JP7279091B2 - Container or flat plate molding, resin composition and method for producing resin pellets thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition and a method for producing a molded container or flat plate, and a resin pellet using the resin composition. In particular, it relates to a molding resin composition having biodegradability.

Conventionally, synthetic plastics such as PP, PE, PET, PC, PMMA, PS, COP, and COC have been used as resin materials for molding. At present, these chemically synthesized plastics have the problems of carbon dioxide generation and environmental pollution, but these problems are almost ignored when they are used.

Under these circumstances, resin compositions made from components of natural materials such as plants have been developed so as not to generate carbon dioxide during production. Also, a biodegradable resin composition has been developed that is degraded into low-molecular-weight compounds that do not adversely affect the environment through the involvement of microorganisms. PLA (polylactic acid) is an example of a biodegradable resin composition that is a plant-derived material. Patent Document 1 discloses a molded product using polylactic acid.

JP 2016-179694 A

However, since PLA is made from corn or sugar cane, it emits little CO ₂ , but has the problem of requiring many production processes and high production costs. Also, PLA is a material that does not biodegrade unless it is at a temperature of 50° C. or higher. Therefore, no biodegradability is obtained in the discarded environment. In addition, there is a problem that moldings such as beverage containers such as cups, which have poor heat resistance, are deformed when hot water is poured into them. In addition, it is weak in strength, and if the molded product is dropped, bent, or pushed, cracks, scratches, or breakage may occur. Furthermore, when it is attempted to produce a molded product by injection molding, PLA has poor fluidity, which results in a long cycle time for injection molding, and problems in mass production of molded products, such as easy occurrence of injection molding defects. In other words, conventional PLA has problems in terms of heat resistance, hardness, cost and biodegradability.

As a result of intensive research by the present inventors, by applying an amorphous resin material component extracted from plant-derived wood, a resin composition for molding that is excellent in terms of heat resistance, hardness, cost, and biodegradability has been developed. offer. Also provided is a molding method using this resin composition.

The resin composition of the present embodiment is a plant-derived first resin represented by the following structural formula (Formula 1). Chemical 1

さらに第２樹脂として、ポリカーボネート（ＰＣ）、環状オレフィンポリマー（ＣＯＰ）、環状オレフィンコポリマー（ＣＯＣ）、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリスチレン（ＰＳ）、ＡＢＳ樹脂（ＡＢＳ）、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリ酢酸ビニル（ＰＶＡＣ）、ポリメチルペンテン（ＰＭＰ）、ポリブテン（ＰＢ）、ヒドロキシ安息香酸ポリエステル（ＨＢＰ）、ポリエーテルイミド（ＰＥＩ）、ポリアセタール（ＰＯＭ）、ポリフェニレンエーテル（ＰＰＥ）、ポリフェニレンオキシド（ＰＰＯ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリウレタン（ＰＵＲ）、アイオノマー樹脂（ＩＯ）、フッ素樹脂（ＦＲ）、ポリ四フッ化エチレン（ＰＴＦＥ）、ポリシクロへキシレンジメチレンテレフタレート（ＰＣＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリアリレート（ＰＡＲ）、ポリアクリロニトリル（ＰＡＮ）、ポリアリルサルホン（ＰＡＳＦ）、ポリアミド（ＰＡ）、ポリビニルアルコール（ＰＶＡ）、ポリメタクリルスチレン（ＭＳ）、ブタジエン樹脂（ＢＤＲ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエステルカーボネート（ＰＰＣ）、ポリブチレンサクシネート（ＰＢＳ）、ノルボルネン樹脂（ＮＢ）、ポリアミド（ナイロン）（ＰＡ）、テフロン（登録商標）、繊維強化プラスチック（ＦＲＰ）、ポリヒドロキシアルカン酸（ＰＨＡ）、ポリヒドロキシ酪酸（ＰＨＢ）、ヒドロキシ酪酸・ヒドロキシヘキサン酸共重合体（ＰＨＢＨ）、アセチルセルロース（ＣＡ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリスルホン（ＰＳＦ）、ポリエーテルスルホン（ＰＥＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、液晶ポリマー（ＬＣＰ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、シリコン樹脂（ＳＩ）、エポキシ樹脂（ＥＰ）及びポリ乳酸（ＰＬＡ）のいずれかでもよい。またはそれらの複数でもよい。 In addition, a second resin represented by the following structural formula (Chemical Formula 2) may also be included.

Furthermore, as the second resin, polycarbonate (PC), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PS), ABS resin (ABS ), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl acetate (PVAC), polymethylpentene (PMP), polybutene (PB), hydroxybenzoic acid polyester (HBP), polyetherimide (PEI), Polyacetal (POM), polyphenylene ether (PPE), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyurethane (PUR), ionomer resin (IO), fluorine resin (FR), polytetrafluoroethylene (PTFE), polycyclo Hexylene dimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polyarylate (PAR), polyacrylonitrile (PAN), polyallylsulfone (PASF), polyamide (PA), polyvinyl alcohol (PVA), polymethacrylstyrene (MS), butadiene resin (BDR), polybutylene terephthalate (PBT), polyester carbonate (PPC), polybutylene succinate (PBS), norbornene resin (NB), polyamide (nylon) (PA), Teflon (registered trademark) , fiber reinforced plastic (FRP), polyhydroxyalkanoic acid (PHA), polyhydroxybutyric acid (PHB), hydroxybutyric acid/hydroxyhexanoic acid copolymer (PHBH), acetylcellulose (CA), polyimide (PI), polyamideimide ( PAI), polysulfone (PSF), polyethersulfone (PES), polyetheretherketone (PEEK), liquid crystal polymer (LCP), polychlorotrifluoroethylene (PCTFE), silicone resin (SI), epoxy resin (EP) and Either polylactic acid (PLA) may be used. or a plurality of them.

In addition, wood powder or wood pellets made by freezing and pulverizing trees, bamboo or grass into powder or pellet form, bamboo powder or bamboo pellets, grass powder or grass pellets, or paper made by freezing and pulverizing paper into powder The powder may be kneaded with the first resin, or may be kneaded with the first resin and the second resin. Since these are very inexpensive, it is possible to reduce the cost of the kneaded resin pellets themselves, and a reduction in price can be expected. If wood powder, wood pellets, bamboo powder, bamboo pellets, grass powder, grass pellets, paper powder, or paper pellets are mixed with the second resin as they are, the heat resistance, strength, and fluidity will deteriorate, but they will be kneaded with the first resin. As a result, heat resistance, strength and fluidity are improved, and biodegradability is also obtained.

The resin composition may contain a second resin represented by the following structural formula (Chemical Formula 3) as a second resin. Chemical 3

The resin composition preferably contains 10 to 90% by weight of the first resin and 90 to 10% by weight of the second resin. One or more of R1 or R2 of the first resin is an acetyl group, the second resin contains any one or more of polymethyl methacrylate, polycarbonate, polyethylene, polypropylene or polyethylene terephthalate, and the first resin is 10 to 90% by weight. , the second resin is preferably 90 to 10% by weight.

