JP7371978B1 - biomass masterbatch - Google Patents

Abstract

An object of the present invention is to provide a technology that facilitates the design of physical properties and moldability of a final molded product. One aspect of the present invention includes starch and at least one resin selected from the group consisting of polyethylene, ionomer resin, and acrylate copolymer, and has an MFR of 3.30 to 3.30 at 190° C. and 10 kgf. This is a biomass masterbatch having a rate of 4.20 g/10 min and a starch content of more than 60% by weight. [Selection diagram] None

Description

The present invention relates to a biomass masterbatch.

Compositions produced by processing biomass (resources that are organic substances derived from animals and plants (excluding crude oil, oil gas, flammable natural gas, and coal)) by chemical methods or methods that utilize biological effects. If the biomass material accounts for 25% or more of the weight of a product or its molded product (for example, a plastic shopping bag), the biomass material is a carbon-neutral material and serves as a countermeasure against global warming.

In order to create a composition of biomass material with such a blending ratio, the composition can be created at once by mixing the biomass material with a resin at a predetermined blending ratio, or It is also possible to create a composition by once creating a composition (biomass masterbatch) with a high blending ratio of materials, and then mixing it with a diluent resin for adjusting the blending ratio of biomass materials. The latter form is preferable in that it can facilitate the design of physical properties, moldability, etc. of the final composition by appropriately selecting the physical properties of the diluting resin.

On the other hand, in order to use the latter type of diluent resin to increase the blending ratio of biomass material to 25% by weight or more, it is necessary to considerably increase the blending ratio of biomass material in the biomass masterbatch. When producing a biomass masterbatch with a high blending ratio of such biomass materials, when mixing starch as the biomass material and polyethylene, ionomer resin, acrylate copolymer, etc. as the resin, the melt viscosity becomes high. Conventionally, biomass materials in biomass masterbatches have been used in biomass masterbatches because this can cause agglomeration of biomass materials in the composition, resulting in over-torque in equipment and reduction in processing capacity due to lack of thermal fluidity. It has been realistic to keep the blending ratio at most 60% by weight or less (particularly 50% by weight or less) (for example, Patent Document 1).

Patent No. 5183455

However, in order to create a composition with a biomass material content of 25% by weight or more using a biomass masterbatch with a low biomass material content and a diluent resin, the physical properties of the final composition must be adjusted. The mixing ratio of the diluent resin, which is an important factor for facilitating the design and moldability of the final composition, must be reduced, making it difficult to design the physical properties and moldability of the final composition. I found out.

Therefore, it is an object of the present invention to provide a technology that facilitates the design of the physical properties and moldability of the final molded product.

One embodiment of the present invention includes starch and at least one selected from the group consisting of at least one polyethylene, an ionomer resin, and an acrylate copolymer, and has an MFR of 3.30 to 4.0 at 190° C. and 10 kgf. The biomass masterbatch is 20g/10min and has a starch content of more than 60% by weight.

According to the present invention, it is possible to provide a technique that facilitates the design of physical properties and moldability of a final molded product.

1 is a perspective view showing a biomass masterbatch manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a front view of FIG. 1; FIG. 2 is a plan view of FIG. 1; It is a figure showing the 1st accommodation space of the 1st accommodation part which constitutes a manufacturing device of a biomass masterbatch. FIG. 2 is a diagram showing a plurality of rotating members arranged in a first storage space of a first storage part that constitutes the biomass masterbatch manufacturing apparatus of FIG. 1. FIG. 1 is a flowchart showing a method for producing a biomass masterbatch according to an embodiment of the present invention.

The present invention will be explained in detail below. In this specification, "X to Y" is used to include the numerical values (X and Y) written before and after it as lower and upper limits, and means "more than or equal to X and less than or equal to Y." When multiple "X to Y" are listed, for example, "X1 to Y1, or X2 to Y2", disclosures with each numerical value as the upper limit, disclosures with each numerical value as the lower limit, and , all combinations of upper and lower limits are disclosed (that is, they are legal grounds for amendment). Specifically, corrections with X1 or more, Y2 or less, X1 or less, Y2 or more, X1 to X2, X1 to Y2, etc. must all be considered legal. Must be.

<Biomass masterbatch>
One embodiment of the present invention includes starch and at least one resin selected from the group consisting of polyethylene, ionomer resin, and acrylate copolymer, and has an MFR of 3.30 to 4.20 g/f at 190° C. and 10 kgf. This is a biomass masterbatch in which the production time is 10 min and the starch content is more than 60% by weight. Such an aspect makes it possible to easily design the physical properties and moldability of the final molded product.

(MFR of biomass masterbatch at 190℃ 10kgf)
The melt flow rate (MFR) of the biomass masterbatch according to one embodiment of the present invention at 190° C. and 10 kgf is 3.30 to 4.20 g/10 min. In one embodiment of the present invention, the MFR of the biomass masterbatch at 190°C and 10 kgf is 3.32 g/10 min or more, 3.34 g/10 min or more, 3.36 g/10 min or more, 3.38 g/10 min or more, 3. 40g/10min or more, 3.42g/10min or more, 3.44g/10min or more, 3.46g/10min or more, 3.48g/10min or more, 3.50g/10min or more, 3.60g/10min or more, 3.70g /10min or more, 3.80g/10min or more, or 3.90g/10min or more. In one embodiment of the present invention, the MFR of the biomass masterbatch at 190°C and 10 kgf is 4.15 g/10 min or less, 4.13 g/10 min or less, 4.11 g/10 min or less, 4.09 g/10 min or less, 4. 07g/10min or less, 4.05g/10min or less, 4.03g/10min or less, 4.01g/10min or less, 3.99g/10min or less, 3.98g/10min or less, 3.96g/10min or less, 3.90g /10min or less, 3.80g/10min or less, 3.70g/10min or less, 3.60g/10min or less, 3.50g/10min or less, 3.48g/10min or less, or 3.46g/10min or less.

(starch)
The biomass masterbatch of one embodiment of the present invention contains starch, and the content ratio thereof is more than 60% by weight in the biomass masterbatch. If it is less than 60% by weight, the mixing ratio of the diluent resin, which is an important factor to facilitate the design and moldability of the physical properties of the final composition, must be reduced, and the physical properties of the final composition will be reduced. etc. design and moldability may be difficult. In this specification, when referring to the content, content ratio, etc. of at least starch, the content, content ratio, etc. are based on the solid content calculated from the water content. In addition, in this specification, calculation of water content can be based on the method of Karl Fischer coulometric titration (JIS K0113:2005).

In one embodiment of the present invention, the content ratio of starch in the biomass masterbatch is 61% by weight or more, 62% by weight or more, 63% by weight or more, 64% by weight or more, 65% by weight or more, 66% by weight or more, 67% by weight or more. % or more, 68% by weight or more, or 69% by weight or more. In one embodiment of the present invention, the content ratio of starch in the biomass masterbatch is 90% by weight or less, 85% by weight or less, 80% by weight or less, 78% by weight or less, 76% by weight or less, 74% by weight or less, 73% by weight or less. % or less, 71% by weight or less, 69% by weight or less, 67% by weight or less, 65% by weight or less, or 63% by weight or less.

