JP2002322355A - Resin composition, formed article using the same and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a biodegradable resin composition having excellent extrusion forming workability, good mechanical properties and high thermal resistance, in particular, a resin composition simultaneously having both biodegradability and thermal resistance at the formation; a formed article using the resin composition; and a production method therefor. SOLUTION: The formed article having biodegradability and ensuring high thermal resistance or good mechanical properties is provided by forming the resin composition which contains a polyhydroxy alkanoate having a 3-hydroxy-5- benzoyl valeric acid unit or by forming a resin composition which is obtained by kneading the polyhydroxy alkanoate and a thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, a molded article using the same, and a method for producing the same. More specifically, among various polyhydroxyalkanoates produced by microorganisms, they exhibit a high melting point and glass transition temperature.
The present invention relates to a resin composition having at least polyhydroxyalkanoate having a -hydroxy-5-benzoylvaleric acid unit, having biodegradability, improved heat resistance and mechanical properties, a molded article, and a method for producing the same.

[0002] The resin composition of the present invention can be used for applications restricted by the thermal properties of conventional microbial polyhydroxyalkanoates, for example, various types, heat appliances, containers, automobile parts, and the like. Specifically, for example, it can be used for containers such as food containers, beverage containers, toiletry containers such as shampoo containers and rinse containers, chemical containers, and cosmetic containers.

[0003]

BACKGROUND ART Conventionally, polyethylene terephthalate (PE)
T) Plastics such as resins, polyester resins, vinyl chloride resins, and polyolefin resins have been used in various applications as molded articles, for example, containers for food containers, beverage bottles, cosmetic containers, flowerpots, and the like. Was.

Most of these plastics are discarded after use. Conventionally, such plastic waste is treated by incineration or landfill. However, since the waste generates a large amount of combustion energy by incineration, there is a problem of durability of the incinerator due to high combustion temperature. Problems of processing costs due to installation of blast furnace, carbon monoxide, sulfur compounds, chlorine gas, dioxin, etc.
It has problems such as air pollution due to generation of harmful incineration gas. Further, in the landfill treatment, the waste remains semi-permanently without being decomposed and is deposited as waste at a disposal site, which has become a social problem as a garbage problem.
In addition, since the waste is present in the ground as it is, there is a problem that the ground of the landfill is not stable, and there is a risk of adversely affecting the natural environment and various organisms in the landfill and its surrounding area. is there.

Therefore, in order to solve these problems,
In recent years, biodegradable resins have attracted attention. Here, the biodegradable resin has almost the same physical properties as general-purpose plastics when used as a material, but after disposal, on soil, in soil,
Under natural environments such as compost, activated sludge, and water, it refers to a resin that is rapidly decomposed by microorganisms, is finely decomposed, and eventually turns into carbon dioxide and water.

Conventionally, as a biodegradable resin, in addition to a specific polyester-based biodegradable resin, a starch-ethylene-vinyl alcohol copolymer resin, an ethylene-vinyl alcohol copolymer resin, in addition to a specific polyester biodegradable resin. Blend-based resin compositions such as aliphatic polyester resins, aliphatic polyester resins and polyolefin resins are known, and these resins or resin compositions are molded into various shapes such as bottles and put to practical use. Have been. However, in addition to various physical properties required for containers, biodegradability required after disposal, etc., excellent resin compositions balanced in moldability required in manufacturing, for example, biodegradability during molding and heat resistance Resin compositions having both properties have not yet been proposed.

In recent years, as one method for solving environmental pollution caused by waste such as plastic molded articles,
It has been proposed to use biodegradable resins synthesized by microorganisms as molding materials. For example, as biodegradable resins derived from microorganisms, poly-3-hydroxy-n-butyric acid (hereinafter sometimes abbreviated as PHB) or 3-hydroxy-n-butyric acid is used.
Polyhydroxyalkanoates (hereinafter sometimes abbreviated as PHA) such as copolymers of butyric acid and 3-hydroxy-n-valeric acid (hereinafter sometimes abbreviated as PHB / V), bacterial cellulose and pullulan Polysaccharide, poly-γ-
Polyamino acids such as glutamic acid and polylysine are known. In particular, PHA, like conventional plastic,
It can be used for various products by melt processing and the like, and has excellent biocompatibility, and is also expected to be used as a medical soft member.

[0008] It has been reported that many microorganisms produce PHA and accumulate in the cells. For example, Alcaligenes jutrofus H16 strain (Alcaligenes
eutropus H16, ATCC No. 17699), Methylobacterium sp., Paracoccus (Pa)
racoccus sp. ), Alcaligenes
sp. ), Production of PHB / V by microorganisms of the genus Pseudomonas (Pseudomonas sp.) Has been reported (JP-A-5-74492, JP-B-6-15604,
JP-B-7-14352, JP-B-8-19227, etc.). Also, Comamonas Acidophilus IF
O13852 strain (Comamonas acidovorans IFO13852)
Is 3-hydroxy-n-butyric acid and 4-hydroxy-n-
It is disclosed that PHA having butyric acid as a monomer unit is produced (JP-A-9-191893).
In addition, Aeromonas cavia
e) discloses that a copolymer of 3-hydroxy-n-butyric acid and 3-hydroxyhexanoic acid is produced (JP-A-5-93049, JP-A-7-265).
No. 065).