The molding method of the resin composition of the present embodiment comprises a step of charging the above-described resin composition in a solidified state into a resin injection section, and a step of heating and compressing the resin composition in the resin injection section to liquefy it. a step of pressurizing the liquefied resin composition and injecting it from the resin injection part into the mold part; cooling and solidifying the resin composition in the mold part; and a step of taking out. Moreover, it is preferable to include a step of introducing a gas into the liquefied resin composition and diffusing the gas into the resin composition.

The resin composition of the present invention is excellent in heat resistance, hardness, cost and biodegradability.

1 is a conceptual diagram of molding an injection-molded product using an injection molding machine 10 and a mold 50 (without gas); FIG. 1 is a conceptual diagram of molding an injection-molded product using an injection molding machine 10 and a mold 50 (with gas); FIG.

<Hemicellulose, hemicellulose polymer, and hemicellulose polymer>
The resin composition in this embodiment contains a plant-derived resin component. This resin component is one of the components that mainly constitute wood. Wood is primarily composed of three components: cellulose, hemicellulose, and lignin. Hemicellulose is amorphous and very uniform, and the liquid after melting has good fluidity and is suitable as an injection molding material. Cellulose is highly crystalline and fibrous, and is not suitable as a main component of injection molding materials. Lignin is also highly crystalline and poor in fluidity, so it is not suitable as a main component of injection molding materials. Hemicellulose is the only amorphous material that can flow uniformly inside the cylinder in injection molding when liquefied.

Hemicellulose includes complex polysaccharides such as mannan, glucan, xylan, and xyloglucan. Any of these can be used in this embodiment. In addition, the hemicellulose may contain a small amount of cellulose or a small amount of lignin. Among the hemicelluloses preferably xylan is used. The molecular weight (weight-average molecular weight Mw) of hemicellulose is generally 1,000 to 100,000, but when the molecular weight is 30,000 to 100,000, the molded product obtained by injection molding has good strength.

Hemicellulose has good biodegradability. Hemicellulose has a faster biodegradation rate than cellulose and lignin, and is also biodegradable at low temperatures, eg, 5 degrees Celsius to high temperatures. Even at room temperature, hemicellulose is decomposed by microorganisms and becomes water and carbon dioxide after 3 months. When buried in soil, hemicellulose is degraded by microorganisms in the soil. Even in seawater, hemicellulose is decomposed by microorganisms. Hemicellulose is an environmentally friendly material.

Since hemicellulose is a component of wood, chemical synthesis itself is unnecessary. That is, the plant-derived tree consumes carbon dioxide through photosynthesis without generating carbon dioxide associated with chemical synthesis of raw materials.

Hemicellulose has the following structural formula. Molecular structures containing the following structures can be used in this embodiment. Chemical 3

R5 and R6 represent substituents. R5 and R6 are hydrogen, nitrogen, alkyl group, acetyl group, hydroxy group, acyl group, aldehyde group, amino group, imino group, aryl group, phosphonyl group, propenyl group, propanyl group, acetonyl group, carbonyl group, Carboxyl group, cyano group, azo group, azide group, thiol group, sulfo group, nitro group, vinyl group, allyl group, cycloalkyl group, phenyl group, naphthyl group, araalkyl group, benzyl group, Schiff group, alkylene group, amyl group, acetamidomethyl group, adamantyl group, adamantyloxycarbonyl group, allyloxycarbonyl group, tert-butoxycarbonyl group, benzyloxymethyl group, biphenylisopropyloxycarbonyl group, benzoyl group, benzyloxycarbonyl group, cyanoethyl group, cyclo xyl group, carboxymethyl group, cyclopentadienyl group, pentamethylcyclopentadienyl group, cyclohexyl group, glucose, hexyl group, isobutyl group, isopropyl group, mesityl group, trimethylphenyl group, methoxymethyl group, mesitylene sulfonyl group, mesyl group, nosyl group, octadecylsilyl group, pivaloyl group, methoxybenzyl group, methoxyphenyl group, propyl group, ethoxymethyl group, trimethylsilyl group, trimethylsilylethoxymethyl group, cyamyl group, tert-butyl group, tert-butyl group dimethylsilyl group, tert-butyldiphenylsilyl group, triethylsilyl group, tetrahydropyranyl group, triisopropylsilyl group, tolyl group, tosyl group, triisopropylbenzenesulfonyl group, trityl group, trichloroethoxycarbonyl group, benzyloxycarbonyl group, methylene group, valeryl group, methoxy group, acetamide group, trimethylammonium group, diazo group, hydrocarbon group and the like, but not limited thereto. Substituents that include them in the structure may also be used. Fluorine, bromine, chlorine, iodine, etc., or substituents containing these in the structure may also be used. Further, it may be an ionizable substituent such as a cation or anion that forms an ionic liquid structure, or a substituent containing them in the structure. The substituent for R5 and the substituent for R6 may be different.

By including this basic structure, biodegradability is obtained, and heat resistance, strength, fluidity, and transparency are obtained. It can be injection molded, and the molding obtained by injection molding is biodegradable and has good heat resistance, strength, fluidity and transparency. Note that n is an integer of 2 or more. As will be described later, R5 and R6 are hydrogen when the hemicellulose component is extracted from wood chips. When R5 and R6 are hydrogen, it is commonly called "hemicellulose". Hemicellulose itself, in which R5 and R6 are hydrogen, is highly hydrophilic and therefore easily absorbs moisture. If the water absorbency is high, depending on the intended use of the molded article, the dimensions, volume, and weight tend to change over time, which may be undesirable. In addition, depending on the use of the molded product, the strength, transparency or heat resistance of the molded product may deteriorate. In order to solve such a problem due to water absorption, it is preferable to change R in the hemicellulose molecule to a substituent such as the above-described substituent, acetyl group, acetonyl group, ionizable substituent. Those substituted with various substituents other than hydrogen are called hemicellulose derivatives. In typical hemicellulose derivatives, R5 and R6 are acetyl groups.

Further, the hemicellulose polymer, which is the first resin of the present embodiment, has a molecular structure in which other resin is bound to hemicellulose itself or a hemicellulose derivative. A hemicellulose polymer has the following structural formula. Molecular structures containing the following structures can be used in this embodiment. Chemical 1

