5) Hydroxyl group-containing aromatic monomer o-, m-, p-hydroxystyrene, etc. (6) AO adducts of (1) to (5) above (1) to (5) at least one of the hydroxyl groups A monomer substituted with —O— (A—O) _m H, wherein A and m are the same as those in the general formula (1).

  Among (y), (1), (2), (4), (5) and (6) are preferable from the viewpoint of compatibility of (A) and (B), and (1-1) is more preferable. ), Particularly preferred are HEA and HEMA, and most preferred is HEMA.

Specific methods for producing the hydroxyl group-containing modified polyolefin (C12) obtained by modifying the polyolefin (C0) with (y) include the following methods [1] and [2].
[1] (C0) and (y) are heated and melted, or suspended or dissolved in an appropriate organic solvent (same as above), and if necessary, the radical initiator (d) [or (d) is appropriately used. A solution dissolved in an organic solvent (same as above)], a method of adding the chain transfer agent (t) and the polymerization inhibitor (u) and stirring with heating (melting method, suspension method and solution method), and [2] A method (melt kneading method) in which (C0), (y) and, if necessary, (d), (t), (u) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like. included.
Among these, the method [1] is preferable from the viewpoint of the reactivity between (C0) and (y), and the melting method and the solution method are more preferable.

  The melting temperature in the melting method may be a temperature at which (C0) melts, and is preferably 120 to 260 ° C. from the viewpoint of the reactivity between (C0) and (y) and the decomposition temperature of (C12) obtained. More preferably, it is 130-240 degreeC.

  The solution temperature in the solution method may be a temperature at which (C0) is dissolved in a solvent, and is preferable from the viewpoint of the reactivity between (C0) and (y), the decomposition temperature of (C12) to be obtained, and an industrial viewpoint. Is 50 to 220 ° C, more preferably 110 to 210 ° C, and particularly preferably 120 to 180 ° C.

  The amount of (d) used is usually 30% or less based on the weight of (y), preferably 0.001 to 20%, more preferably from the viewpoint of the reactivity between (C0) and (y) and from an industrial viewpoint. 0.01 to 10%, particularly preferably 0.1 to 5%.

  The amount of (t) used is usually 40% or less based on the weight of (y), preferably 0 from the viewpoint of the reactivity between (C0) and (y) and the compatibility between (C0) and (t). 0.05 to 20%.

  The amount of (u) to be used is preferably 5% or less based on the weight of (y), preferably 0 from the viewpoint of the reactivity between (C0) and (y) and the compatibility between (C0) and (y). 0.01 to 0.5%.

  The Mn of the hydroxyl group-modified polyolefin (C1) is preferably 500 to 30,000, more preferably 1,000 to 20 from the viewpoint of the mechanical properties of the resin molded product and the compatibility between the biomass-derived resin (A) and the polyolefin resin (B). , 000.

  Of the hydroxyl group-modified polyolefin (C1), from the viewpoint of compatibility between the compatibilizer (C) and the biomass-derived resin (A) and the polyolefin resin (B), the (C1) is preferably the above-described thermal degradation. It is a hydroxyl group-modified polyolefin obtained by modifying a polyolefin. That is, the hydroxyl group-modified polyolefin is obtained by further modifying the acid anhydride-modified polyolefin of the heat-degraded polyolefin with a hydroxyl group.

[Biodegradable resin composition (Z)]
The biodegradable resin composition (Z) of the present invention contains a biomass-derived resin (A), a polyolefin resin (B) and a compatibilizer (C), and the (C) is 0.1 to 0.1 in the molecule. It consists only of hydroxyl group-modified polyolefin (C1) having 20 hydroxyl groups.
The weight ratio of (A) and (B) in (Z) is preferably 10/90 to 60/40, more preferably 25/75 to 50/50, from the viewpoint of environmental protection and the mechanical properties of the molded product described later. is there.
Further, the ratio of (C) based on the total weight of (A), (B), and (C) is preferable from the viewpoint of the mechanical properties of the molded article and the compatibility with (A) and (B) of (C). Is 0.1 to 30%, more preferably 1 to 20%, particularly preferably 2 to 10%.