However, these 3-hydroxy-
Linear aliphatic polyesters, which are copolymers of n-butyric acid and / or 3-hydroxy-n-valeric acid, are prone to thermal decomposition because of their close melting points and thermal decomposition temperatures. Poor. In addition, the linear aliphatic polyester has a high crystallinity, so that it is brittle, has a small elongation, and tends to have low mechanical properties. Therefore, this alone is not preferable for the material of the molded article.

In recent years, polyhydroxyalkanoates comprising a 3-hydroxyalkanoic acid unit having a medium-chain-length of about 3 to 12 carbon atoms (hereinafter abbreviated as mcl-PHA) are sometimes used. ) Is being actively researched.

For example, in Japanese Patent Publication No. 2642937, Pseudomonas oleovorans ATCC 29
By giving acyclic aliphatic hydrocarbons to strain 347 (Pseudomonas oleovorans ATCC 29347), the number of carbon atoms becomes 6
It is disclosed that PHAs having up to -12 monomer units of 3-hydroxyalkanoic acid are produced. Appl. Environ. Microbiol. , 58, 746 (199
2) Pseudomonas reginoborans (Pseudomon
as resinovorans) produce PHA using octanoic acid as a single carbon source and 3-hydroxy-n-butyric acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, and 3-hydroxydecanoic acid as monomer units; ,
3-hydroxy-n-
PH containing butyric acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid and 3-hydroxydecanoic acid as units
It is reported to produce A.

Int. J. Biol. Macromol. , 16 (3), 119
(1994) include Pseudomonas sp. 61-3 strains (Pseu
domonas sp. strain 61-3) using sodium gluconate as a single carbon source, 3-hydroxy-n-butyric acid, 3
-Hydroxyhexanoic acid, 3-hydroxyoctanoic acid,
3-hydroxyalkanoic acids such as 3-hydroxydecanoic acid and 3-hydroxydodecanoic acid, and 3-hydroxy-5-cis-decenoic acid, 3-hydroxy-5-c
It has been reported to produce PHA using 3-hydroxyalkenoic acid as a unit, such as is-dodecenoic acid.

However, these mcl-PHA
Has a low melting point, and if it exceeds 50 ° C., becomes sticky and softens severely, and a molded product by itself is of low practicality.

By the way, the above PHA is composed of a monomer unit having an alkyl group in a side chain (hereinafter referred to as uA).
common-PHA). But,
In consideration of a wider range of applications, substituents other than alkyl groups (eg, phenyl group, unsaturated hydrocarbon, ester group, allyl group, cyano group, halogenated hydrocarbon, epoxide, etc.) are introduced into the side chain. PHA (hereinafter referred to as unu
sua-PHA) is very useful.

Unusual-PH having a phenyl group
Examples of the biosynthesis of A include, for example, Macromolecules, 2
4, 5256-5260 (1991), Macromol. Chem. , 191,1957
-1965 (1990), Chirality, 3, 492-494 (1991), etc., reported that Pseudomonas oleovorans produces PHA containing 5-hydroxy-5-phenylvaleric acid unit from 5-phenylvaleric acid. I have. Also,
In Macromolecules, 29, 1761-1766 (1996), Pseudomonas oleovorans was converted from 5- (4-tolyl) valeric acid (5- (4-methylphenyl) valeric acid) to 3-hydroxy-5- (4-tolyl). P) containing valeric acid unit
It is reported to produce HA. In addition, Macromol
In ecules, 32, 2889-2895 (1999), Pseudomonas oleovorans is based on 5- (2,4-dinitrophenyl) valeric acid from 3-hydroxy-5- (2,4-dinitrophenyl) valeric acid unit and 3-hydroxy-
PH containing 5- (4-nitrophenyl) valeric acid unit
A is reported to be produced.