In this specification, starch may be a starch-containing material (also simply referred to as "starch") whose main component is starch, such as polished rice (raw rice) or rice bran, in addition to a material consisting only of starch as a component. The main component may be more than 50% by weight, 60% by weight or more, or 70% by weight or more of starch in the starch-containing material.

The type of starch is not particularly limited, but from the viewpoint of market price and stable supply, it may be selected from rice such as milled rice (raw rice) or rice bran (white flour), potatoes, taro, corn, wheat, rye, beans, and sweet potatoes. It is preferable that it is one or more selected from the group consisting of or derived from these. It should be noted that tofu derived from at least one of these types is processed, and for example, in the case of soybeans, it may be tofu obtained by processing using ingredients such as bittern. That's what it means. It may be rice that has been subjected to some kind of processing, such as polished rice (raw rice) or rice bran (white flour).

If rice is used as starch as raw material, it can be of β structure (crystalline structure). Note that polished rice (raw rice) can be prepared by removing rice bran from brown rice. Polished rice (raw rice) may be in the form of ginjo rice (for example, 3-minute to 7-minute polished rice, 4-minute to 6-minute polished rice, etc.). Among these, it is preferable that the rice be milled rice because it is similar in size to the general size of resin pellets that are the raw material for biomass masterbatch and is easy to handle. Note that since rice bran is often discarded during the rice milling process, the use of rice bran has a low environmental impact, is ecological, and is also suitable from the perspective of life cycle assessment.

According to one embodiment of the present invention, the average diameter of the starch as a raw material is 100 μm or more (here, the diameter is the maximum diameter when two arbitrary points are taken, and the same is the same in this specification), and 110 μm or more. , 500 μm or more, 750 μm or more, 1 mm or more, 2 mm or more, 3 mm or more, 4 mm or more, or 4.5 mm or more. According to an embodiment of the invention, the average diameter of the raw starch may be 15 mm or less, 10 mm or less, 9 mm or less, 8 mm or less, 7 mm or less, or 6 mm or less. Specifically, a statistically reliable number (or 10, 50, 100, 500, 1000 or more) is arbitrarily selected from a plurality of starches, and the arithmetic average is taken. Examples of instruments used for measurement include calipers (JIS B 7507:2016) and microscopes.

Moreover, when using rice as starch, rice flour can also be used. As mentioned above, the raw materials for rice flour include polished rice, ginjo rice (3-minute to 7-minute polished rice, 4-minute to 6-minute polished rice, etc.), rice bran (medium white flour), etc., which have a β structure (crystalline structure). suitable. The average diameter of the rice flour may be less than 100 μm, alternatively less than 80 μm. The average diameter of the rice flour may be 30 μm or more, 40 μm or more, 50 μm or more, or 60 μm or more. Instruments used to measure the average diameter include, for example, a microscope, which measures a statistically reliable number (or 10, 50, 100, 500, 1000, or more) from multiple starches. Select them arbitrarily and take the arithmetic average of them.

When the starch is rice, the content ratio of rice in the biomass masterbatch is 61% by weight or more, 62% by weight or more, 63% by weight or more, 64% by weight or more, 65% by weight or more, 66% by weight or more, 67% by weight. The content is 68% by weight or more, or 69% by weight or more. In one embodiment of the present invention, the content ratio of rice in the biomass masterbatch is 90% by weight or less, 85% by weight or less, 80% by weight or less, 78% by weight or less, 76% by weight or less, 74% by weight or less, 73% by weight or less. % or less, 71% by weight or less, 69% by weight or less, 67% by weight or less, 65% by weight or less, or 63% by weight or less. In this manner, starch may be read as rice (polished rice and/or rice bran) in this specification.

(resin)
The biomass masterbatch of one embodiment of the present invention contains at least one selected from the group consisting of polyethylene, ionomer resin, and acrylate copolymer. Such resins have a property that their melt viscosity increases during kneading, making them difficult to handle.

In one embodiment of the invention, the polyethylene is low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or high density polyethylene (HDPE). These may be used alone or in combination of two or more.

In one embodiment of the present invention, examples of commercially available polyethylene include Kernel KS340T, Kernel KJ640T, KS560T, KS240T, and KF260T manufactured by Japan Polyethylene Co., Ltd.

In one embodiment of the present invention, the polyethylene is composed of at least two types.

In one embodiment of the invention, at least one of the resins is biopolyethylene. By adopting such an embodiment, the degree of biomass can be increased. Here, the degree of biomass may be the proportion (% by weight) derived from biomass in the resin mixture. In one embodiment of the present invention, the biomass content is 60% by weight or more, 62% by weight or more, 64% by weight or more, 66% by weight or more, 68% by weight or more, 70% by weight or more, 72% by weight or more, or 74% by weight or more. % by weight. In one embodiment of the present invention, the upper limit of the biomass degree is not particularly limited, but may be 70% by weight or less, 68% by weight or less, 66% by weight or less, or 65% by weight or less.

In one embodiment of the present invention, examples of commercially available biopolyethylene include SPB608, SPB208, SLH218, and SLH118 from Braskem; NOBON Masterbatch NOBON BN2 Bio from Novon Japan.

In one embodiment of the present invention, the ionomer resin is a synthetic resin in which metal ions are bonded between polymer structures made of at least one of ethylene, acrylic acid, methacrylic acid, etc. to form a crosslinked structure. Here, examples of metal ions include zinc ions and sodium ions. Examples of commercially available products include Himilan (registered trademark) 1706 and 1707 manufactured by Mitsui Dow Chemical Company.

In one embodiment of the invention, the acrylate copolymer is preferably an ethylene-methyl acrylate copolymer. Examples of commercially available products include LEXPAR EMA EB140F and EB050S manufactured by Nippon Polyethylene Co., Ltd.

In one embodiment of the present invention, the content ratio of the resin (the total when two or more types are used together) in the biomass masterbatch is 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, 18% by weight or more. It is at least 20% by weight, at least 22% by weight, at least 24% by weight, at least 26% by weight, or at least 28% by weight. In one embodiment of the present invention, the content ratio of the resin (the total when two or more types are used together) in the biomass masterbatch is 60% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, % by weight or less, 32% by weight or less, 30% by weight or less, 28% by weight or less, 26% by weight or less, or 25% by weight or less.

In one embodiment of the present invention, two or more resins are used in combination, and the melt flow rate values of these resins are different, and at least one resin (also referred to as "low melt flow rate resin") is used in combination. Melt flow rate (MFR (190°C/2.16 kgf)) is 0.5 g/10 min or more and less than 15 g/10 min, 0.8 to 14 g/10 min, 1.2 to 13 g/10 min, 1.4 to 12 g/10 min , 1.8-11g/10min, 2.0-10g/10min, 2.2-9g/10min, 2.4-8g/10min, 2.8-7g/10min, 3-6g/10min, 3.2 ~5g/10min, or 3.3~4g/10min, and the melt flow rate (MFR (190°C/2.16kgf)) of at least one resin (also referred to as "high melt flow rate resin") are 15-50g/10min, 18-48g/10min, 20-46g/10min, 22-44g/10min, 24-42g/10min, 26-40g/10min, 28-38g/10min, 29-36g/10min, 29 to 34 g/10 min, or 29 to 32 g/10 min. That is, in one embodiment of the present invention, the MFR of at least one of the resins at 190° C. 2.16 kgf is 15 g/10 min or more, and the MFR of at least one of the resins at 2.16 kgf of 190° C. MFR is less than 15g/10min. By appropriately using a plurality of resins having melt flow rates as described above, high strength and fluidity can be achieved at the same time, and the resin can be suitably used for inflation processing. However, it is not limited to inflation processing, and can also be used, for example, in sheet extrusion processing, injection molding processing, etc.