The biodegradable resin composition (Z) of the present invention can further contain various additives (H) as necessary within the range not inhibiting the effects of the present invention.
(H) includes colorant (H1), flame retardant (H2), filler (H3), antistatic agent (H4), dispersant (H5), antioxidant (H6) and ultraviolet absorber (H7). 1 type (s) or 2 or more types chosen from the group which consists of are mentioned.

  Examples of the colorant (H1) include pigments [white (such as titanium oxide), black (such as carbon black) and yellow pigment (such as cadmium yellow)], dyes [such as azo, anthraquinone, indigoid and sulfur dyes];

  Examples of the flame retardant (H2) include organic flame retardants [phosphorus-containing compounds (such as phosphate esters), bromine-containing compounds (such as tetrabromobisphenol A), chlorine-containing compounds (such as chlorinated paraffin))]; inorganic flame retardants [three Antimony oxide, etc.].

  As filler (H3), metal powder (aluminum powder, etc.), metal oxide (alumina, talc, etc.), metal hydroxide (aluminum hydroxide, etc.), metal salt (calcium carbonate, etc.), fiber [inorganic fiber ( Glass fibers, etc.), organic fibers (nylon fibers, etc.)], microballoons (glass, etc.), carbons (carbon black, etc.), metal sulfides (molybdenum disulfide, etc.), organic powders (wood flour, etc.), etc. It is done.

Antistatic agents (H4) include nonionic, cationic, anionic and amphoteric surfactants described below and in US Pat. Nos. 3,929,678 and 4,331,447. .
(1) Nonionic surfactant AO-added nonionics, such as active hydrogen atom-containing compounds having a hydrophobic group (C8-24 or higher) [higher alcohol, higher aliphatic amine, higher fatty acid, etc.] ) Oxyalkylene derivatives, (poly) oxyalkylene derivatives of higher fatty acid esters of polyhydric alcohols [above, eg GR, PE and sorbitan], (poly) oxyalkylene derivatives of (alkanol) amides of higher fatty acids, polyhydric alcohols (Poly) oxyalkylene derivatives of alkyl ethers and polyoxypropylene polyols; polyhydric alcohol type nonionics, such as fatty acid esters of polyhydric alcohols, polyhydric alcohol alkyl ethers, and fatty acid alkanolamides; and amine oxide type nonionic Such as (hydroxy) alkyldi (hydroxy) alkylamine oxide.

(2) Cationic surfactants Quaternary ammonium salt type cationics, for example, tetraalkylammonium salts (C11-100); trialkylbenzylammonium salts (C17-80); alkyl (C8-60) pyridinium salts; ) Oxyalkylene (C2-4, degree of polymerization 1-100 or higher) trialkylammonium salt (C12-100); and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4)] ammonium salts; and amine salt-type cationics, such as primary to tertiary amines [eg higher aliphatic amines and polyoxyalkylene derivatives of aliphatic amines, and Acylaminoalkyl or acyloxyalkyldi (H Inorganic and organic acid salts of droxy) alkylamines].

(3) Anionic surfactant Carboxylic acid (salt) such as higher fatty acid, ether carboxylic acid and salts thereof; Sulfate ester salt such as sulfate ester salt or sulfated fatty acid ester of the above higher alcohol or its AO adduct And sulfated olefins; sulfonate salts; and phosphate ester salts, such as phosphate esters of higher alcohols or AO adducts thereof or AO adducts of alkyl (C4-60) phenols.

(4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics, such as amino acid type amphoterics, and betaine type amphoterics; sulfate ester (salt) type amphoterics, such as alkylamine sulfates (salts), and hydroxy Alkyl imidazoline sulfate (salt); sulfonic acid (salt) type amphoterics, such as alkyl sulfotaurine, and imidazoline sulfonic acid (salt); and phosphate ester (salt) type amphoterics, such as GR higher fatty acid esters The phosphate ester (salt).

Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts and quaternary ammonium salts.
The amine constituting the salt includes C1-20 amines such as hydroxylamine, tertiary amino group-containing diols and primary monoamines, secondary monoamines, and their alkylation (C1-4) and / or hydroxyalkylation ( C2-4) products (AO adducts): for example mono-, di- and tri- (hydroxy) alkyl (amines) (mono-, di- and tri-ethanolamine and ethylamine, diethylethanolamine, morpholine, N-methyl Morpholine, N-hydroxyethylmorpholine and the like). The quaternary ammonium salt includes a quaternized product of these amines [a quaternized product of a quaternizing agent or a dialkyl carbonate (described above) described in US Pat. No. 4,271,217].