Also, unusua having a phenoxy group
Examples of l-PHA include Macromol. Chem. Phys. , 19
5,1665-1672 (1994), a PHA containing 11-phenoxyundecanoic acid to 3-hydroxy-5-phenoxyvaleric acid and 3-hydroxy-9-phenoxynonanoic acid units.
Is reported to be produced. Also, Macromolecule
s, 29, 3432-3435 (1996) discloses that Pseudomonas oleovorans comprises a PHA containing 6-phenoxyhexanoic acid to 3-hydroxy-4-phenoxybutyric acid and 3-hydroxy-6-phenoxyhexanoic acid units.
From 8-phenoxyoctanoic acid to 3-hydroxy-4
-Phenoxybutyric acid unit, 3-hydroxy-6-phenoxyhexanoic acid unit and 3-hydroxy-8-
PHA containing a phenoxyoctanoic acid unit is
It has been reported that phenoxyundecanoic acid produces a PHA containing a 3-hydroxy-5-phenoxyvaleric acid unit and a 3-hydroxy-7-phenoxyheptanoic acid unit. Further, Can. J. Microbiol. ,Four
1, 32-43 (1995), Pseudomonas oleovorans ATCC 29347 and Pseudomonas putida KT2442 (Pseudomonas putida KT2442)
Can be converted from p-cyanophenoxyhexanoic acid or p-nitrophenoxyhexanoic acid to a PH containing a 3-hydroxy-p-cyanophenoxyhexanoic acid unit or a 3-hydroxy-p-nitrophenoxyhexanoic acid unit.
A is reported to be produced.

In addition, unus having a cyclohexyl group
Examples of ual-PHA include Macromolecules, 30, 16
11-1515 (1997) reports that Pseudomonas oleovorans produces the PHA from cyclohexylbutyric acid or cyclohexylvaleric acid.

[0018]

As described above, since conventional plastic molded products are made of a material such as vinyl chloride resin or PET, which is difficult to dispose of, if they are discarded as they are, in the natural world, Without decomposition, it can cause various environmental problems. Furthermore, plastic molded articles are used in large quantities, and their usage tends to increase year by year. Therefore, urgent measures for waste disposal are strongly desired.

The present invention has been made in order to solve the above-mentioned problems, and a resin composition capable of preventing various environmental problems due to disposal, a molded article using the same, and a method of manufacturing the same. Is provided.

Further, the present invention provides a molded article made of a biodegradable resin excellent in extrusion processability, mechanical properties, heat resistance, etc., and in particular, a resin composition having both biodegradability during molding and heat resistance. It is intended to be.

Further, as described above, by applying the biotechnological technique to the production of the resin composition and the molded article, a new resin composition and a molding method which are difficult to realize by the conventional organic synthetic chemistry technique. Products can be manufactured. Furthermore, there are many cases where a conventional manufacturing process that requires a multi-step reaction in an organic synthetic chemistry method can be realized with only a single step, thereby simplifying the manufacturing process, reducing costs, and shortening the required time. Effects such as are expected. Furthermore, it is possible to reduce the use of organic solvents, acids and alkalis, surfactants, etc., set mild reaction conditions, synthesize from non-petroleum-based raw materials and low-purity raw materials, etc. The synthesis process can be realized.

The above-mentioned synthesis from a low-purity raw material will be described in more detail. In general, in a biotechnological synthesis process, the enzyme, which is a catalyst, has high substrate specificity. The reaction can proceed selectively. Therefore, the use of waste and recycled materials can be expected.

[0023]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, it has been found that a microorganism-producing PHA having a 3-hydroxy-5-benzoylvaleric acid unit has a high melting point (hereinafter referred to as "high melting point"). , Tm) and a glass transition temperature (hereinafter sometimes abbreviated as Tg), and by using the PHA in a resin composition, extrudability, mechanical properties, heat resistance The present inventors have found that a resin composition having excellent properties and the like and further having biodegradability can be obtained, and have reached the present invention.

That is, the present invention provides the following chemical formula [1]:

[0025]

Embedded image

The present invention relates to a resin composition containing at least a PHA having a 3-hydroxy-5-benzoylvaleric acid unit represented by the formula (1), a molded article using the resin composition, and a method for producing the same.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Generally, Tm and Tg are important physical properties related to heat resistance and mechanical strength (for example, elastic modulus) of a resin material. For example, a resin material having a high Tm or Tg is excellent in heat resistance and strength, while a resin material having a low Tm or Tg has advantages such as easy molding, but is inferior in heat resistance and strength. You. Many conventional PHAs have relatively low Tm and Tg, so that extrudability,
There are limitations on mechanical properties, heat resistance, and the like, and there is a limit in expanding its use.

The resin composition of the present invention comprises 3-hydroxy-
The resin composition contains at least PHA having a 5-benzoylvaleric acid unit, and the resin composition is a conventional mcl-P
It has improved thermal properties as compared with resin compositions using HA or unusual-PHA. The resin composition of the present invention comprises a conventional mcl-PHA or unusual-PHA
Compared with a resin composition using a resin composition, physical properties such as heat resistance and mechanical properties are improved, and in applications where these physical properties are required, for example, in an environment of relatively high temperature (140 ° C. or lower) It can be applied to the use of. Hereinafter, the present invention will be described in more detail.

<PHA> The PHA of the present invention is a PHA having at least a 3-hydroxy-5-benzoylvaleric acid unit.
This is performed using a microorganism capable of producing.