In one embodiment of the present invention, the content weight of the low melt flow rate resin relative to the content weight of the high melt flow rate resin (low melt flow rate resin/high melt flow rate resin) is more than 1.00, 1.10 or more, 1.20 or more, 1.30 or more, 1.40 or more, 1.50 or more, 1.60 or more, 1.70 or more, 1.80 or more, 1.90 or more, 1.93 or more, 1.94 or more, It is 1.95 or more, 1.96 or more, 1.97 or more, 1.98 or more, 1.99 or more, 2.00 or more, or 2.01 or more. In one embodiment of the present invention, the content weight of the low melt flow rate resin relative to the content weight of the high melt flow rate resin (low melt flow rate resin/high melt flow rate resin) is less than 5.00, 4.50 or less, 4.00 or less, 3.50 or less, 3.00 or less, 2.80 or less, 2.60 or less, 2.40 or less, 2.26 or less, 2.25 or less, 2.24 or less, 2.23 or less, It is 2.22 or less, 2.21 or less, 2.20 or less, 2.15 or less, 2.10 or less, or 2.05 or less.

In one embodiment of the invention, the number of types of resins used is, for example, 4 or less, 3 or less, or 2 or less. For example, if four types of resins are used, three types of resins may be high melt flow rate resins and one type of resin may be low melt flow rate resins, or three types of resins may be low melt flow rate resins. One type of resin may be a high melt flow rate resin, or two types of resin may be high melt flow rate resins. For example, when three types of resins are used, two types of resins may be high melt flow rate resins and one type of resin may be low melt flow rate resins, or two types of resins may be low melt flow rate resins. One type of resin may be a high melt flow rate resin. The biomass masterbatch can be appropriately combined so that the MFR at 190° C. and 10 kgf is 3.3 to 4.2 g/10 min, and the starch content is more than 60% by weight.

In one embodiment of the present invention, the melting point of the resin is (individually when two or more resins are used) 120°C or less, 110°C or less, 100°C or less, 90°C or less, 80°C or less, 70°C or less. ℃ or lower, 65℃ or lower, or 60℃ or lower. In one embodiment of the present invention, the melting point of the resin is (individually when two or more resins are used) 45°C or higher, 50°C or higher, 55°C or higher, 59°C or higher, 60°C or higher, and 70°C or higher. ℃ or higher, 80℃ or higher, or 90℃ or higher. According to one embodiment of the present invention, at least one of the resins has a melting point of 110°C or less. In this specification, the melting point can be measured using, for example, a constant test force extrusion type capillary rheometer flow tester (CFT-500EX) manufactured by Shimadzu Corporation.

(Additive)
According to one embodiment of the invention, the biomass masterbatch consists of glycerol, polyglycerol, glycerin fatty acid esters, polyglycerin fatty acid esters, polyalkylene glycols, and polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof. At least one additive selected from the group consisting of:

According to one embodiment of the present invention, the glycerin fatty acid ester includes three types: monoester, diester, and triester, and more specifically, for example, acetic acid monoglyceride, lactic acid monoglyceride, citric acid monoglyceride, and diacetyl tartaric acid. Examples include monoglyceride, acetylated glyceride (diacetyl fatty acid monoglyceride) such as glycerin diacetomonolaurate, succinic acid monoglyceride, polyglycerin condensed linosylic acid ester, and glycerin diacetomonolaurate. According to one embodiment of the invention, the diacetyl fatty acid monoglyceride has an alkyl group having 8 to 15 carbon atoms, 9 to 14 carbon atoms, or 10 to 13 carbon atoms. According to one embodiment of the present invention, the polyglycerin fatty acid ester has the following structure, where n is, for example, 2 to 6, or alternatively 2 to 5, R has 11 to 20 carbon atoms, It is an alkyl group of 13 to 19 or 15 to 18.

According to one embodiment of the invention, unsaturated carboxylic acids include maleic acid, maleic anhydride, nadic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, sorbic acid, acrylic acid, etc. . As the derivative of unsaturated carboxylic acid, metal salts, amides, imides, esters, etc. of unsaturated carboxylic acids can be used.

According to one embodiment, the polyalkylene glycol is:
H(OA) _n OH
Here, A is an alkylene group, and n is 1 to 5. According to an embodiment of the invention, the alkylene group may have 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 or 2 carbon atoms.

According to one embodiment of the present invention, the polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof includes polyethylene or polypropylene modified with an unsaturated carboxylic acid or a derivative thereof. This can be obtained by heating and mixing a polyolefin, an unsaturated carboxylic acid or a derivative thereof, and a radical generator in the presence or absence of a solvent. In one embodiment of the present invention, the amount of unsaturated carboxylic acid or its derivative added to the polyolefin resin (modification amount) is 0.1 to 15% by mass, or 1 to 10% by mass. As the additive, a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, which is odorless and has low acidity, is suitable.

In one embodiment of the present invention, one type of additive may be used alone, or two or more types may be used in combination.

In one embodiment of the invention, the additive may be in liquid form.

The content ratio of additives (the total when two or more types are used together) in the biomass masterbatch of one embodiment of the present invention is 0.2% by weight or more (in terms of solid content if the additives are liquid), and 0. .5% by weight or more, 1.0% by weight or more, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3.0% by weight or more, 3.5% by weight or more, 4.0% by weight % or more, 4.5 weight % or more, 5.0 weight % or more, 5.2 weight % or more, 5.4 weight % or more, 5.6 weight % or more, or 5.8 weight % or more. In the biomass masterbatch of one embodiment of the present invention, the content ratio of additives (if two or more types are used together, the total) is 20% by weight or less (in terms of solid content if the additives are liquid), and 18% by weight. % or less, 16% by weight or less, 14% by weight or less, 12% by weight or less, 10% by weight or less, 8.0% by weight or less, or 7.0% by weight or less.

In one embodiment of the invention, the additive comprises a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof.

In one embodiment of the invention, the additive comprises a glycerin fatty acid ester.

In one embodiment of the present invention, when two or more types of additives are used in combination, at least a combination of a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and a glycerin fatty acid ester is included. The "carboxyl group" and "polyolefin structure" in a polyolefin resin modified with an unsaturated carboxylic acid or its derivative interact with the hydroxyl group of starch and the polyethylene resin, respectively, thereby increasing the compatibilization effect. . In addition, glycerin fatty acid ester can promote gelatinization of starch, increase compatibility with resin, and impart plasticity. Note that the present invention is not limited by such a mechanism.