R1, R2 and R3 represent substituents. R1, R2 and R3 are hydrogen, nitrogen, alkyl group, acetyl group, hydroxy group, acyl group, aldehyde group, amino group, imino group, aryl group, phosphonyl group, propenyl group, propanyl group, acetonyl group, carbonyl group, carboxyl group, cyano group, azo group, azide group, thiol group, sulfo group, nitro group, vinyl group, allyl group, cycloalkyl group, phenyl group, naphthyl group, araalkyl group, benzyl group, Schiff group, alkylene group , amyl group, acetamidomethyl group, adamantyl group, adamantyloxycarbonyl group, allyloxycarbonyl group, tert-butoxycarbonyl group, benzyloxymethyl group, biphenylisopropyloxycarbonyl group, benzoyl group, benzyloxycarbonyl group, cyanoethyl group, cyclohexyl group, carboxymethyl group, cyclopentadienyl group, pentamethylcyclopentadienyl group, cyclohexyl group, glucose, hexyl group, isobutyl group, isopropyl group, mesityl group, trimethylphenyl group, methoxymethyl group , mesitylenesulfonyl group, mesyl group, nosyl group, octadecylsilyl group, pivaloyl group, methoxybenzyl group, methoxyphenyl group, propyl group, ethoxymethyl group, trimethylsilyl group, trimethylsilylethoxymethyl group, cyamyl group, tert-butyl group, tert -butyldimethylsilyl group, tert-butyldiphenylsilyl group, triethylsilyl group, tetrahydropyranyl group, triisopropylsilyl group, tolyl group, tosyl group, triisopropylbenzenesulfonyl group, trityl group, trichloroethoxycarbonyl group, benzyloxycarbonyl groups, methylene groups, valeryl groups, methoxy groups, acetamide groups, trimethylammonium groups, diazo groups, hydrocarbon groups, and the like, but are not limited to these. Substituents that include them in the structure may also be used. Fluorine, bromine, chlorine, iodine, etc., or substituents containing these in the structure may also be used. Further, it may be an ionizable substituent such as a cation or anion that forms an ionic liquid structure, or a substituent containing them in the structure. The substituent of R1 and the substituent of R2 may be different.

A and Q each independently represent a single bond or a linking group, and when Q is a linking group, Q includes a group containing an alkylene group, -O-, -NH2-, a carbonyl group, and the like. When A is a linking group, A includes groups including an alkylene group, -O-, -C(=O)O- and the like. Note that n is an integer of 2 or more, and m is an integer of 1 or more. When m is 2 or more, R3 in the above structural formula may be the same or different, Q may be the same or different, and A and Q may be the same or different. The molecular weight (weight average molecular weight Mw) of the hemicellulose polymer is 1,000 to 10,000,000. Good.

<Preparation of hemicellulose, hemicellulose derivative, and hemicellulose monomer>
Small pieces of wood are called wood chips. The wood chips are heated in an aqueous solution containing butanol. The liquid then separates into a phase of butanol and lignin and a phase of water and hemicellulose. Cellulose precipitates as a solid. A hemicellulose powder can be obtained by removing water from the water and hemicellulose phases. This powdered hemicellulose has a structural formula in which R5 and R6 are hydrogen. In this case, it is easy to take in moisture due to its high hydrophilicity. If the water absorbency is high, the dimension, volume and weight of the molded product tend to change with time, and the strength, transparency and heat resistance of the molded product itself may deteriorate.

Therefore, the hemicellulose itself undergoes an acetylation reaction to change the hydrogens of R5 and R6 in the structural formula to acetyl groups, thereby producing a hemicellulose derivative. In addition to the acetyl group, these hemicellulose derivatives can be prepared by chemically changing R1 and R2 in the structural formula to substituents such as acetonyl group, propenyl group and carboxyl group. Preparation of this hemicellulose derivative was carried out by a conventional sugar derivative preparation technique. This sugar derivative preparation technology is proposed by Yamagata University, Nippon Kayaku Co., Ltd., Horiba Estech Co., Ltd., Kobe Natural Chemicals Co., Ltd., or Hayashibara Co., Ltd., respectively.

Hemicellulose itself and hemicellulose derivatives can be subjected to methacrylate or acrylate chemistry. By applying this chemical reaction, monomers such as hemicellulose methacrylate and hemicellulose acrylate are obtained. This monomer has a molecular structure in which hemicellulose itself or a hemicellulose derivative is attached with a methacryl group or an acryloyl group. In particular, it is not limited to methacrylates and acrylates. This is called a hemicellulose monomer. A hemicellulose polymer is obtained by polymerizing a hemicellulose monomer into a resin. Hemicellulose polymers can have the properties of a variety of resinous materials. Polyhemicellulose methacrylate obtained by polymerizing hemicellulose methacrylate has the properties of both hemicellulose and polymethyl methacrylate (PMMA), making it a biodegradable plastic with high transparency and good strength. . For methacrylate and acrylate, techniques for synthesizing methacrylate monomers and acrylate monomers, which are raw material monomers for conventional UV-curable resins, can be used. Preparation of the hemicellulose monomer in this embodiment was carried out using conventional monomer synthesis technology owned by Kobe Natural Chemicals Co., Ltd., Nippon Kayaku Co., Ltd., or Osaka Organic Chemical Industry Co., Ltd. For the polymerization reaction of the hemicellulose monomer, polymerization techniques such as radical polymerization, anionic polymerization, living radical polymerization, and living anionic polymerization, which are used for polymerization of conventional polymers and polymerization of block copolymers, can be used. Conventional techniques were also used to prepare the hemicellulose polymer in this embodiment. This polymerization reaction was carried out by using the polymer source polymerization technology proposed by Horiba Estec Co., Ltd., Arkema Co., Ltd. or Nippon Kayaku Co., Ltd.

またヘミセルロース自体及びヘミセルロース誘導体は、以下のように、アクリレート化され（以下の式中、Ｒがヘミセルロース又は及びヘミセルロース誘導体）、このヘミセルロースアクリレートを重合することでポリヘミセルロースアクリレートが得られる。

Hemicellulose itself and a hemicellulose derivative are methacrylated as follows (wherein R is hemicellulose or a hemicellulose derivative), and polyhemicellulose methacrylate is obtained by polymerizing this hemicellulose methacrylate.

Hemicellulose itself and a hemicellulose derivative are acrylated as follows (wherein R is hemicellulose or a hemicellulose derivative), and polyhemicellulose acrylate is obtained by polymerizing this hemicellulose acrylate.

<Resin composition for molding>
The first resin, the hemicellulose polymer, by itself becomes an injection moldable resin composition and resin pellets for injection molding. A first resin, a hemicellulose polymer, can be mixed with a second resin. In order to obtain an injection-moldable resin composition, the powder of the hemicellulose polymer and the powder of the second resin, pellets of the second resin, or the like may be mixed and fed into an extrusion kneading device.

The extrusion kneading device melt-kneads the first resin and the second resin, and the kneaded resin composition is extruded in a cylindrical shape from a nozzle of the extrusion kneading device. By cutting the cylindrical resin with a pelletizer, resin pellets of the resin composition are produced. Resin pellets are resin strips with a diameter of 0.2-3 mm and a length of 0.2-5 mm.

The second resin is polycarbonate (PC), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PS), polylactic acid (PLA). etc., but not limited to these resins.

The second resin can also be mixed with a resin having the following structural formula. An example includes polymethyl methacrylate (PMMA, acrylic). chemical 2

Here, R4 represents a substituent and is the same as the substituent of R1, R2 or R3.
A represents a single bond, and Q represents a single bond or a linking group, which are the same as A and Q described above.
n is an integer of 2 or more.
The molecular weight (weight average molecular weight Mw) of the second resin is 1,000 to 10,000,000. is good.