If appropriate conditions are prepared using the microorganism, it is possible to synthesize a copolymer of a 3-hydroxy-5-benzoylvaleric acid unit and another 3-hydroxyalkanoic acid unit. is there. Specific examples of such a monomer unit include a 3-hydroxyhexanoic acid unit, a 3-hydroxyheptanoic acid unit, a 3-hydroxyoctanoic acid unit, a 3-hydroxynonanoic acid unit, a 3-hydroxydecanoic acid unit, and a 3-hydroxycarboxylic acid unit. Examples thereof include 3-hydroxyalkanoic acid units constituting mcl-PHA, such as dodecanoic acid units and 3-hydroxytetraic acid units. Also, P
HA can contain a plurality of these monomer units, and it is possible to control the physical properties of PHA using the characteristics of each monomer unit and the contained functional groups, to provide a plurality of functions, and to provide new functions utilizing the interaction between functional groups. Can be expressed.

The molecular weight of PHA is 100 in number average molecular weight.
It is desirable to set it to about 0 to 10,000,000.

The microorganism-produced PHA used in the resin composition of the present invention is generally an isotactic polymer composed of only the R-form.

<PHA-producing bacteria> Examples of microorganisms having a PHA-synthesizing ability include mcl-PHA and unusual-PH.
Any of the A-producing bacteria can be used. Examples of such microorganisms include the aforementioned Pseudomonas oleovorans, Pseudomonas reginovorans, Pseudomonas sp. Strain 61-3, Pseudomonas putida KT2.
442 strains, etc., isolated by the present inventors,
Pseudomonas putida P91 strain (Pseudomonas put
ida P91), Pseudomonas cichorii H45 strain, Pseudomonas cichorii H45
Chicory eye YN2 strain (Pseudomonas cichorii YN
2), Pseudomonas jessenii P161 strain (Pse
microorganisms such as Pseudomonas jessenii P161) and Burkholderia sp. OK3 strain (Burkholderiasp. OK3, FER) described in JP-A-2001-78753.
MP-17370) and Burkholderia sp. OK4 strain described in JP-A-2001-69968 (Burkholderia sp.
Burkholderia microorganisms such as OK4, FERM P-17371) can be used. In addition to these microorganisms, it is also possible to use microorganisms belonging to the genus Aeromonas sp., The genus Comamonas sp. And producing mcl-PHA and unusual-PHA.

The P91 strain has a deposit number of FERM BP.
H-7 strain as accession number FERM BP
No.-7374, the strain YN2 has the accession number FERM BP.
Strain P161 as accession number FERM B
P-7376 has been internationally deposited at the Patented Microorganisms Depositary, the National Institute of Advanced Industrial Science and Technology, under the Budapest Treaty on the International Recognition of the Deposit of Microorganisms in Patent Procedures.

<Culture> The above microorganism was subjected to the introduction of a carbon source for introducing 3-hydroxy-5-benzoylvaleric acid unit and the introduction of a desired monomer unit other than 3-hydroxy-5-benzoylvaleric acid unit. Culturing in a medium containing at least a carbon source for the production of PHA. Such a PHA
Is an isotactic polymer generally composed only of the R-isomer.

The microorganisms used for ordinary cultivation of the microorganisms used in the production of PHA according to the present invention, for example, for the preparation of a preserved strain and for the growth to ensure the number of bacteria and the active state required for the production of PHA, etc. A medium containing components necessary for the growth of E. coli is appropriately selected and used. For example, as long as it does not adversely affect the growth and survival of the microorganism, any type of medium such as a general natural medium (meat medium, yeast extract, etc.) or a synthetic medium to which a nutrient is added can be used.

The culture can be carried out by any culture method such as liquid culture and solid culture, as long as the microorganism grows and PHA is produced. Further, any type of batch culture, fed-batch culture, semi-continuous culture, continuous culture, etc. may be used. As a form of the liquid batch culture, there are a method of supplying oxygen by shaking with a shaking flask and a method of supplying oxygen by stirring and aeration using a jar fermenter. Further, a multi-stage system in which these steps are connected in a plurality of stages may be adopted.

When a PHA containing a 3-hydroxy-5-benzoylvaleric acid unit is produced using the above-mentioned PHA-producing microorganism, 3-hydroxy-5-benzoylvaleric acid is used as a raw material for producing the PHA. An inorganic medium or the like containing at least a carbon source for introducing the unit and a carbon source for growing microorganisms can be used.

As the carbon source for introducing the 3-hydroxy-5-benzoylvaleric acid unit, any carbon source may be used as long as it can be converted into the monomer unit by the microorganism used. And benzoylalkanoic acids such as 5-benzoylvaleric acid and 7-benzoylheptanoic acid. Especially, it is preferable to use 5-benzoylvaleric acid.

As the growth carbon source, nutrients such as yeast extract, polypeptone, and meat extract can be used, and further, saccharides such as glyceraldehyde,
Aldose such as erythrose, arabinose, xylose, glucose, galactose, mannose and fructose; alditols such as glycerol, erythritol and xylitol; aldonic acids such as gluconic acid; uronic acids such as glucuronic acid and galacturonic acid; maltose; sucrose; Organic compounds involved in the TCA cycle, such as lactic acid, pyruvic acid, malic acid, citric acid, succinic acid, fumaric acid and salts thereof, other than sugars, etc. Any compound can be used, and it can be appropriately selected according to its usefulness as a substrate for the strain to be used. It is also possible to select and use a plurality of compounds.