In one embodiment of the present invention, the content weight of the polyolefin resin modified with an unsaturated carboxylic acid or its derivative relative to the content weight of the glycerin fatty acid ester is more than 1.0, 1.2 or more, 1.4 or more, 1. It is 6 or more, 1.8 or more, 2.0 or more, 2.2 or more, 2.4 or more, or 2.5 or more. In one embodiment of the present invention, the content weight of the polyolefin resin modified with an unsaturated carboxylic acid or its derivative relative to the content weight of the glycerin fatty acid ester is 4.0 or less, 3.5 or less, 3.0 or less, or It is 2.8 or less.

In one embodiment of the present invention, the additive may be a commercially available product, and specifically, RIKEAID MG-440P (manufactured by Riken Vitamin Co., Ltd.), MG-441P (manufactured by Riken Vitamin Co., Ltd.), MG -250P (manufactured by Riken Vitamin Co., Ltd.), Poem J-4081V (manufactured by Riken Vitamin Co., Ltd.), Umex 1001 (manufactured by Sanyo Chemical Industries, Ltd.), Umex 1010 (manufactured by Sanyo Chemical Industries, Ltd.), Tirabazole VR-01 (Taiyo Chemical Co., Ltd.) (manufactured by Taiyo Kagaku Co., Ltd.), Tirabazole VR-07 (manufactured by Taiyo Kagaku Co., Ltd.), and Biosizer (manufactured by Riken Vitamin Co., Ltd.).

In one embodiment of the invention, the additive is biodegradable. By having the additive have biodegradability, it is possible to prevent the additive from remaining in nature. Additionally, when non-biodegradable additives are used, there is a possibility that the biodegradation of the entire composition may be inhibited, but when biodegradable additives are used, there is a possibility that the biodegradation of the entire composition is inhibited. is extremely low. The substances listed in the Japan Bioplastics Association (JBPA) Biodegradable Plastic Positive List (PL) (classification number B-3 (lubricants)) are cited in their entirety by reference and are incorporated herein by reference. , is a legal basis for amendment.

Here, biodegradation refers to the breaking of the molecular bonds of substances by enzymes produced by microorganisms in the soil and water, and the final decomposition into water and carbon dioxide. According to one embodiment, biodegradability is one that satisfies at least one of ISO 9408, ISO 9439, ISO 10707, JIS K 6950, JIS K 6951, JIS K 6953, or JIS K 6955.

<Production method of biomass masterbatch>
In one embodiment of the present invention, starch and at least one resin (hereinafter also referred to as material) selected from the group consisting of polyethylene, ionomer resin, and acrylate copolymer are kneaded in a manufacturing apparatus. , a method for producing a biomass masterbatch is provided. In this embodiment, the starch content ratio in the biomass masterbatch is set to exceed 60% by weight, and the MFR of the biomass masterbatch at 190°C and 10kgf is set to be 3.30 to 4.20 g/10 min. is set to . In order to set the MFR of the biomass masterbatch at 190°C and 10 kgf to be 3.30 to 4.20 g/10 min, as mentioned above, it is necessary to select the MFR of the raw material resin and adjust the melting point of the raw material resin. For example, it may be selected or used in combination with a compatibilizer or a plasticizer (gelatinization accelerator) as appropriate.

A wide variety of manufacturing equipment can be used without limitation for mixing the materials. However, if the starch input into the production equipment is air-dried, it is preferable to introduce water into the production equipment, so that the starch is mixed in a heated state in the presence of water. As a result, the starch begins to pregelatinate in the apparatus, and as a result, the resin and starch become amorphous when mixed, making mixing easier. Therefore, the device is preferably one that can be used when water is introduced.

(Manufacturing equipment)
In one embodiment of the present invention, the manufacturing device may be a twin-screw kneading device 100. As shown in FIGS. 1 to 5, the two-screw kneading device 100 includes a first storage section 10, an input section 20, a rotating section 30, a dehydration section 50, a first degassing section 60, and a second degassing section 50. It has a section 70, a discharge section 80, a cooling section 90, and a cutting section 110.

In addition, in explaining the biaxial kneading apparatus 100, an orthogonal coordinate system is depicted in the drawings. X is a direction in which a rotating shaft of the rotating section 30, which will be described later, extends, and is referred to as a longitudinal direction. Y corresponds to the width direction of the first accommodating portion 10 that intersects with the longitudinal direction X, and is referred to as the width direction Y. Z is a direction intersecting the longitudinal direction X and the width direction Y, and is defined as the height direction Z. The details will be explained below.

(First storage part 10)
The first accommodating portion 10 forms a first accommodating space S1 in which starch, resin, compatibilizer (material), etc. can be accommodated together with water as needed. The first accommodating portion 10 is configured to be elongated so as to extend in the longitudinal direction X of the space in which the biaxial kneading device 100 is installed.

The first accommodating section 10 forms a first accommodating space S1 that accommodates a plurality of rotating members 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, and 42 constituting the rotating section 30. It is composed of The first accommodating space S1 formed by the first accommodating section 10 is configured to be continuous from directly below the input section 20 to a portion connected to the second degassing section 70. As shown in FIG. 4, the first accommodation space S1 has an inner peripheral portion of the cross section shaped like a combination of two circular arcs so that the rotating member of the rotating part 30 has two rotating axes in this embodiment. It consists of The first housing part 10 can be provided with a heating device (not shown) such as a heater for adjusting the temperature of the first housing space S1. A plurality of the above-mentioned heaters can be arranged, for example, in the longitudinal direction X so that the temperature can be adjusted for each specific section of the rotating member, which will be described later, in the longitudinal direction X of the first accommodation space S1 of the first accommodation part 10.

(Insertion section)
As shown in FIG. 1, the charging unit 20 includes a hopper (feeder) capable of charging the above-described materials and water into the first storage space S1. The hopper of the input section 20 is shaped like a funnel.

(rotating part)
The rotating part 30 is rotatably arranged in the first accommodation space S1. The rotating section 30 is configured such that a plurality of rotating members 31 to 39, 41, and 42 are arranged side by side along a rotation axis with a direction parallel to the longitudinal direction X as the rotation axis. The rotating members 31 to 39, 41, and 42 are biaxially arranged along the width direction Y, as shown in FIG. In this specification, the rotating member 31 is the first screw, the rotating member 32 is the first paddle, the rotating member 33 is the second screw, the rotating member 34 is the second paddle, the rotating member 35 is the fourth screw, and the rotating member 41 is the fourth screw. The 6th screw and the rotating member 42 correspond to the 7th screw. Each rotating member will be explained in detail below.

(Rotating member 31)
The rotating member 31 is arranged directly below the hopper of the input section 20 in the first storage space S1 of the first storage section 10. The rotating member 31 is configured to form a screw. In this specification, a portion of the first housing space S1 where the rotating member 31 is arranged is referred to as a material inputting section into which materials and water are inputted.