  As the dispersant (H5), a polymer having Mn of 1,000 to 20,000, for example, a vinyl resin {for example, polyolefin [for example, polyethylene, polypropylene, ethylene / butene copolymer [copolymerization weight ratio 1 to 99/1 to 99], Propylene / butene copolymer [copolymerization weight ratio 1 to 99/1 to 99] and ethylene / propylene / butene copolymer [copolymerization weight ratio 1 to 98/1 to 98/1 to 98], modified polyolefin [for example Oxidized polyethylene (polyethylene is oxidized with ozone, etc., and carboxyl groups, carbonyl groups and / or hydroxyl groups are introduced), polypropylene oxide (obtained in the same manner as the above oxidized polyethylene by replacing polyethylene with polypropylene), epoxy-modified polyethylene (Epoxy equivalent 100-20,000), Epoxy Modified polypropylene (epoxy equivalent 100 to 20,000), hydroxyl modified polyethylene (hydroxyl value 0.1 to 60), hydroxyl modified polypropylene (hydroxyl value 0.1 to 60), hydroxyl modified ethylene / butene copolymer (hydroxyl value 0) 1-60, copolymer weight ratio 1-99 / 99-1) and hydroxyl-modified propylene / butene copolymer (hydroxyl value 0.1-60, copolymer weight ratio 1-99 / 99-1)]]] and Vinyl resins other than the above polyolefins [for example, polyhalogenated vinyl [for example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride and polyiodide], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meth) acrylic acid, Poly (meth) acrylic ester [eg poly (meth) acrylic ester Acid-methyl, -ethyl, -n- and i-propyl and -n- and t-butyl] and styrene resins [eg polystyrene, acrylonitrile / styrene (AS) resin and acrylonitrile / butadiene / styrene (ABS) resin]]} ;

Polyester resins [eg polyalkylene (C2-24) terephthalate [eg polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)], polyalkylene (C2-24) isophthalate [eg polyethylene isophthalate and polybutylene isophthalate] and poly -P-phenylene esters [eg poly-p-phenylene malonate, poly-p-phenylene adipate and poly-p-phenylene terephthalate]]; polyamides [eg polycoupleramide (6-nylon), polyhexamethylene adipamide (6, 6-nylon), polyhexamethylene sebacamide (6,10-nylon), polyundecanamide (11-nylon), poly-ω-aminoheptanoic acid (7-nylon) and poly-ω- Aminononanoic acid (9-nylon)]; polyether resins [eg polyoxymethylene, polyoxyethylene, polyoxyphenylene and poly-1,3-dioxolane]; polycarbonate resins; polyphenylene resins (PPO); Examples include coalescence.

  Antioxidants (H6) include hindered phenols [pt-amylphenol-formaldehyde resin, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-tert-butyl-4- Methylphenol (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B) and the like];

Sulfur-containing systems [N, N'-diphenylthiourea, 6- (4-oxy-3,5-di-t-butylanilino) 2,4-bis (n-octylthio) -1,3,5-triazine, etc.];

Phosphorus-containing [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, phosphite ester resin, tris (nonylphenyl) phosphite, Dioctadecyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate etc.] and the like.

  Examples of the ultraviolet absorber (H7) include salicylates [phenyl salicylates and the like]; benzophenones [2,4-dihydroxyzenzophenones and the like]; benzotriazoles [2- (2′-hydroxy-5′-methylphenyl). ) -Benzotriazole and the like].

The total content of (H) in the masterbatch resin composition to be described later is usually 30% or less based on the weight of the composition, preferably 0.1 to 0.1 from the functional expression of (H) and an industrial viewpoint. 10%.
The amount of each additive based on the weight of the composition is as follows: (H1) is usually 10% or less, preferably 1 to 5%; (H2) is usually 15% or less, preferably 3 to 10%; (H3) Is usually 15% or less, preferably 3 to 10%; (H4) is usually 10% or less, preferably 1 to 5%; (H5) is usually 2% or less, preferably 0 to 0.5%, particularly preferably 0%; (H6) is usually 3% or less, preferably 0.01 to 1%, and (H7) is usually 3% or less, preferably 0.01 to 1%.