As a method for producing and accumulating PHA in a microorganism, once the cells are sufficiently grown, the cells are transferred to a medium having a limited nitrogen source such as ammonium chloride, and a compound serving as a substrate of the target unit is added. Further culturing in this state may improve the productivity. Specifically, adoption of a multi-stage system in which the above-described steps are connected in a plurality of stages is exemplified. For example, D-glucose is 0.05% to 5.0%,
After culturing from the late logarithmic phase to the stationary phase in an inorganic medium or the like containing about 0.01% to 1.0% of 5-benzoylvaleric acid, the cells are collected by centrifugation or the like, and then 5-benzoylvaleric acid is recovered. Containing about 0.01% to 1.0% of folic acid,
There is a method of further culturing in an inorganic medium in which the nitrogen source is limited or substantially absent. Also, instead of D-glucose, the same amount of organic acids involved in the TCA cycle,
Yeast extract and polypeptone may be provided, or a combination thereof may be used.

The inorganic medium used in the above-mentioned culture method includes a phosphorus source (for example, phosphate) and a nitrogen source (for example,
Any material may be used as long as it contains a component that allows the growth of microorganisms such as ammonium salts and nitrates. For example, as the inorganic salt medium, MSB medium, E medium (J. Bio
l. Chem. , 218, 97-106 (1956)), M9 medium and the like.

The M9 used in the embodiment of the present invention
The composition of the medium is as follows.

Na ₂ HPO ₄ : 6.2 g KH ₂ PO ₄ : 3.0 g NaCl: 0.5 g NH ₄ Cl: 1.0 g (in 1 liter of medium, pH 7.0) Further good growth For the production of PHA synthase, it is preferable to add about 0.3% (v / v) of a minor component solution shown below to the above-mentioned inorganic salt medium.

[0045] (trace component solution) nitrilotriacetic _{acid: 1.5 g MgSO 4: 3.0 g} MnSO 4: 0.5 g NaCl: 1.0 g FeSO 4: 0.1 g CaCl 2: 0.1 g CoCl ₂ : 0.1 g ZnSO ₄ : 0.1 g CuSO ₄ : 0.1 g AlK (SO ₄ ) ₂ : 0.1 g H ₃ BO ₃ : 0.1 g Na ₂ MoO ₄ : 0.1 g NiCl ₂ : 0.1 g (in 1 liter) The culture temperature may be any temperature at which the above strain can grow well, for example, 15 to 40 ° C., preferably 20 to 40 ° C.
About 35 ° C. is appropriate.

<Recovery of PHA> For obtaining PHA from the culture solution according to the present invention, a commonly used method can be applied. When PHA is secreted into the culture solution, an extraction and purification method from the culture solution is used, and when PHA is accumulated in the cells, an extraction and purification method from the cells is used. For example, for recovery of PHA from cultured microbial cells of microorganisms, the usual extraction with an organic solvent such as chloroform or dichloromethane is the simplest, but acetone may be used in addition to chloroform or dichloromethane. In environments where organic solvents are difficult to use,
PHA by treatment with a surfactant such as SDS, treatment with an enzyme such as lysozyme, treatment with an agent such as EDTA, sodium hypochlorite, ammonia, hydrogen peroxide, etc.
A method for removing PHA by removing bacterial cell components other than the above can also be used.

<Resin Composition and Molded Article> The PHA obtained by the above-mentioned method can be appropriately molded and processed as necessary to obtain a molded article in a desired form.

The above-mentioned PHA can be used alone as a biodegradable resin composition. However, as long as desired properties can be obtained, the PHA may be blended with other resin components according to the purpose. Can also. The mixing ratio of the PHA and the thermoplastic resin is preferably in the range of 1 to 99% by mass based on the PHA. Specific examples of the resin component include polyester resins, polystyrene resins,
Examples thereof include a polypropylene resin, a polyethylene terephthalate resin, a polyurethane resin, a polyvinyl resin, and a polyamide resin. Among them, poly-
By using a polyester resin such as ε-caprolactone or polylactic acid, it is possible to obtain a resin composition having excellent biodegradability, but other resin components such as polystyrene can be produced by the method of the present invention. Degradability can be improved. This is because, in a molded product obtained by blending the above-mentioned resin with PHA in the present invention, the PHA is rapidly decomposed in a natural environment, so that the molded product is rapidly disintegrated. It is considered that the biodegradation can be easily performed.

Further, if necessary, a resin additive may be added to the resin composition for use. Resin additives include plasticizers, heat stabilizers, lubricants, antiblocking agents, nucleating agents, photolytic agents, biodegradation accelerators, antioxidants, ultraviolet stabilizers, antistatic agents, flame retardants, droplets, antibacterial agents Agents, deodorants, fillers, colorants or mixtures thereof.