Resin pellets of a resin composition composed of the first resin and the second resin are put into an injection molding apparatus, and moldings having various shapes can be obtained according to molding dies. When a molded article using the resin composition of the present embodiment is placed in soil or seawater, the first resin in the resin composition is mixed with the second resin at the molecular level. When the first resin is biodegraded by microorganisms or the like, the second resin itself is also degraded at the molecular level, and biodegradation progresses. That is, the first resin plays a role in imparting biodegradability to the second resin itself. It was completely unexpected that the first resin would play a role in imparting biodegradability to the second resin as well. This is something that a person skilled in the art of plastics, bioplastics, and biodegradable plastics cannot easily guess, and has been demonstrated in the experiments of the examples of this invention. It is thought that the molecules of the second resin themselves biodegrade more easily when the first resin biodegrades because the molecules of the first resin enter between the molecules of the second resin.

It was also found that when the first resin and the second resin are mixed at the molecular level, heat resistance, strength, fluidity, transferability, and optical properties are improved as compared to the first resin alone. This was totally unexpected. This is something that a person skilled in the art of plastics, bioplastics, and biodegradable plastics cannot easily guess, and has been demonstrated in the experiments of the examples of this invention. This is because the molecules of the first resin and the molecules of the second resin are intricately entwined, so that the material is stable even at high temperatures, has improved strength, and is optically uniform. It is thought that the index and birefringence were improved. Furthermore, it is thought that the first resin also functions as a solvent for the second resin when melted, so that the viscosity is lowered, the fluidity is improved, and the transferability is improved.

この化学式４は化学式１の構造式でＲ３がＣＨ３（メチル基）でありＱがメチレン基でありＡが－Ｃ（＝Ｏ）Ｏ－を含む構造である。ｍは１以上の整数である。 <<Molded product by optical molding>>
<First Embodiment>
Polyhemicellulose methacrylate was used as the hemicellulose polymer. The molecular structure of polyhemicellulose methacrylate is shown below. Chemical 4

This chemical formula 4 is a structural formula of chemical formula 1, wherein R3 is CH3 (methyl group), Q is a methylene group, and A contains -C(=O)O-. m is an integer of 1 or more.

In the first embodiment, as the first resin, resin pellets (Example 10) of a resin composition of 100% by weight of polyhemicellulose methacrylate using a hemicellulose derivative having the structural formula of chemical formula 4 and R1 and R2 being acetyl groups are used. Created. Similarly, as the first resin, resin pellets of a resin composition containing 100% by weight of polyhemicellulose methacrylate using a hemicellulose derivative in which R1 and R2 are acetonyl groups (Example 60), and a hemicellulose derivative in which R1 and R2 are carboxyl groups. Resin pellets (Example 110) of a resin composition of 100% by weight polyhemicellulose methacrylate using These polyhemicellulose methacrylates have the structural formula of Chemical Formula 4. The molecular weight (weight average molecular weight Mw) of these polyhemicellulose methacrylates is 100,000. Using these resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups and flat plate samples were produced by photoforming. As a comparative example, PLA (polylactic acid) (the molecular weight of PLA ((weight average molecular weight Mw) is 100,000)) 100% by weight dumbbell test piece, strip test piece, disk substrate, cup and flat plate sample products. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated.The evaluation results are shown in Table 1.

A sample product of 100% by weight of polyhemicellulose methacrylate exceeded target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradation rate. Moreover, the sample product of 100% by weight of polyhemicellulose methacrylate is superior to the sample product of 100% by weight of PLA (polylactic acid) in all evaluation items. There was no significant difference between polyhemicellulose methacrylate with acetyl groups, polyhemicellulose methacrylate with acetonyl groups, and polyhemicellulose methacrylate with carboxyl groups.

For comparison with Examples 10, 60, and 110 in the fifth to tenth embodiments described later, polyhemicellulose methacrylate having an acetyl group, which was formed by photoforming, was used in Example 10, acetonyl The base polyhemicellulose methacrylate is referred to as Example 60, and the carboxyl base polyhemicellulose methacrylate as Example 110.

<Second Embodiment Acetyl Group>
(PMMA)
Next, polyhemicellulose methacrylate having an acetyl group, which is a hemicellulose polymer, and PMMA were melt-kneaded in an extrusion kneader at different ratios to prepare 3 kg of resin pellets of these resin compositions. The molecular weight (weight average molecular weight Mw) of PMMA is 120,000.

In Example 1, resin pellets were prepared from a resin composition containing 10% by weight of polyhemicellulose methacrylate and 90% by weight of PMMA.
In Example 2, resin pellets were prepared from a resin composition containing 20% by weight of polyhemicellulose methacrylate and 80% by weight of PMMA.
In Example 3, resin pellets were prepared from a resin composition containing 30% by weight of polyhemicellulose methacrylate and 70% by weight of PMMA.
In Example 4, resin pellets were prepared from a resin composition containing 40% by weight of polyhemicellulose methacrylate and 60% by weight of PMMA.
In Example 5, resin pellets were prepared from a resin composition containing 50% by weight of polyhemicellulose methacrylate and 50% by weight of PMMA.
In Example 6, resin pellets were prepared from a resin composition containing 60% by weight of polyhemicellulose methacrylate and 40% by weight of PMMA.
In Example 7, resin pellets were prepared from a resin composition containing 70% by weight of polyhemicellulose methacrylate and 30% by weight of PMMA.
In Example 8, resin pellets were prepared from a resin composition containing 80% by weight of polyhemicellulose methacrylate and 20% by weight of PMMA.
In Example 9, resin pellets were prepared from a resin composition containing 90% by weight of polyhemicellulose methacrylate and 10% by weight of PMMA.

Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 2A. Although Table 2A does not list the measurement method, it is the same as the measurement method in Table 1. The same applies to Tables 2B to 4E below.

When the second resin is PMMA, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the PMMA ratio. Exceeded the target value. Varying from 10% to 90% by weight of PMMA (90% to 10% by weight of hemicellulose polymer) has advantages in each resin composition. For example, a resin composition containing 60% to 50% by weight of PMMA is preferable in consideration of heat resistance temperature, and a resin composition containing 40% to 10% by weight of PMMA is preferable in consideration of tensile strength.

Similarly, a combination of polyhemicellulose methacrylate having an acetyl group, which is a hemicellulose polymer, and PC, PE, PP, and PET in different proportions, is melt-kneaded by an extrusion kneader to produce these resin compositions. 3 kg of resin pellets were prepared. The molecular weight (weight average molecular weight Mw) of PC is 140,000, PE is 160,000, PP is 200,000, and PET is 300,000.

(PC)
In Examples 11 to 19, PC was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 2B.

When the second resin is PC, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the proportion of PC. Exceeded the target value. In particular, a resin composition containing 60% to 30% by weight of PC (40% to 70% by weight of hemicellulose polymer) has excellent heat resistance temperature, tensile strength, bending strength, and the like. A resin composition containing 10% by weight to 90% by weight of PC gives good results in most evaluation items even when compared with a resin composition containing 100% by weight of polyhemicellulose methacrylate (Example 10).

(PE)
In Examples 21 to 29, PE was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 2C.