Further, the total content of (H) in the molding resin composition to be described later is usually 20% or less based on the weight of the composition, preferably from the viewpoint of the functional expression of (H) and the industrial viewpoint. 05 to 5%.
The amount of each additive used based on the weight of the composition is such that (H1) is usually 5% or less, preferably 1.5 to 5%; (H2) is usually 8% or less, preferably 1.5 to 5%. ; (H3) is usually 8% or less, preferably 1.5 to 5%; (H4) is usually 8% or less, preferably 1.5 to 5%; (H5) is usually 1% or less, preferably 0 to 0%; 0.03%, particularly preferably 0%; (H6) is usually 2% or less, preferably 0.005 to 0.5%, (H7) is usually 2% or less, preferably 0.005 to 0.5%. It is.

  When the additive is the same and overlaps between (H1) to (H7) above, the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive, 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.

The production method of the biodegradable resin composition (Z) includes the following methods [1] and [2].
[1] A method in which (A), (B), (C), and if necessary, additive (H) are mixed together at the same ratio as the ratio in the molded product to obtain (Z) (resin composition for molding). (Batch mixing method);
[2] Master containing high concentration of (C) by mixing the total amount of (C), a part of (A) and / or a part of (B), and a part or the whole of (H) if necessary A method in which a batch resin composition (MZ) is prepared once, and then the remaining (A), (B) and, if necessary, the remaining (H) are added and mixed to obtain (Z) (molding resin composition) ( Masterbatch method).
Among these methods, the method [2] is preferable from the viewpoint of the miscibility of (A), (B) and (C).

  The content of (C) in the above (MZ) is based on the total weight of (A) and / or (B) and (C) from the viewpoint of compatibility between (A) and (B) and from an industrial viewpoint. It is preferably 30 to 80%, more preferably 40 to 60%.

As a specific manufacturing method of the molding resin composition (Z) and the masterbatch resin composition (MZ), for example, in the case of <1> the batch mixing method, (A), (B), (C) And, if necessary, (H), and in the case of the masterbatch method, (C), (A) and / or (B), and (H) if necessary, respectively, for example, a powder mixer [Henschel After mixing at, for example, 0 to 80 ° C. with a mixer, Nauter mixer, Banbury mixer [trade name, manufactured by Farrel Co., Ltd.], etc., a melt-kneader {batch kneader (reaction vessel etc.), continuous kneader [FCM [ Product name, manufactured by Farrel Co., Ltd.], LCM [trade name, manufactured by Kobe Steel Co., Ltd.], CIM [trade name, manufactured by Nippon Steel Works, Ltd.], etc.], single screw extruder, twin screw extruder, etc. } At 120-220 ° C. for 2-30 minutes How to kneading;
<2> A method of directly kneading the same composition as the above <1> under the same conditions using the same melt kneader without mixing the powder.
Among these methods, the method <1> is preferable from the viewpoint of kneading efficiency.

  The molded article of the biodegradable resin composition of the present invention can be obtained by molding the 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 the like. Molding can be performed by any method that incorporates means such as layer molding, multilayer molding, and foam molding.

The biodegradable resin molded article comprising the resin composition of the present invention has excellent mechanical strength and good paintability and printability, and the molded article can be formed by painting and / or printing on the molded article. can get.
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.

In addition, as a method of 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 , Screen printing, pad printing, dry offset printing, offset printing, and the like.
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”.