(Rotating members 32, 33)
As shown in FIG. 5, the rotating member 32 is provided adjacent to the rotating member 31 on the downstream side of the rotating member 31 in the first accommodation space S1. The rotating member 32 is configured such that plate-like members are arranged side by side along the rotation axis. The rotating member 32 is arranged between the rotating member 31 and the rotating member 33.

The rotating member 33 is provided adjacent to the rotating member 32 on the downstream side of the rotating member 32 in the first accommodation space S1. The rotating member 33 is configured to form a screw similarly to the rotating member 31. The rotating member 33 has a shallower spiral groove than the rotating member 31. The rotating member 33 is configured such that the difference between the outermost circumference and the innermost circumference in the radial direction of the spiral is larger than that of the rotating member 31. The rotating member 33 is configured such that its outermost circumference has the same size as the rotating member 31 and its innermost circumference is smaller than that of the rotating member 31. The portion of the first accommodation space S1 where the rotating members 32 and 33 are arranged can be referred to as a resin melting section that melts the resin input from the input section 20.

(Rotating member 34)
Like the rotating member 32, the rotating member 34 has a plurality of plate-like members arranged along the rotating shaft, and is arranged on the downstream side of the rotating shaft than the rotating member 33 in the first accommodation space S1. It consists of Although the rotating member 34 is illustrated in FIG. 5 so that the thickness of the plate-like member is one type, it is not necessary to have one type. The rotating member 34 is formed thinner than the rotating member 32 so as to exert more shear stress to disperse the material and uniformly stir the material. The portion of the first accommodation space S1 where the rotating member 34 is arranged can be referred to as a kneading section that kneads the material input from the input section 20. A dehydration section 50 is connected near the boundary between the rotating member 33 and the rotating member 34 in order to discharge gas-liquid components such as water added to the above-mentioned material. Details will be described later.

(Rotating member 35)
The rotating member 35 is provided adjacent to the rotating member 34 on the downstream side of the rotating member 34 in the first accommodation space S1. The rotating member 35 is configured to form a screw similarly to the rotating member 33. The rotating member 35 is configured such that the depth of the spiral groove is the same as that of the rotating member 33. The rotating member 35 is connected to a first deaeration section 60 that deaerates the material kneaded in the first accommodation space S1. The details will be described later.

(Rotating members 36 to 39)
The rotating members 36 and 37 are provided adjacent to the rotating member 35 on the downstream side of the rotating member 35 in the first accommodation space S1. The rotating members 36 and 37 are configured to have plate-like members arranged in a similar manner to the rotating member 32. The rotating members 36 and 37 have spirals with small undulations, and the rotating directions of the spirals of the rotating members 36 and 37 are different from each other.

The rotating members 38 and 39 are provided adjacent to the rotating member 37 on the downstream side of the rotating member 37 in the first accommodation space S1. The rotating members 38 and 39 are configured to form a screw similarly to the rotating member 33. The screws of the rotating members 38 and 39 have the same depth of spiral grooves as the rotating member 33. The rotating member 38 and the rotating member 39 are configured so that the directions of spiral rotation are reversed.

By reversing the spiral rotation directions of the rotating members 36, 38 and 37, 39, the material sent from the rotating member 35 is temporarily pushed back to the upstream side of the rotating shaft by the rotating members 37, 39. Then, move downstream. As a result, the material remains in the rotating members 36 to 39 for a relatively long time, and compression is performed so that the density of the material is improved. The portion of the first accommodation space S1 where the rotating members 36 to 39 are arranged can be called a compression section that compresses the material.

(Rotating members 41, 42)
The rotating member 41 is provided adjacent to the rotating member 39 on the downstream side of the rotating members 35 and 39 in the first accommodation space S1. The rotating member 42 is provided adjacent to the rotating member 41 on the downstream side of the rotating member 41 in the first accommodation space S1. The rotating members 41 and 42 are configured to form screws similarly to the rotating member 33, and the rotating member 42 is configured to have a shorter spiral pitch than the rotating member 41. The rotating members 41 and 42 are connected to a second deaeration section 70 that deaerates the material accommodated in the first accommodation space S1.

In this way, the rotating members 31 to 39, 41, and 42 have a spiral shape, and the rotating member 31 is arranged directly below the input part 20, and the rotating member 31 is arranged downstream of the rotating shaft than the rotating member 31, and the rotating member The rotating member 33 is provided with a spiral groove formed shallower than that of the rotating member 31. With this configuration, even if at least part of the material is normally difficult to be sent downstream by the screw in a twin-screw kneading device, at least part of the material can be sent downstream by the rotating member 31 for kneading. By doing so, a biomass masterbatch can be efficiently produced.

Further, the rotating members 31 to 39, 41, and 42 include a rotating member 35 provided downstream of the rotating member 34 in the first accommodation space S1. A first degassing section 60 is connected near the rotating member 35 . The first degassing section 60 includes a screw 61 and a third accommodating section 62. The screws 61 rotate in a direction parallel to the direction intersecting the rotation axes of the rotating members 31 to 39, 41, and 42, and are arranged in pairs. The third accommodating part 62 includes a third accommodating space S3 that accommodates the screw 61, is connected to the first accommodating part 10, and is connected to a pump or the like that can discharge gas generated in the first accommodating space S1 by suction. . By configuring in this way, it is possible to further discharge unnecessary moisture while leaving the solid components of the material in the first storage space S1, similar to the dehydration section 50.

Further, the rotating members 31 to 39, 41, and 42 include a rotating member 41 provided downstream of the rotating member 35 in the first accommodation space S1, and a rotating member 42 provided adjacent to the rotating member 41. . A second degassing section 70 is connected near the rotating member 41. The second degassing section 70 includes a screw 71 and a fourth accommodating section 72. The screws 71 rotate in a direction parallel to a direction intersecting the rotation axis of the rotating member 41, and are arranged in pairs. The fourth accommodating part 72 includes a fourth accommodating space S4 that accommodates the screw 71, is connected to the first accommodating part 10, and is connected to a pump that can discharge gas generated in the first accommodating space S1 by suction. By configuring in this way, unnecessary moisture can be further discharged while leaving the solid components of the material in the first accommodation space S1, similarly to the first degassing section 60. Further, by connecting the second degassing section 70 not to the rotating member 42 but near the rotating member 41 whose spiral pitch is relatively large, unnecessary moisture can be easily discharged from the first accommodation space S1. .

Note that the ratio of the rotating members 32 and 34 to the overall length in the longitudinal direction It can be.

(Dehydration section 50)
The dehydration section 50 is configured to discharge (dehydrate) gas-liquid components such as moisture kneaded in the first storage section 10. As shown in FIG. 5, the dewatering section 50 is connected to the first accommodating section 10 near the boundary between the rotating members 33 and 34 from a direction intersecting the rotation axes of the rotating members 33 and 34. Near the boundary between the rotating member 33 and the rotating member 34 in the first housing space S1, the internal pressure in the first housing space S1 at least during kneading can be configured to be the saturated vapor pressure.