When the second resin is PE, the total light transmittance and birefringence phase difference are poor, so it cannot be applied to optical parts or moldings that require transparency. However, other evaluation items exceeded the target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, impurity concentration, and biodegradation rate. Varying from 10 wt% to 90 wt% PE (90 wt% to 10 wt% hemicellulose polymer) each has its advantages. Even when compared with 100% by weight polyhemicellulose methacrylate, the results are good in many evaluation items.

(PP)
In Examples 31 to 39, PP was changed from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 2D.

When the second resin is PP, the total light transmittance and birefringence phase difference are poor, so it cannot be applied to optical parts or moldings that require transparency. However, other evaluation items exceeded the target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, impurity concentration, and biodegradation rate. Even if the PP is varied from 10% to 90% by weight (90% to 10% by weight of the hemicellulose polymer), each resin composition has advantages. Even when compared with 100% by weight of polyhemicellulose methacrylate, the evaluation items of heat resistance temperature, tensile strength, bending strength and fluidity are good.

(PET)
In Examples 41 to 49, PET was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 2E.

When the second resin is PET, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the PET ratio. Exceeded the target value. In particular, a resin composition containing 60% to 30% by weight of PET (40% to 70% by weight of hemicellulose polymer) has good heat resistance temperature, tensile strength, bending strength, and the like. A resin composition containing 10% by weight to 90% by weight of PET shows good results in most evaluation items even when compared with a resin composition containing 100% by weight of polyhemicellulose methacrylate (Example 10).

<Third Embodiment Acetonyl Group>
(PMMA)
Next, polyhemicellulose methacrylate having an acetonyl group, which is a hemicellulose polymer, and PMMA were melt-kneaded in an extrusion kneader at different ratios to prepare 3 kg of resin pellets of these resin compositions. The molecular weight (weight average molecular weight Mw) of PMMA is 120,000.

In Examples 51 to 59, PMMA was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 3A.

When the second resin is PMMA, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the PMMA ratio. Exceeded the target value. Varying from 10% to 90% by weight of PMMA (90% to 10% by weight of hemicellulose polymer) has advantages in each resin composition. For example, a resin composition containing 60% to 50% by weight of PMMA is preferable in consideration of heat resistance temperature, and a resin composition containing 40% to 10% by weight of PMMA is preferable in consideration of tensile strength. Even when compared with 100% by weight polyhemicellulose methacrylate, the results are good in many evaluation items.

Similarly, a combination of polyhemicellulose methacrylate having an acetonyl group, which is a hemicellulose polymer, and PC, PE, PP, and PET are melt-kneaded in an extrusion kneader at different ratios to produce these resin compositions. 3 kg of resin pellets were prepared. The molecular weight (weight average molecular weight Mw) of PC is 140,000, PE is 160,000, PP is 200,000, and PET is 300,000.

(PC)
In Examples 61 to 69, PC was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 3B.

When the second resin is PC, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the proportion of PC. Exceeded the target value. In particular, a resin composition containing 60% to 30% by weight of PC (40% to 70% by weight of hemicellulose polymer) has excellent heat resistance temperature, tensile strength, bending strength, and the like. A resin composition containing 10% by weight to 90% by weight of PC gives good results in most evaluation items even when compared with a resin composition containing 100% by weight of polyhemicellulose methacrylate (Example 60).

(PE)
In Examples 71 to 79, PE was changed from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 3C.

When the second resin is PE, the total light transmittance and birefringence phase difference are poor, so it cannot be applied to optical parts or moldings that require transparency. However, other evaluation items exceeded the target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, impurity concentration, and biodegradation rate. Varying from 10 wt% to 90 wt% PE (90 wt% to 10 wt% hemicellulose polymer) each has its advantages. Even when compared with 100% by weight polyhemicellulose methacrylate, the results are good in many evaluation items.

(PP)
In Examples 81 to 89, PP was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 3D.

When the second resin is PP, the total light transmittance and birefringence phase difference are poor, so it cannot be applied to optical parts or moldings that require transparency. However, other evaluation items exceeded the target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, impurity concentration, and biodegradation rate. Even if the PP is varied from 10% to 90% by weight (90% to 10% by weight of the hemicellulose polymer), each resin composition has advantages. Even when compared with 100% by weight of polyhemicellulose methacrylate, the evaluation items of heat resistance temperature, tensile strength, bending strength and fluidity are good.

(PET)
In Examples 91 to 99, PET was changed from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 3E.

When the second resin is PET, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the PET ratio. Exceeded the target value. In particular, a resin composition containing 60% to 30% by weight of PET (40% to 70% by weight of hemicellulose polymer) has good heat resistance temperature, tensile strength, bending strength, and the like. A resin composition containing 10% by weight to 90% by weight of PET shows good results in most evaluation items even when compared with a resin composition containing 100% by weight of polyhemicellulose methacrylate (Example 60).

<Fourth Embodiment Carboxyl Group>
(PMMA)
Next, polyhemicellulose methacrylate having a carboxyl group, which is a hemicellulose polymer, and PMMA were melt-kneaded in an extrusion kneader at different ratios to prepare 3 kg of resin pellets of these resin compositions. The molecular weight (weight average molecular weight Mw) of PMMA is 120,000.

In Examples 101 to 109, PMMA was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 4A.

Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 4A.

When the second resin is PMMA, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the PMMA ratio. Exceeded the target value. Varying from 10% to 90% by weight of PMMA (90% to 10% by weight of hemicellulose polymer) has advantages in each resin composition. For example, a resin composition containing 60% to 50% by weight of PMMA is preferable in consideration of heat resistance temperature, and a resin composition containing 40% to 10% by weight of PMMA is preferable in consideration of tensile strength. Even when compared with 100% by weight polyhemicellulose methacrylate, the results are good in many evaluation items.

Similarly, a combination of polyhemicellulose methacrylate having a carboxyl group, which is a hemicellulose polymer, and PC, PE, PP, and PET in different proportions, is melt-kneaded by an extrusion kneader to produce these resin compositions. 3 kg of resin pellets were prepared. The molecular weight (weight average molecular weight Mw) of PC is 140,000, PE is 160,000, PP is 200,000, and PET is 300,000.

(PC)
In Examples 111 to 119, PC was changed from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 4B.

When the second resin is PC, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the proportion of PC. Exceeded the target value. In particular, a resin composition containing 60% to 30% by weight of PC (40% to 70% by weight of hemicellulose polymer) has excellent heat resistance temperature, tensile strength, bending strength, and the like. A resin composition containing 10% by weight to 90% by weight of PC gives good results in most evaluation items even when compared with a resin composition containing 100% by weight of polyhemicellulose methacrylate (Example 110).

(PE)
In Examples 121 to 129, PE was changed from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 4C.

When the second resin is PE, the total light transmittance and birefringence phase difference are poor, so it cannot be applied to optical parts or moldings that require transparency. However, other evaluation items exceeded the target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, impurity concentration, and biodegradation rate. Varying from 10 wt% to 90 wt% PE (90 wt% to 10 wt% hemicellulose polymer) each has its advantages. Even when compared with 100% by weight polyhemicellulose methacrylate, the results are good in many evaluation items.

(PP)
In Examples 131 to 139, PP was varied from 90% to 10% by weight (10% to 90% by weight of polyhemicellulose methacrylate). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 4D.