Production Example 1
In a reaction vessel, 100 parts of polyolefin (Mn 70,000) having 98 mol% of propylene and 2 mol% of ethylene as structural units was placed in a nitrogen atmosphere, and heated and melted while bubbling nitrogen through the gas phase part. Thermal degradation was performed at 60 ° C. for 60 minutes to obtain a thermal degradation product (C0-1). (C0-1) had 13.9 double bonds per 1,000 carbon atoms and 2,000 Mn.
In a separate reaction vessel, 55 parts of (C0-1), 45 parts of maleic anhydride and 100 parts of xylene were placed. After purging with nitrogen, the mixture was heated to 130 ° C. under nitrogen flow to dissolve uniformly. A solution prepared by dissolving 0.5 part of dicumyl peroxide in 10 parts of xylene was added dropwise thereto, and then the temperature was raised to xylene reflux temperature and stirring was continued for 3 hours. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to have 18 acid anhydride groups per molecule, and Mn4,800 acid anhydride. A modified polyolefin (C0a-1) was obtained.

Production Example 2
(C0a-1) 15 parts of 2-aminoethanol are added to 85 parts, and the mixture is stirred at 180 ° C. for 1 hour. The hydroxyl group-modified polyolefin (C11-1) having 18 hydroxyl groups per molecule and Mn 4,400 is obtained. Obtained.

Production Example 3
In Production Example 1, instead of heat degradation at 360 ° C. for 60 minutes, a heat degradation product (C0-2) was produced in the same manner as in Production Example 1 except that heat degradation was performed at 360 ° C. for 10 minutes. Got. (C0-2) had 6 double bonds per 1,000 carbon atoms and Mn 4,000.
Further, in Production Example 1, in the same manner as Production Example 1 except that (C0-2) 80 parts and maleic anhydride 20 parts were used instead of (C0-1) 55 parts and maleic anhydride 45 parts. An acid anhydride-modified polyolefin (C0a-2) having Mn5,000 having 8 acid anhydride groups per molecule was obtained.

Production Example 4
(C0a-2) 11 parts of 2-aminoethanol are added to 89 parts, and the mixture is stirred at 180 ° C. for 1 hour, and has a hydroxyl group-modified polyolefin (C11-2) having 8 hydroxyl groups per molecule and Mn 6,000. Obtained.

Production Example 5
In Production Example 1, instead of a polyolefin (Mn 70,000) having 98 mol% of propylene and 2 mol% of ethylene as structural units, a polyolefin (Mn 70,000) having 80 mol% of propylene and 20 mol% of 1-butene. ), And instead of thermal degradation at 360 ° C. for 60 minutes, double bonding per 1,000 carbon atoms was performed in the same manner as in Production Example 1 except that thermal degradation was performed at 360 ° C. for 5 minutes. A thermal degradation product (C0-3) having a number of 2.0 and Mn of 12,000 was obtained, and further having 5 acid anhydride groups per molecule, and an acid anhydride-modified polyolefin having a Mn of 12,500 ( C0a-3) was obtained.

Production Example 6
(C0a-3) 4 parts of 2-aminoethanol are added to 96 parts, and the mixture is stirred at 180 ° C. for 1 hour, and has a hydroxyl group-modified polyolefin (C11-3) having 5 hydroxyl groups per molecule and Mn of 13,000. Obtained.

Production Example 7
In Production Example 1, a polyolefin having 100 mol% of propylene as a structural unit (Mn 60,000) was used instead of polyolefin having 98 mol% of propylene and 2 mol% of ethylene as a structural unit (Mn 70,000). Instead of heat degradation for 60 minutes, the number of double bonds per 1,000 carbons was 2.1 in the same manner as in Production Example 1 except that heat degradation was performed at 360 ° C. for 5 minutes. A thermal degradation product (C0-4) of Mn 12,000 was obtained, and further an acid anhydride-modified polyolefin (C0a-4) having Mn 12,500 having 6 acid anhydride groups per molecule was obtained. .

Production Example 8
(C0a-4) 96 parts of 2-aminoethanol 4 parts, stirred at 180 ° C. for 1 hour, having 6 hydroxyl groups per molecule, Mn 13,000 hydroxyl-modified polyolefin (C11-4) Obtained.

Production Example 9
In Production Example 1, in place of heat degradation at 360 ° C. for 60 minutes, heat degradation at 360 ° C. for 5 minutes was carried out in the same manner as in Production Example 1 except that double per 1,000 carbons was produced. A heat-degraded product (C0-5) having 2 bonds and Mn of 14,000 was obtained, and further having two acid anhydride groups per molecule, and an acid anhydride-modified polyolefin (C0a having Mn of 14,200). -5) was obtained.
(C0a-5) 1 part of 2-aminoethanol is added to 99 parts, and the mixture is stirred at 180 ° C. for 1 hour, and has a hydroxyl group-modified polyolefin (C11-5) having two hydroxyl groups per molecule and Mn 14,500. Obtained.