As shown in FIG. 5, the dewatering section 50 includes a screw 51 (corresponding to a third screw), a second storage section 52, and a drive section 53. The screw 51 rotates in a direction intersecting the rotating members 31 to 39, 41, and 42, and is configured to form a pair. The drive unit 53 is configured to include a motor that rotates the screw 51. The second accommodating part 52 is connected to the first accommodating part 10 as shown in FIG. 5, and includes a casing etc. in which a second accommodating space S2 for accommodating the screw 51 is provided. The second accommodating portion 52 discharges moisture from the second accommodating space S2. The second accommodating portion 52 is provided with an opening (not shown) through which moisture can be discharged. The opening can be provided in the upper part of the second accommodating part 52 or the like.

As described above, the rotating members 31 to 39, 41, and 42 are arranged between the rotating member 31 and the rotating member 33, and the rotating member 32, which has plate-like members arranged side by side on the rotating shaft, and and a plate-shaped rotating member 34 disposed on the downstream side of. A dewatering section 50 is connected near the rotating member 33 and the rotating member 34. The dewatering section 50 includes a screw 51 and a second accommodating section 52. The screws 51 rotate in a direction parallel to the width direction Y that intersects with the rotation axis, and are arranged in pairs. The second accommodating part 52 includes a second accommodating space S2 that accommodates the screw 51, and has an opening that is connected to the first accommodating part 10 and can drain water. With this configuration, unnecessary water and the like can be removed while leaving the solid components contained in the material in the first storage space S1 of the first storage section 10.

(First degassing section 60)
The first degassing section 60 is configured to be connected to the first housing section 10 near where the rotating member 35 is arranged. The first degassing section 60 includes a screw 61 (corresponding to the fifth screw), a third accommodating section 62, and a driving section 63, as shown in FIG. The screws 61 rotate in a direction intersecting the rotational axes of the rotating members 31 to 39, 41, and 42, and are arranged in pairs. The drive unit 63 is configured to include a motor and the like that rotate the screw 61 similarly to the dewatering unit 50. The third accommodating part 62 is connected to the first accommodating part 10 in the vicinity of the rotating member 35, and includes a casing and the like in which a third accommodating space S3 for accommodating the screw 61 is provided. The third storage section 62 is connected to a vacuum pump or the like capable of sucking the gas-liquid component generated in the first storage space S1 via the third storage space S3.

(Second deaeration section 70)
The second degassing section 70 is configured to be connected to the first accommodating section 10 near where the rotating member 41 is arranged. As shown in FIG. 5, the second degassing section 70 includes a screw 71 (corresponding to the eighth screw), a fourth accommodating section 72, and a driving section 73. The screws 71 rotate in a direction intersecting the rotational axes of the rotating members 31 to 39, 41, and 42, and are arranged in pairs. The drive unit 73 is configured to include a motor and the like that rotate the screw 71 similarly to the first deaeration unit 60 . The fourth accommodating part 72 is connected to the first accommodating part 10 in the vicinity of the rotating member 41, and includes a casing etc. in which a fourth accommodating space S4 for accommodating the screw 71 is provided. The screw 51 of the dewatering section 50, the screw 61 of the first degassing section 60, and the screw 71 of the second degassing section 70 are rotated along the width direction Y to the extent that the operations of the rotating members 31 to 39, 41, and 42 are not hindered. It extends to approach the rotating members 31-39, 41, and 42. The fourth storage section 72 is connected to a vacuum pump or the like capable of sucking the gas-liquid component generated in the first storage space S1 via the fourth storage space S4. Note that the second accommodating part 52, the third accommodating part 62, and the fourth accommodating part 72 are illustrated in a simplified manner in FIG. 5 for convenience.

In this way, by configuring the twin-screw kneading device 1 to include the first degassing part 60 and the second degassing part 70 as the two degassing parts, kneading was performed using a material with a high moisture content. At this time, the first degassing section 60 and the second degassing section 70 can perform dehydration more efficiently, and remove unnecessary water and the like from the biomass masterbatch.

(Discharge section 80)
The discharge section 80 is provided adjacent to the outside of the first storage section 10 on the downstream side, as shown in FIG. 1 and the like. The discharge section 80 is provided to form the material (hereinafter also referred to as a kneaded material) deaerated in the first storage space S1 of the first storage section 10 into a string shape. In this embodiment, the discharge part 80 is provided with a plurality of hole shapes provided at the end in the longitudinal direction It is configured to include a member. The discharge section 80 can be heated by providing a heating device such as a heater in the same manner as the rotating members 31 to 39, 41, 42, etc. arranged in the first storage section 10.

(Cooling section 90)
The cooling unit 90 is provided to cool the string-like kneaded material discharged from the first storage unit 10. The cooling unit 90 includes a conveyor 91, a liquid supply unit 92, and a gas supply unit 93, as shown in FIG.

The conveyor 91 is provided adjacent to the discharge section 80. The conveyor 91 is configured to convey the kneaded material discharged from the discharge section 80 to the cutting section 110, as shown in FIG. In this embodiment, the conveyor 91 is configured to extend along an oblique direction that is inclined from the longitudinal direction X toward the positive direction of the height direction Z, as shown in FIG. However, the extending direction of the conveyor 91 is an example, and the specific conveying direction of the conveyor is not limited to that shown in FIG. 2 and the like as long as the kneaded material can be conveyed to the cutting section 110.

The liquid supply section 92 is configured to supply relatively low temperature cooling water to the kneaded material conveyed on the conveyor 91. The liquid supply section 92 is configured by arranging a plurality of injection nozzles in the transport direction of the conveyor 91, which are connected to a cooling water supply source through a hose or the like.

The gas supply unit 93 is configured to supply a gas such as air adjusted to a predetermined temperature to the kneaded material conveyed on the conveyor 91. The gas supply section 93 is configured to include a duct (not shown) and a blower connected to the duct and capable of injecting gas toward the kneaded material on the conveyor 91.

(Cutting section 110)
The cutting section 110 is configured to cut the kneaded material discharged from the discharge section 80 and cooled in the cooling section 90 into a predetermined length. As shown in FIG. 1, the cutting section 110 can include a feed roller 111 for feeding the kneaded material, and a cutting roller 112 equipped with a blade for cutting the fed kneaded material. Moreover, the cooled kneaded material can be subjected to a drying process in equipment such as a drying chamber (which can be called a drying section).

The average diameter of the biomass masterbatch that has become pelleted through the cutting section 110 is 0.5 to 30 mm, 0.5 to 20 mm, 0.5 to 10 mm, 1 to 8 mm, 2 to 6 mm, or 2 to 5 mm. be. Note that the average diameter of the biomass masterbatches obtained in Examples was 4 to 5 mm. The method for measuring the average diameter of the biomass masterbatch can be the same as the method for measuring the average diameter of starch.

In this way, a biomass masterbatch according to one embodiment of the present invention can be obtained. In addition, biomass masterbatches can be used for packaging materials, agricultural materials, electronic equipment housings, home appliance housings, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily miscellaneous goods. It can be applied to at least one type of use selected from the group consisting of: Among these, it is suitable for application to packaging materials and agricultural materials.

More preferably, a molded article obtained by molding a resin mixture containing a masterbatch and a diluent resin is applied to the above-mentioned use.

Below, a resin mixture and its manufacturing method, a molded article, and its manufacturing method will be explained.