When the second resin is PP, the total light transmittance and birefringence phase difference are poor, so it cannot be applied to optical parts or moldings that require transparency. However, other evaluation items exceeded the target values in heat resistance temperature, tensile strength, bending strength, fluidity, transferability, impurity concentration, and biodegradation rate. Even if the PP is varied from 10% to 90% by weight (90% to 10% by weight of the hemicellulose polymer), each resin composition has advantages. Even when compared with 100% by weight of polyhemicellulose methacrylate, the evaluation items of heat resistance temperature, tensile strength, bending strength and fluidity are good.

(PET)
In Examples 141 to 149, PET was changed from 90% to 10% by weight (polyhemicellulose methacrylate from 10% to 90% by weight). Using these 9 types of resin pellets, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared by photoforming. Using these sample products, heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability were evaluated. The evaluation results are shown in Table 4E.

When the second resin is PET, the heat resistance temperature, tensile strength, bending strength, fluidity, transferability, total light transmittance, birefringence phase difference, impurity concentration, and biodegradability are improved regardless of the PET ratio. Exceeded the target value. In particular, a resin composition containing 60% to 30% by weight of PET (40% to 70% by weight of hemicellulose polymer) has good heat resistance temperature, tensile strength, bending strength, and the like. A resin composition containing 10% by weight to 90% by weight of PET gives good results in most evaluation items even when compared with a resin composition containing 100% by weight of polyhemicellulose methacrylate (Example 110).

In summary, compared to the conventional PLA of 100% weight, 100% by weight of the hemicellulose polymer with acetyl groups, 100% by weight of the hemicellulose polymer with acetonyl groups, and 100% by weight of the hemicellulose polymer with carboxyl groups are superior in all evaluation items. Good results have been obtained. Furthermore, in the resin composition composed of the first resin and the second resin, which are hemicellulose polymers, good results are obtained when the first resin is 10 to 90% by weight and the second resin is 90 to 10% by weight. It is understood that it is obtained.

<<Injection molding by injection molding (without gas)>>
<Fifth to Seventh Embodiments>
An injection-molded product was produced using the resin pellets of the resin composition composed of the first resin and the second resin described in the first to fourth embodiments (Examples 1 to 149).

FIG. 1 is a conceptual diagram of molding an injection-molded product using an injection molding machine 10 and a mold 50. As shown in FIG. FIG. 1(a) is a diagram showing a state in which resin pellets RP of a resin composition are heated and liquefied in a resin injection section. (b) is a diagram showing a state in which a liquefied resin composition is injected from a resin injection section into a mold section. (c) is a diagram showing a state in which the mold part is opened and the resin molding is taken out.

(Configuration of injection molding machine)
The injection molding machine 10 includes a hopper 11 for receiving resin pellets RP of a resin composition, a cylinder 12 for receiving the resin pellets RP from the hopper 11, a rotatable screw 13 disposed inside the cylinder 12, and a and a heater 14 disposed thereon. Further, the screw 13 can be moved in the mold direction and in the opposite direction by the drive unit 15 . A liquefied resin composition is injected from a nozzle 16 at the tip of the cylinder 12 .

The mold 50 is composed of a stationary mold 52 and a movable mold 54, and a hollow cavity 56 is formed with the stationary mold 52 and the movable mold 54 in close contact with each other. A spool bushing 55 is formed in the cavity 56 as a hole into which the liquefied resin composition enters.

(Molding method for injection molding machine)
The resin pellets RP fall from the hopper 11 while being weighed by the rotation of the screw 13 . The resin pellets RP are melted (liquefied) by the frictional heat generated by the rotation and kneading of the screw 13 and the heat of the heater 14 . The weighed and liquefied resin composition moves the screw 13 in the direction of the mold by the drive unit 15, so that the resin composition passes through the spool bush 55 of the mold 50 from the nozzle 16 at the tip of the cylinder 12. It is injected into cavity 56 . The resin composition injected into the cavity 56 is cooled and solidified within the mold 50 . After that, the movable mold 54 is moved, the nozzle 16 of the injection molding machine 10 is also separated from the spool bushing 55, and the molded product MD is taken out. The molded product MD is taken out from the mold 50 by automatic dropping or taken out by a picker (not shown).

As for the moldings MD, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared in the same manner as in the first to fourth embodiments. Evaluation results are shown in Table 5A (5A embodiment) to Table 7E (7E embodiment). Since it is a molded product, items such as molding cycle time, molded product defect density, and molded product weight were newly added as evaluation targets. On the other hand, items such as fluidity, birefringence phase difference, and impurity concentration were not evaluated. Regarding the resin composition, the first embodiment (Examples 10, 60 and 110) and Example 1 of the 2A embodiment to Example 149 of the 4E embodiment are the implementation of the 5A embodiment. Examples 1 to 149 of the 7E embodiment correspond.

As can be seen by comparing Example 10 of the first embodiment with Example 10 of the 5A embodiment, a sample product of 100% by weight photoformed acetyl-grouped hemicellulose polymer and an injection-molded acetyl-grouped hemicellulose polymer The heat resistance strength, tensile strength, etc. are almost the same as the sample product of 100% by weight of polymer. Also, as can be understood by comparing Example 60 of the first embodiment with Example 60 of the 6A embodiment, a sample product of 100% by weight of a hemicellulose polymer having acetonyl groups by photomolding and a sample product of 100% by weight of a hemicellulose polymer having acetonyl groups by injection molding. The heat resistance strength, tensile strength, etc. are almost the same as the sample product of 100% by weight of the hemicellulose polymer. Further, as can be understood by comparing Example 110 of the first embodiment with Example 110 of the 7A embodiment, a sample product of 100% by weight of a hemicellulose polymer having carboxyl groups by photomolding and a sample product of 100% by weight of a hemicellulose polymer having carboxyl groups by injection molding were used. The heat resistance strength, tensile strength, etc. are almost the same as the sample product of 100% by weight of the hemicellulose polymer.

As shown in the 5A embodiment, the 6A embodiment, and the 7A embodiment, the resin composition consisting of the first resin and the second resin has a higher injection molding Good results were obtained in the evaluation items of cycle time, molding defect density, and molding weight. Also, it is understood that good results are obtained when the first resin is 40 to 70% by weight and the second resin is 60 to 30% by weight. The resin composition composed of the first resin and the second resin is highly biodegradable to solve environmental problems and marine pollution problems, and allows easy production of injection molded articles.

<<Injection molding by injection molding (with gas)>>
<Eighth to Tenth Embodiments>
An injection-molded product was produced using the resin pellets of the resin composition composed of the first resin and the second resin described in the first to fifth embodiments (Examples 1 to 149). Unlike the fifth to seventh embodiments, inert gas is supplied to at least one of the injection molding machine 10 and the mold 50 in the eighth to tenth embodiments.

FIG. 2 is a conceptual diagram of molding an injection-molded product using the injection molding machine 10 and the mold 50. As shown in FIG. FIG. 2(a) is a view showing a state in which the resin pellets RP of the resin composition are heated and liquefied in the resin injection section. (b) is a diagram showing a state in which a liquefied resin composition is injected from a resin injection section into a mold section. (c) is a diagram showing a state in which the mold part is opened and the resin molding is taken out.