Specific examples of the plasticizer include aliphatic dibasic acid esters, phthalic acid esters, hydroxy polycarboxylic acid esters, polyester plasticizers, fatty acid esters, and the like.
An epoxy plasticizer or a mixture thereof is exemplified.
The amount of these plasticizers varies depending on the application, but it is preferable to add them in the range of 3 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

Specific examples of the heat stabilizer include aliphatic carboxylate salts, specifically, sodium, calcium, aluminum, barium, magnesium, manganese, iron, zinc, lead, silver, and copper such as lactic acid and hydroxybutyric acid. Salts. The amount of addition is 0.1 to 100 parts by mass of the resin composition.
The range of 5 to 10 parts by mass is preferred.

Specific examples of the lubricant include fatty acid esters,
Hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester,
Aliphatic alcohol, polyhydric alcohol, polyglycol,
Polyglycerol, metal soap, modified silicone or a mixture thereof can be used. The amount of the lubricant is preferably 0.05 to 5 parts by mass based on 100 parts by mass of the resin composition.

Specific examples of the photodegradation promoter include benzophenones such as benzoins, benzoin alkyl ethers, benzophenone, 4,4-bis (dimethylamino) benzophenone and derivatives thereof, acetophenone,
Acetophenones such as α, α-diethoxyacetophenone and derivatives thereof, photoexciters such as quinones, thioxanthones, phthalocyanines, anatase-type titanium oxide, ethylene-carbon oxide copolymer, sensitization of aromatic ketones with metal salts And the like. These photolysis accelerators are
It is also possible to use a mixture of two or more.

Specific examples of the biodegradation accelerator include glycolic acid, lactic acid, citric acid, tartaric acid, malic acid, oxalic acid,
Examples thereof include organic acids such as malonic acid, succinic acid, succinic anhydride, and glutaric acid, and coconut shell activated carbon. It is also possible to use a mixture of two or more of these biodegradation promoters.

The resin composition of the present invention comprises a conventional mcl-P
It can be used for applications restricted by the thermal characteristics of HA and unusual-PHA, for example, mechanical parts, electric / electronic parts, various heat appliances, packaging containers, automobile parts and the like.

For example, a food packaging container can be formed by any one of foam extrusion molding, non-stretched extrusion sheet molding, biaxially stretched extrusion sheet molding, injection hollow molding, and injection molding. It is manufactured through the following molding process. For example, in the case of foam extrusion molding, a molten resin is first impregnated with a gas as a foaming agent before molding into a tray for fresh food, an instant noodle-shaped container having a dough-shaped or square shape, and a foamed sheet is formed. By subjecting the obtained foamed sheet to secondary molding into a desired shape, the food packaging container aimed at by the present invention can be obtained. In addition, a lunch box or its lid, a food package, and the like are formed once or not through a stretching step, and then subjected to secondary molding to obtain a desired food packaging material. On the other hand, food containers and cups obtained by injection hollow molding and injection molding are also included in the category of the food packaging container.

The cultivation of the microorganism of the present invention, the recovery of PHA from the microbial cells, and the resin composition and molded article are not limited to the above-mentioned methods.

Examples will be described below. In the following, “%” is based on mass, unless otherwise specified.

(Preparation Example 1) Pseudomonas chicoryi H45 strain was inoculated into 200 ml of M9 medium containing 0.5% yeast extract (manufactured by Oriental Yeast Kogyo Co., Ltd.).
The culture was shake-cultured at 125 strokes / min. 25 L of M9 medium containing 0.1% of 5-benzoylvaleric acid and 0.5% of D-glucose was prepared in a 50 L jar fermenter, and the inoculum was added thereto.
The culture was carried out with aeration and stirring at an aeration rate of 9.4 L / min. 48
After a time, the cells are collected by centrifugation and contain 0.1% of 5-benzoylvaleric acid and 0.5% of D-glucose.
The cells were resuspended in 25 L of an M9 medium not containing a nitrogen source (NH ₄ Cl), and cultured under aeration and stirring at 30 ° C., 70 rpm, and a flow rate of 9.4 L / min. After 48 hours, the cells were collected by centrifugation, washed once with cold methanol and freeze-dried.

The lyophilized pellet was suspended in 200 ml of chloroform and extracted by stirring at 60 ° C. for 20 hours. After the extract was filtered through a membrane filter having a pore size of 0.45 μm, the extract was concentrated using a rotary evaporator, the concentrate was reprecipitated in cold methanol, and only the precipitate was recovered and dried under vacuum to obtain 11.0 g of a resin composition. Obtained.