<Resin mixture and its manufacturing method>
In one aspect of the invention, a resin mixture is provided that includes a biomass masterbatch and a diluent resin. Moreover, in one aspect of the present invention, a method for producing a resin mixture is provided, which includes mixing a biomass masterbatch and a diluent resin.

In one embodiment of the present invention, the biomass masterbatch and the diluting resin can be mixed using known techniques as appropriate. For example, the biomass masterbatch and the diluent resin can be mixed using a known mixing device such as a tumbler mixer, a ribbon blender, or a V-type mixer.

In one embodiment of the present invention, the content ratio of the biomass masterbatch in the resin mixture is 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, or , 40% by weight or more. In one embodiment of the present invention, the content ratio of the biomass masterbatch in the resin mixture is 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, or 45% by weight or less. It is.

In one embodiment of the present invention, the content ratio of the diluting resin in the resin mixture is 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, or , 60% by weight or less. In one embodiment of the present invention, the content ratio of the diluting resin in the resin mixture is 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, or 55% by weight or more. It is.

In one embodiment of the present invention, the content ratio of starch in the resin mixture is 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 65% by weight or more. % by weight or more. In particular, biomass materials that account for 25% by weight or more are carbon-neutral materials and serve as a countermeasure against global warming. In one embodiment of the present invention, the content ratio of starch in the resin mixture is 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight It can be:

In one embodiment of the invention, the diluent resin can be a polyethylene, such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or high density polyethylene (HDPE). A commercially available polyethylene may be, but is not particularly limited to, Evolu® SP1510 from Prime Polymer Co., Ltd.

<Molded product and its manufacturing method>
In one aspect of the present invention, a molded article is provided by molding a resin mixture.

In one embodiment of the present invention, the molding process is inflation molding, sheet molding, or injection molding. Among these, inflation molding is preferred.

In one embodiment of the present invention, the molded article is a film or a sheet. When the molded product is a film, the thickness is preferably from 10 μm to 100 μm, and when the molded product is a sheet, the thickness is preferably more than 100 μm and 1 mm or less. Note that the thickness of the molded product can be measured according to JIS B7503:2017. In one embodiment, the molded article may be molded into a form other than a film or sheet.

In one embodiment of the present invention, the molded product may include packaging materials, agricultural materials, electronic device casings, home appliance casings, building material parts, automobile parts, motorcycle parts, aircraft parts, and railway vehicle parts. and daily necessities. Among these, when molded products are made into films, garbage bags (bags made of resin that collect garbage) and plastic shopping bags (resin bags handed out at the cash register in retail stores such as convenience stores and supermarkets to put purchased items to take home) are used. It can be used for packaging materials such as bags made of Note that examples of agricultural uses include, but are not limited to, agricultural mulch sheets and the like.

The temperature at which the resin mixture is molded into a film or sheet, etc. is preferably 120 to 190°C, from the viewpoint of suppressing discoloration and maintaining strength of the resulting molded product, preferably 140 to 180°C. It is more preferable that there be.

This application includes the following aspects and forms.

1. It contains starch and at least one resin selected from the group consisting of polyethylene, ionomer resins and acrylate copolymers, and has an MFR of 3.3 to 4.2 g/10 min at 190°C and 10 kgf, and A biomass masterbatch having a content ratio of more than 60% by weight.

2. The starch is rice or derived therefrom, 1. Biomass masterbatch described in.

3. The polyethylene is composed of at least two types, 1. or 2. Biomass masterbatch described in.

4. 1. At least one of the resins is biopolyethylene. ~3. The biomass masterbatch according to any of the above.

5. 1 containing at least one additive selected from the group consisting of glycerol, polyglycerol, glycerin fatty acid ester, polyglycerin fatty acid ester, polyalkylene glycol, and polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof. ．． ~4. The biomass masterbatch according to any of the above.

6. 5. The additive contains a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and a glycerin fatty acid ester. Biomass masterbatch described in.

7. A method for producing a biomass masterbatch, comprising kneading starch and at least one resin selected from the group consisting of polyethylene, an ionomer resin, and an acrylate copolymer in a production apparatus.

8. 7. The starch is rice or derived therefrom. The manufacturing method described in.

9. 7. At least one of the resins has a melting point of 110°C or less. or 8. The manufacturing method described in.

10. MFR of at least one of the resins at 190° C. 2.16 kgf is 15 g/10 min or more, and MFR of at least one of the resins at 190° C. 2.16 kgf is less than 15 g/10 min. 7. ~9. The manufacturing method according to any one of.

11. 7. At least one of the resins is biopolyethylene. ~10. The manufacturing method according to any one of.

12. 7. Containing at least one additive selected from the group consisting of glycerol, polyglycerol, glycerin fatty acid ester, polyglycerin fatty acid ester, polyalkylene glycol, and polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof. ．． ~11. The manufacturing method according to any one of.

13. 12. The additive contains a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and a glycerin fatty acid ester. The manufacturing method described in.

14. 7. Pregelatinization of the starch is initiated within the manufacturing device. ~13. The manufacturing method according to any one of.

15.1. ~6. A resin mixture containing the masterbatch according to any one of the above and a diluting resin and having a starch content ratio of 25% by weight or more.

16.15. A molded product obtained by molding the resin mixture described in .

17. 16. The molding process is inflation molding. Molded products described in .

18. 16. It is a film or sheet. or 17. Molded products described in .

19. At least one selected from the group consisting of packaging materials, agricultural materials, electronic device casings, home appliance casings, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily necessities. 16. Used for one type of purpose. ~18. Molded products described in any of the above.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the technical scope of the present invention is not limited only to the following examples.

<Preparation of biomass masterbatch>
(Experiment example 1)
As a material,
As starch, 78.7 parts by weight (rice solid weight: 70 parts by weight) of polished rice with an average diameter of 5 mm (manufactured by Niigata Kenbei Co., Ltd., medium polished rice, moisture content 11% by weight),
As resin A, 19.7 parts by weight of polyethylene (kernel KS340T, manufactured by Japan Polyethylene Co., Ltd.) with an MFR (190° C./2.16 kgf) of 3.4 g/10 min,
As resin C, 8 parts by weight of polyethylene (Kernel KJ640T, manufactured by Japan Polyethylene Co., Ltd.) with an MFR (190° C./2.16 kgf) of 30 g/10 min,
As additive A, 4 parts by mass of maleic anhydride-modified polypropylene (MG-441P manufactured by Riken Vitamin Co., Ltd.) (MAPP 3 wt%/total amount (solid equivalent)), and
As additive B, 2 parts by weight (solid equivalent) of glycerin fatty acid ester (acetylated monoglyceride; glycerin diacetomonolaurate, manufactured by Riken Vitamin Co., Ltd., Biosizer, listed on the positive list of Japan Bioplastics Association (JBPA)),
was used.

The above materials were kneaded using a twin-screw kneading device 100 that rotates in the same direction as shown in FIG.

The L/D ((total screw length in the x direction)/(cross-sectional diameter length of one screw) in FIG. 5) of the rotating member of the twin-screw kneading device 100 was set to 50.