(Configuration of injection molding machine)
The same reference numerals are given to the same members as the injection molding machine 10 and the mold 50 depicted in FIG. Differences from FIG. 1 will be described, and descriptions of the same reference numerals will be omitted. The cylinder 12 is provided with a gas supply pipe 18 to which a pump PP is connected. A gas supply pipe 58 to which a pump PP is connected is also provided. The pump PP supplies an inert gas or the like to the liquefied resin composition. This causes the molding to have foam. It should be noted that at least one of the injection molding machine 10 and the mold 50 may be provided to supply the inert gas or the like to the liquefied resin composition.

Gases for foaming include nitrogen, inert gases typified by rare gases such as helium and argon, carbon dioxide which is easily soluble in thermoplastic resins and exhibits a good plasticizer effect, saturated hydrocarbons having 1 to 5 carbon atoms, and They include chlorofluorocarbons in which some of the hydrogen atoms are substituted with fluorine, water, vapors of liquids such as alcohol, and the like. In this embodiment, carbon dioxide is used as the foaming gas.

(Molding method for injection molding machine)
The following molding method is a method of supplying gas to the resin composition liquefied in both the injection molding machine 10 and the mold 50 .
The resin pellets RP fall from the hopper 11 while being weighed by the rotation of the screw 13 . The resin pellets RP are melted (liquefied) by the frictional heat generated by the rotation and kneading of the screw 13 and the heat of the heater 14 . A gas is introduced from the pump PP into the molten resin composition and diffused into the liquid. Then, the measured and liquefied resin composition moves the screw 13 in the direction of the mold by the driving unit 15, and the resin composition in which the gas diffuses from the nozzle 16 at the tip of the cylinder 12 is transferred to the spool bush of the mold 50. It is injected through 55 into cavity 56 .

The resin composition injected into the cavity 56 is first introduced with gas from the pump PP and diffused into the liquid. After that, the gas-containing resin composition is cooled and solidified in the mold 50 . After that, the movable mold 54 is moved, the nozzle 16 of the injection molding machine 10 is also separated from the spool bushing 55, and the molded product MD is taken out. The molding MD is taken out from the mold 50 by automatic dropping or taken out by a take-out device (not shown).

As for the moldings MD, dumbbell test pieces, strip test pieces, disk substrates, cups, and flat plate samples were prepared in the same manner as in the first to fourth embodiments. Evaluation results are shown in Table 8A (8A embodiment) to Table 10E (10E embodiment). Since it is a molded product, items such as molding cycle time, molded product defect density, and molded product weight were newly added as evaluation targets. On the other hand, items such as fluidity, birefringence phase difference, and impurity concentration were not evaluated. Regarding the resin composition, the first embodiment (Examples 10, 60 and 110) and Example 1 of the 2A embodiment to Example 149 of the 4E embodiment are the implementation of the 8A embodiment. Examples 1 to 149 of the 10E embodiment correspond.

Comparing Example 10 of the 5A embodiment and Example 10 of the 8A embodiment, there is no significant difference in evaluation items. Comparing Example 60 of the 6A embodiment and Example 60 of the 9A embodiment, there is no significant difference in evaluation items. Comparing Example 110 of the 7A embodiment and Example 110 of the 10A embodiment, there is no significant difference in evaluation items.

On the other hand, when the first resin is 30 to 70% by weight and the second resin is 30 to 70% by weight, it is understood that good results are obtained for the resin composition samples obtained by foam injection molding. A sample of the acetyl group hemicellulose polymer and the second resin obtained by injection molding and a sample of the hemicellulose polymer and the second resin obtained by foam injection molding were obtained according to the molding cycle time. Evaluation items related to injection molding such as heat resistance strength and tensile strength have also improved.

Furthermore, as can be seen by comparing the tables of the 5A to 7E embodiments with the tables of the 8A to 10E embodiments, the second resin is all of PMMA, PC, PE, PP, and PET, and molding Cycle time, molded product defect density, molded product weight, heat resistant temperature, tensile strength, bending strength, transferability, total light transmittance, and biodegradability have been improved. From this result, the resin composition of the present embodiment is preferably molded by foaming injection molding using gas.

Although not mentioned as an example, there is a technique of supplying a foaming agent from a hopper together with resin pellets and performing foaming injection molding. The resin composition of the present embodiment can be expected to have improved performance even when the foaming agent is supplied from a hopper. Alternatively, resin pellets containing a foaming agent may be supplied. Furthermore, as a gas for foaming in the resin pellet, nitrogen, an inert gas typified by rare gases such as helium and argon, carbon dioxide that easily dissolves in thermoplastic resin and exhibits a good plasticizer effect, carbon number 1 It is also possible to supply a gas containing the saturated hydrocarbon of No. 5 and a gas obtained by partially substituting fluorine for hydrogen.

DESCRIPTION OF SYMBOLS 10... Injection molding machine 11... Hopper 12... Cylinder 13... Screw 14... Heater 15... Driving part 16... Nozzle 18... Gas supply pipe 50... Mold 52... Fixed side mold 54... Movement Side mold 55 Spool bush 56 Cavity 58 Gas supply pipe PP Gas pump

Claims (9)