Production Example 10
In Production Example 1, in place of heat degradation at 360 ° C. for 60 minutes, heat degradation at 360 ° C. for 3 minutes was carried out in the same manner as in Production Example 1 except that double per 1,000 carbons was produced. A heat-degraded product (C0-6) having a bond number of 1 and Mn of 28,000 was obtained, and an acid anhydride-modified polyolefin having Mn of 28,100 having 0.5 acid anhydride groups per molecule. (C0a-6) was obtained.
(C0a-6) 0.5 part of 2-aminoethanol was added to 99.5 parts, and the mixture was stirred at 180 ° C. for 1 hour, having 0.5 hydroxyl groups per molecule, and Mn 28,200 hydroxyl group-modified polyolefin. (C11-6) was obtained.

Production Example 11
A reaction vessel was charged with 100 parts of a thermal degradation product (C0-1) and 100 parts of xylene, and the thermal degradation product was dissolved at 130 ° C. In a separate glass beaker, 14 parts of HEMA, 0.5 part of dicumyl peroxide and 10 parts of xylene were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution in the gas phase part of the reaction vessel, the monomer solution was added dropwise over 2 hours at 130 ° C. under reflux, and after aging at 130 ° C. for 2 hours from the end of the addition, xylene was distilled off under reduced pressure, A hydroxyl group-modified polyolefin (C11-7) having 3 hydroxyl groups per molecule and having Mn 2,300 was obtained.

Production Example 12
In Production Example 1, a polyolefin (Mn 80,000) having 100 mol% of ethylene as a structural unit was used instead of polyolefin (Mn 70,000) having 98 mol% of propylene and 2% of ethylene as a structural unit. The number of double bonds per 1,000 carbons was 6.5, and Mn3 in the same manner as in Production Example 1 except that heat degradation was performed at 340 ° C. for 20 minutes instead of heat degradation for minutes. , 500 thermal degradation product (C0-8) was obtained, and further 10 acid anhydride groups per molecule were obtained to obtain an acid anhydride-modified polyolefin (C0a-8) having Mn 4,500.

Production Example 13
(C0a-8) 22 parts of 2-aminoethanol were added to 88 parts, and the mixture was stirred at 170 ° C. for 1 hour, having 10 hydroxyl groups per molecule, and having a Mn5,000 hydroxyl group-modified polyolefin (C11-8). Obtained.

Production Example 14
Hydroxyl-modified polyolefin (C11-1) 50 parts and commercially available polypropylene (B-1) [trade name “Sun Allomer PL500A”, manufactured by Sun Allomer Co., Ltd., hereinafter the same. After blending 50 parts with a Henschel mixer for 3 minutes, a master batch resin composition (MZ-1) was obtained by melting and kneading in a twin screw extruder with a vent at 200 ° C., 100 rpm, and a residence time of 5 minutes. It was.

Comparative production example 1
In a reaction vessel, 100 parts of polyolefin (Mn 60,000) having 50 mol% of propylene and 50 mol% of ethylene as a structural unit is charged in a nitrogen atmosphere, heated and melted while ventilating nitrogen in the gas phase part, and stirred while stirring. Thermal degradation was carried out at 120 ° C. for 120 minutes to obtain a thermal degradation product (ratio C0-1). (Ratio C0-1) had 18.5 double bonds per 1,000 carbon atoms and Mn 1,500.

Comparative production example 2
(C0a-6) 0.3 part of 2-aminoethanol was added to 99.7 parts, and the mixture was stirred at 180 ° C. for 1 hour, having 0.04 hydroxyl groups per molecule, and Mn 28,100 hydroxyl group-modified polyolefin. (Ratio C11-1) was obtained.

Comparative production example 3
(C0a-1) 20 parts of 2-aminoethanol are added to 80 parts, stirred at 180 ° C. for 1 hour, hydroxyl group-modified polyolefin of Mn 5,000 having 22 hydroxyl groups per molecule (ratio C11-2) Got.