A part of this resin composition was taken, subjected to methanolysis according to a conventional method, and then subjected to gas chromatography-mass spectrometry (GC-MS, Shimadzu QP-5050, E
Analysis by Method I) to identify a methyl esterified product of a monomer unit constituting the resin composition. as a result,
The resin composition contained 81% of 3-hydroxy-5-benzoylvaleric acid unit and 1 unit of 3-hydroxydecanoic acid unit.
0%, 3-hydroxyoctanoic acid unit 5%, 3-hydroxyhexanoic acid unit 3%, 3-hydroxydodecanoic acid unit 1% (GC-MS, TI
C peak area ratio).

(Preparation Example 2) Pseudomonas chicory H45 strain was inoculated into 200 ml of M9 medium containing 0.5% yeast extract (manufactured by Oriental Yeast Co., Ltd.)
The culture was shake-cultured at 125 strokes / min. M9 medium containing 0.1% of 5-phenylvaleric acid and 0.5% of D-glucose in a 50 L jar fermenter
25 L was prepared, and the inoculum was added thereto.
The culture was carried out with aeration and stirring at 9.4 L / min. After 48 hours, the cells were collected by centrifugation, and resuspended in 25 L of a M9 medium containing 0.1% of 5-phenylvaleric acid and 0.5% of D-glucose without a nitrogen source (NH ₄ Cl). hand,
Further, aeration and agitation culture was performed at 30 ° C., 70 rpm, and aeration rate of 9.4 L / min. After 48 hours, the cells were collected by centrifugation, washed once with cold methanol and freeze-dried.

The lyophilized pellet was suspended in 200 ml of chloroform and extracted by stirring at 60 ° C. for 20 hours. After the extract was filtered through a membrane filter having a pore size of 0.45 μm, the extract was concentrated with a rotary evaporator, the concentrate was reprecipitated in cold methanol, and only the precipitate was recovered and dried under vacuum to obtain 15.0 g of a resin composition. I got

A part of this resin composition was subjected to methanolysis according to a conventional method, and then subjected to gas chromatography-mass spectrometry (GC-MS, Shimadzu QP-5050, E
Analysis by Method I) to identify a methyl esterified product of a monomer unit constituting the resin composition. as a result,
It was confirmed that the resin composition consisted of PHA containing only 3-hydroxy-5-phenylvaleric acid unit.

Example 1 Using the resin composition described in Preparation Example 1, a foamed extruded sheet was formed, and then subjected to secondary molding to prepare an instant noodle container 1. On the other hand, the resin composition described in Preparation Example 1 and a polystyrene polymer (Styrone 685, manufactured by Asahi Kasei Kogyo Co., Ltd.) were blended at a mass ratio of 50:50, and an instant noodle container 2 was prepared in the same manner. . The mass was 3.0 g per container.

(Comparative Example 1) A foamed extruded sheet was formed using the resin composition described in Preparation Example 2, and then subjected to secondary forming to prepare an instant noodle container 3. On the other hand, the resin composition described in Preparation Example 2 and a polystyrene-based polymer (Styrone 685, manufactured by Asahi Kasei Corporation) were blended at a mass ratio of 50:50, and an instant noodle container 4 was prepared in the same manner. . Further, an instant noodle container 5 was prepared in the same manner using the polystyrene-based polymer. The mass was 3.0 g per container.

(Example 2) Using the resin composition described in Preparation Example 1, a beverage container 1 was prepared by injection blow molding (injection blow molding). On the other hand, the resin composition described in Preparation Example 1 and a lactone-based polymer (polycaprolactone, manufactured by Daicel Chemical Industries, Ltd.) were mixed in a ratio of 50: 5.
The beverage was blended at a mass ratio of 0 to prepare a beverage container 2 in the same manner. The mass was 3.0 g per container.

(Comparative Example 2) Using the resin composition described in Preparation Example 2, a beverage container 3 was prepared by injection blow molding (injection blow molding). On the other hand, the resin composition described in Preparation Example 2 and a lactone-based polymer (polycaprolactone, manufactured by Daicel Chemical Industries, Ltd.) were mixed at a ratio of 50: 5.
Blend at a mass ratio of 0, and a beverage container 4 was prepared in the same manner. Further, using the lactone-based polymer, a beverage container 5 was prepared in the same manner. The mass was 3.0 g per container.

(Example 3) The instant noodle containers described in Example 1 or Comparative Example 1 were tested for the following evaluation items in order to compare and evaluate the quality of the instant noodle containers. The results are shown in Table 1. ○, suitable, △, usable, ×, unusable,-, not tested.

Biodegradability: It was buried in the soil for 6 months, and it was judged by whether or not it could be almost visually confirmed. In addition, × in the table
Means that biodegradation did not substantially occur in the first period. Quality as instant noodle container: Hardness, brittleness, cracks and leakage at 25 ° C (assuming storage) and 100 ° C (assuming hot water injection) were evaluated. Tg and Tm: Measurements were made with a differential scanning calorimeter (DSC; Pyris1, manufactured by PerkinElmer, temperature rise: 20 ° C./min).