Plant-derived first resin having the following structural formula

Beverage container, cup container or plate photoformed or injection molded product containing
(In the formula, R1 and R2 represent an alkyl group, an acetyl group, an acetonyl group, a carbonyl group, or a substituent containing them.
R3 is hydrogen, nitrogen, alkyl group, acetyl group, hydroxy group, acyl group, aldehyde group, amino group, imino group, aryl group, phosphonyl group, propenyl group, propanyl group, acetonyl group, carbonyl group, carboxyl group , cyano group, azo group, azide group, thiol group, sulfo group, nitro group, vinyl group, allyl group, cycloalkyl group, phenyl group, naphthyl group, araalkyl group, benzyl group, Schiff group, alkylene group, amyl group, acetamidomethyl group, adamantyl group, adamantyloxycarbonyl group, allyloxycarbonyl group, tert-butoxycarbonyl group, benzyloxymethyl group, biphenylisopropyloxycarbonyl group, benzoyl group, benzyloxycarbonyl group, cyanoethyl group, cyclohexyl group , carboxymethyl group, cyclopentadienyl group, pentamethylcyclopentadienyl group, cyclohexyl group, glucose, hexyl group, isobutyl group, isopropyl group, mesityl group, trimethylphenyl group, methoxymethyl group, mesitylenesulfonyl group , mesyl group, nosyl group, octadecylsilyl group, pivaloyl group, methoxybenzyl group, methoxyphenyl group, propyl group, ethoxymethyl group, trimethylsilyl group, trimethylsilylethoxymethyl group, ciamyl group, tert-butyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triethylsilyl group, tetrahydropyranyl group, triisopropylsilyl group, tolyl group, tosyl group, triisopropylbenzenesulfonyl group, trityl group, trichloroethoxycarbonyl group, benzyloxycarbonyl group, methylene group , valeryl group, methoxy group, acetamide group, trimethylammonium group, diazo group, hydrocarbon group, ionizable substituent or fluorine, bromine, chlorine or iodine and substituents containing them.
R1, R2 and R3 are the same or different.
A represents a single bond or a linking group. Q represents a single bond or a linking group.
n represents an integer of 2 or more. m represents an integer of 1 or more. )
2. Photoformed or injection molded beverage container , cup container or plate according to claim 1, further comprising a second resin which is polymethyl methacrylate (PMMA, acrylic) . Polycarbonate (PC), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PS), ABS resin (ABS), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl acetate (PVAC), polymethylpentene (PMP), polybutene (PB), hydroxybenzoic acid polyester (HBP), polyetherimide (PEI), polyacetal (POM), Polyphenylene ether (PPE), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyurethane (PUR), ionomer resin (IO), fluorine resin (FR), polytetrafluoroethylene (PTFE), polycyclohexylene dimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polyarylate (PAR), polyacrylonitrile (PAN), polyarylsulfone (PASF), polyamide (PA), polyvinyl alcohol (PVA), polymethacrylstyrene (MS), butadiene Resin (BDR), polybutylene terephthalate (PBT), polyester carbonate (PPC), polybutylene succinate (PBS), norbornene resin (NB), polyamide (nylon) (PA), Teflon (registered trademark), fiber reinforced plastic ( FRP), polyhydroxyalkanoic acid (PHA), polyhydroxybutyric acid (PHB), hydroxybutyric acid/hydroxyhexanoic acid copolymer (PHBH), acetylcellulose (CA), polyimide (PI), polyamideimide (PAI), polysulfone ( PSF), polyethersulfone (PES), polyetheretherketone (PEEK), liquid crystal polymer (LCP), polychlorotrifluoroethylene (PCTFE), silicone resin (SI), epoxy resin (EP), wood powder, wood pellets , bamboo powder, bamboo pellets, grass powder, grass pellets, paper powder, paper pellets and a second resin containing any one of polylactic acid (PLA),
A photomolded product or an injection molded product of the beverage container , cup container or flat plate according to claim 1 . A second resin having the following structural formula:

2. Photoform or injection molding of beverage container , cup container or plate according to claim 1.
(In the formula, R5 and R6 represent an alkyl group, an acetyl group, an acetonyl group, a carbonyl group, or a substituent containing them. R5 and R6 are the same or different.
n represents an integer of 2 or more. ) The beverage container, cup container or flat plate photoformed product according to any one of claims 2 to 4, wherein the first resin is 10 to 90% by weight and the second resin is 90 to 10% by weight, or injection molding. Plant-derived first resin having the following structural formula

A step of introducing a resin composition containing into an extrusion kneading device;
A step of extruding as a cylindrical resin from the nozzle of the extrusion kneading device;
A step of cutting the extruded cylindrical resin with a pelletizer,
A manufacturing method for producing photo- or injection-moldable resin pellets with a diameter of 0.2-3 mm and a length of 0.2-5 mm.
(In the formula, R1 and R2 represent an alkyl group, an acetyl group, an acetonyl group, a carbonyl group, or a substituent containing them.
R3 is hydrogen, nitrogen, alkyl group, acetyl group, hydroxy group, acyl group, aldehyde group, amino group, imino group, aryl group, phosphonyl group, propenyl group, propanyl group, acetonyl group, carbonyl group, carboxyl group , cyano group, azo group, azide group, thiol group, sulfo group, nitro group, vinyl group, allyl group, cycloalkyl group, phenyl group, naphthyl group, araalkyl group, benzyl group, Schiff group, alkylene group, amyl group, acetamidomethyl group, adamantyl group, adamantyloxycarbonyl group, allyloxycarbonyl group, tert-butoxycarbonyl group, benzyloxymethyl group, biphenylisopropyloxycarbonyl group, benzoyl group, benzyloxycarbonyl group, cyanoethyl group, cyclohexyl group , carboxymethyl group, cyclopentadienyl group, pentamethylcyclopentadienyl group, cyclohexyl group, glucose, hexyl group, isobutyl group, isopropyl group, mesityl group, trimethylphenyl group, methoxymethyl group, mesitylenesulfonyl group , mesyl group, nosyl group, octadecylsilyl group, pivaloyl group, methoxybenzyl group, methoxyphenyl group, propyl group, ethoxymethyl group, trimethylsilyl group, trimethylsilylethoxymethyl group, ciamyl group, tert-butyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triethylsilyl group, tetrahydropyranyl group, triisopropylsilyl group, tolyl group, tosyl group, triisopropylbenzenesulfonyl group, trityl group, trichloroethoxycarbonyl group, benzyloxycarbonyl group, methylene group , valeryl group, methoxy group, acetamide group, trimethylammonium group, diazo group, hydrocarbon group, ionizable substituent or fluorine, bromine, chlorine or iodine and substituents containing them.
R1, R2 and R3 are the same or different.
A represents a single bond or a linking group. Q represents a single bond or a linking group.
n represents an integer of 2 or more. m represents an integer of 1 or more. ) 7. The production method for producing resin pellets according to claim 6, further comprising a second resin that is polymethyl methacrylate (PMMA, acrylic) . Polycarbonate (PC), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PS), ABS resin (ABS), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl acetate (PVAC), polymethylpentene (PMP), polybutene (PB), hydroxybenzoic acid polyester (HBP), polyetherimide (PEI), polyacetal (POM), Polyphenylene ether (PPE), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyurethane (PUR), ionomer resin (IO), fluorine resin (FR), polytetrafluoroethylene (PTFE), polycyclohexylene dimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polyarylate (PAR), polyacrylonitrile (PAN), polyarylsulfone (PASF), polyamide (PA), polyvinyl alcohol (PVA), polymethacrylstyrene (MS), butadiene Resin (BDR), polybutylene terephthalate (PBT), polyester carbonate (PPC), polybutylene succinate (PBS), norbornene resin (NB), polyamide (nylon) (PA), Teflon (registered trademark), fiber reinforced plastic ( FRP), polyhydroxyalkanoic acid (PHA), polyhydroxybutyric acid (PHB), hydroxybutyric acid/hydroxyhexanoic acid copolymer (PHBH), acetylcellulose (CA), polyimide (PI), polyamideimide (PAI), polysulfone ( PSF), polyethersulfone (PES), polyetheretherketone (PEEK), liquid crystal polymer (LCP), polychlorotrifluoroethylene (PCTFE), silicone resin (SI), epoxy resin (EP), wood powder, wood pellets , bamboo powder, bamboo pellets, grass powder, grass pellets, paper powder, paper pellets and a second resin containing any one of polylactic acid (PLA),
A manufacturing method for manufacturing the resin pellet according to claim 6 . a second resin having the following structural formula:

A manufacturing method for manufacturing the resin pellet according to claim 6 .
(In the formula, R5 and R6 represent an alkyl group, an acetyl group, an acetonyl group, a carbonyl group, or a substituent containing them. R5 and R6 are the same or different.
n represents an integer of 2 or more. )

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