Examples 1-18, Comparative Examples 1-12
(C0a-1), (C0a-2), (C11-1) to (C11-8), (Ratio C0-1), (Ratio C11-1), (Ratio C11-2), (MZ-1) And the following commercially available components (parts) shown in Tables 1 and 2 were blended for 3 minutes with a Henschel mixer, respectively, and then in a twin screw extruder with a vent at 200 ° C., 100 rpm, and a residence time of 5 minutes. It was melt-kneaded to obtain a molded product resin composition. Each resin composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 40 ° C. using an injection molding machine [trade name “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was cut out. Evaluation was performed according to the test method. The results are shown in Table 3.

Commercially available polylactic acid (hereinafter abbreviated as PLA) (A-1)
: Trade name “Lacia H-100”, manufactured by Mitsui Chemicals, Inc.
Commercially available polyhydroxybutyrate (hereinafter abbreviated as PHB) (A-2)
: Product name “Biogreen” manufactured by Mitsubishi Gas Chemical Company, Inc.
Commercially available polypropylene (hereinafter abbreviated as PP) (B-1)
: Product name “Sun Allomer PL500A”, manufactured by Sun Allomer Co., Ltd.
Commercially available polyethylene (hereinafter abbreviated as PE) (B-2)
: Product name "Novatec HD HJ490" manufactured by Nippon Polyethylene Co., Ltd.

<Test method>
[1] Izod impact strength (Unit: J / m)
Measured according to ASTM D256. The shape of the test piece is vertical 63.5 mm × width 12.
7mm x 4mm thickness with notches.
[2] Flexural modulus (unit: MPa)
Measured according to ASTM D790. The shape of the test piece is vertical 80 mm x horizontal 10 mm x
Thickness 4mm.
[3] Compatibility (evaluated by number average dispersed particle size μm)
The test piece after the Izod impact strength evaluation was scanned at −100 ° C. using an ultramicrotome [model number “EMFC6”, manufactured by LEICA Co., Ltd.] to create a mirror surface by cutting the fractured surface with a glass cutter and a diamond cutter. This was observed with a scanning electron microscope [model number “S4800”, manufactured by Hitachi, Ltd.], and the number average dispersed particle size of the PLA resin or PHB resin in the matrix resin (PP) was measured to evaluate the compatibility. The unit is μm. The number average dispersed particle diameter is a number average value in a range of 20 μm × 25 μm. The smaller the number average dispersed particle size, the better the compatibility.

  The biodegradable resin composition of the present invention contains a biomass-derived resin (A), a polyolefin resin (B), and a compatibilizer (C), contains a high-content biomass-derived resin, and the resin composition Molded products have excellent mechanical properties (impact resistance, flexural modulus, etc.), so as environmentally friendly molded products, containers and packaging materials (food, medical products, industrial products, and home appliance parts) Etc.), housings (for home appliance parts, etc.), transport materials (containers, etc.), living materials (furniture, gardening products, etc.), building materials (doors, ceiling materials, etc.), etc. It is.

Claims (7)

In the resin composition comprising the biomass-derived resin (A), the polyolefin resin (B) and the compatibilizer (C), (C) is obtained by modifying the heat-degraded polyolefin, and has 0.1 in the molecule. A biodegradable resin composition comprising only a hydroxyl group-modified polyolefin (C1) having -20 hydroxyl groups. The composition according to claim 1 , wherein the weight ratio of (A) to (B) is from 10/90 to 60/40. The composition according to claim 1 or 2, wherein (C) is a compatibilizing agent for adjusting the number average dispersed particle size of (A) to 0.3 to 1.0 µm.   The composition according to any one of claims 1 to 3, wherein the content of (C) is 0.1 to 30% based on the total weight of (A), (B) and (C).   A biomass-derived resin (A) and / or a polyolefin resin (B), and the compatibilizer (C) according to any one of claims 1 to 3, wherein the content of (C) is (A) and / or Or the masterbatch biodegradable resin composition which is 30 to 80% based on the total weight of (B) and (C).   A biodegradable resin molded product obtained by molding the composition according to claim 1. A molded article obtained by coating and / or printing the molded article according to claim 6.