[0071]

[Table 1]

(Example 4) The beverage containers described in Example 2 or Comparative Example 2 were tested for the following evaluation items in order to compare and evaluate the quality as a beverage container. The results are shown in Table 2. ○, suitable, △, usable, ×,
Unusable,-, not tested. Biodegradability: It was buried in soil for 6 months, and it was judged based on whether or not it could be almost visually confirmed. In the table, x means that biodegradation did not substantially occur in the previous period. Quality as instant noodle container: Hardness, brittleness, cracks and leakage at 25 ° C (assuming storage) and 100 ° C (assuming heat sterilization) were evaluated. Tg and Tm: Measurements were made with a differential scanning calorimeter (DSC; Pyris1, manufactured by PerkinElmer, temperature rise: 20 ° C./min).

[0073]

[Table 2]

In addition, in addition to the above-mentioned embodiment, at 40 ° C. and 140 ° C.
Although the molded article of the present invention was similarly tested under an environment of ℃,
It was confirmed that there was no problem in terms of hardness, brittleness, cracks and leakage, and that biodegradability was excellent.

[0075]

Industrial Applicability According to the present invention, a resin composition, molded article, and a resin composition having at least biodegradability, heat resistance and mechanical properties containing at least a polyhydroxyalkanoate having a 3-hydroxy-5-benzoylvaleric acid unit are provided. A manufacturing method is provided.

The resin composition of the present invention can be used for, for example, various kinds of heat appliances, containers, automobile parts and the like, and more specifically, for example, for food containers, beverage containers, shampoo containers and rinse containers. It can be used for containers such as toiletry containers, medicine containers, and cosmetic containers.

Continuing on the front page (72) Inventor Kei Takashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Etsuko Sugawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tetsuya Yano 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 3E033 BA16 BA17 BA18 BA19 BA21 BA22 BA30 BB01 CA06 CA07 CA20 4F071 AA20 AA22 AA43 AA46 AA53 AA54 AC04 AC05 AC07 AC09 AC10 AC12 AC13 AE04 AE05 AE11 AE22 AF52 AH04 AH05 BA01 BB03 BB06 BC01 4J002 BB12X BC03X CF00X CF06X CF18W CF18X CF19X CK02X CL00X DE136 EE026 EF056 EG026 EG036 EG046 EH036 EH046 EH146 EP016 EV346 FD016 FD026 FD056 FD066 FD076 FD096 FD106 FD136 FD176 FD206 4J029 AA02 AB07 AC01 EA05 EB01 ED01

Claims (16)

[Claims] 1. A resin containing at least a resin (A) comprising a polyhydroxyalkanoate having a monomer unit represented by the following chemical formula [1] in a ratio of 1 to 99 mol% and a thermoplastic resin (B): Composition. Embedded image 2. The thermoplastic resin (B) is selected from the group consisting of polyester resin, polystyrene resin, polypropylene resin, polyethylene terephthalate resin, polyurethane resin, polyvinyl resin, and polyamide resin. The resin composition according to claim 1, comprising: 3. The resin composition according to claim 1, comprising 1 to 99% by mass of the thermoplastic resin (B) based on the resin (A). 4. The resin composition according to claim 2, wherein the polystyrene resin is polystyrene. 5. The resin composition according to claim 2, wherein the polyester resin is poly-ε-caprolactone or polylactic acid. 6. The resin composition according to claim 1, further comprising a resin additive. 7. The resin additive may be a plasticizer, a heat stabilizer, a lubricant,
Antiblocking agent, nucleating agent, photolytic agent, biodegradation accelerator,
The resin according to claim 6, wherein the resin is at least one selected from the group consisting of an antioxidant, an ultraviolet stabilizer, an antistatic agent, a flame retardant, a dropping agent, an antibacterial agent, a deodorant, a filler, and a colorant. Composition. 8. A molded article molded from the resin composition according to any one of claims 1 to 7. 9. A molded article molded from a polyhydroxyalkanoate having at least a monomer unit represented by the following chemical formula [1] in a proportion of 1 to 99 mol%. Embedded image 10. The container according to claim 8, which is a container.
The molded article according to the above. 11. The molded article according to claim 10, which is at least one selected from the group consisting of a food container, a beverage container, a toiletry container, a medicine container, and a cosmetic container. 12. The molded article according to claim 8, which is biodegradable. 13. The molded product is used in a temperature environment of 40 ° C. or more and 140 ° C. or less.
The molded article according to any one of claims 1 to 12. 14. A method for producing a molded product, wherein the resin composition according to claim 1 is molded by heating. 15. A method for producing a molded article, comprising heating and molding a polyhydroxyalkanoate having at least a monomer unit represented by the following chemical formula [1] in a proportion of 1 to 99 mol%. Embedded image 16. The heat-molding step is at least one selected from the group consisting of foam extrusion molding, non-stretch extrusion sheet molding, biaxial stretching extrusion sheet molding, injection hollow molding, and injection molding. A method for producing a molded article according to claim 14 or 15.