The rotating members 31 to 39, 41, and 42 described above were used as the rotating members of the rotating section 30. The ratio of the rotating members 32 and 34 (kneading block ratio) to the overall length of the rotating members 31 to 39, 41, and 42 in the longitudinal direction X was set to 25%.

The above materials were supplied from the input section 20 to the first storage space S1. In addition, when the material was solid, it was supplied from a hopper, and when the material was liquid, it was supplied from the hopper using a tube pump. Further, 3 parts by weight (ie, 2.1 parts by weight in Example 1) of distilled water based on 100 parts by weight of starch was also supplied from the hopper to the first storage space S1 using a tube pump.

The rotational speed of the rotating members 31 to 39, 41, and 42 was 280 rpm. Then, in the first housing space S1, a portion corresponding to the input portion was heated to 80° C., a portion corresponding to the resin melting portion was heated to 160° C., and a portion corresponding to the kneading portion was heated to 180° C. Note that when the material was sent from the rotating member 33 to the rotating member 34, water was removed by the dehydrating section 50. Further, the connecting portion between the first degassing section 60 and the second degassing section 70 in the first housing space S1 was heated to 160°C, the portion corresponding to the compression portion was heated to 170°C, and the discharge portion 80 was heated to 180°C.

(Examples 2 and 3 and Comparative Examples 1 to 10)
Biomass masterbatches of Examples 2 and 3 and Comparative Examples 1 to 10 were produced in the same manner as in Example 1, except that the materials and their contents were changed to those shown in Table 1.

<Starch aggregation level>
The aggregation of starch was visually observed using a sample obtained by taking out 3 g of the biomass masterbatch obtained from the cutting section 110 and stretching it into a flat shape by hot pressing at 170 ° C. Then, it was confirmed whether starch agglomerates (diameter of 0.1 mm or more) were observed. Evaluation was performed according to the following criteria.

Evaluation criteria for starch agglomerates A: Agglomerates cannot be confirmed in the sample.

B: 10 or less aggregated particles can be confirmed in the sample.

C: 11 to 20 aggregate particles can be confirmed in the sample.

D: 21 or more aggregated particles can be confirmed in the sample.

<Moldability evaluation>
Using a tumbler mixer, 43 parts by weight of the biomass masterbatch with a rice blending ratio of 70% by weight obtained in Example 1 and 57 parts by weight of Evolu (registered trademark) SP1510 (manufactured by Prime Polymer Co., Ltd.) as a diluting resin were mixed. By uniformly stirring and mixing, a resin mixture having a starch content of 30% by weight was obtained. The resin mixture was formed into a film using an inflation molding machine.

Next, using the biomass masterbatches of Examples 2 and 3 and Comparative Examples 1 to 10, the mixture ratio of these biomass masterbatches and the diluting resin was adjusted as appropriate to achieve a starch content of 30% by weight. A resin mixture was prepared in the same manner as in Example 1, except that a certain resin mixture was prepared. Using these, film formation was performed using an inflation molding machine at a temperature range of 160 to 170°C. The results are shown in Table 1.

Criteria for evaluating moldability ◎: Can be processed with high productivity similar to petroleum-based resins, and no molding defects occur.
○: Can be processed and no molding defects occur.
○△: Processing is possible, but some molding defects occur.
Δ: Can be processed, but many molding defects occur.
×: Can be processed, but molding defects occur extremely often.
XX: Cannot be processed.

<Biomass degree>
The biomass degree is the proportion (weight %) derived from biomass in the resin mixture (resin). For example, since the biomass content of Resin E in Example 3 is 95%, the biomass content in the biomass masterbatch is 65% by weight of rice and 9.3% by weight of biomass in the resin (=9.8% by weight x (95% by weight). /100)) for a total of 74.3% by weight.

<Melt flow rate>
The measurement of MFR (190℃/2.16kgf) is based on JIS K 7210-1:2014 (ISO1133-1:2011), determination of melt flow rate (MFR) and melt volume flow rate (MVR) of plastics and thermoplastics. - Part 1: Values measured in accordance with Standard Test Method.

The measurement of MFR (190° C./10 kgf) was performed in the same manner as in the measurement of MFR (190° C./2.16 kgf) except that only the weight (load) of the weight was changed to 10 kgf.

<Consideration>
The biomass masterbatches of Examples 1 to 3 had MFR values within the standard range (3.30 to 4.20 g/10 min), no agglomerated particles were observed, and had excellent moldability.

Comparative Examples 2, 4 to 8, and 10 and Examples 1 and 2 are combinations of Resin A, which has a relatively low MFR, and Resin C, which has a relatively high MFR. MFR is relatively low compared to a resin with a relatively high MFR.If the content weight is low, the MFR of the biomass masterbatch tends to be high, and vice versa, the MFR of the biomass masterbatch tends to be low. In Examples 1 and 2, since the content weight of resin A relative to the content weight of resin C (resin A/resin C) is appropriate, it is presumed that the MFR of the biomass masterbatch is in an appropriate range. The MFR of the biomass masterbatch of Comparative Example 7 was considerably lower than the standard value, presumably because it did not contain Additive B, which can function as a plasticizer or a pregelatinization accelerator. Moreover, the reason why the aggregation level of Comparative Example 7 was B is presumed to be because the melt viscosity during kneading increased, resulting in over torque in the equipment and reduction in processing capacity due to insufficient thermal fluidity.

Example 3 is a combination of resin A, which has a relatively low MFR, and resin E, which has a relatively high MFR. Since the content weight of resin A relative to the content weight of resin E (resin A/resin E) is appropriate, it is presumed that the MFR of the biomass masterbatch is within an appropriate range.

Comparative Example 3 is a combination of Resin D, which has a relatively low MFR, and Resin B, which has a relatively high MFR. In Comparative Example 3, the ratio of the resin with a relatively low MFR to the resin with a relatively high MFR is the lowest among the examples, and since resin B is polypropylene, the melt viscosity during kneading is low, and the ratio of the resin with a relatively low MFR to the resin with a relatively high MFR is the lowest. The lack of shear resulted in poor agglomeration levels, and the MFR of the biomass masterbatch was the highest among the examples.

On the other hand, Comparative Example 1 is a combination of resin A with a relatively low MFR and resin B with a relatively high MFR, and the ratio of the resin with a relatively low MFR to the resin with a relatively high MFR is relatively high. Therefore, it seems that the MFR of biomass masterbatch should tend to be lower. However, polypropylene and polyethylene were not uniformly miscible in the biomass masterbatch, and MFR measurements of the biomass masterbatch showed strong properties of polypropylene.Also, due to the presence of free polypropylene with insufficient compatibility, It is presumed that the MFR of the biomass masterbatch exceeded the upper limit of the standard value.

Comparative Example 9 is a combination of Resin C, which has a relatively high MFR, and Resin D, which has a relatively low MFR. It is thought that the MFR of the biomass masterbatch is low because the ratio of the resin with a relatively low MFR to the resin with a relatively high MFR is relatively high.

Next, we will discuss moldability.

The biomass masterbatch of Example 1 has a significantly high starch blending ratio of 70% by weight and has an appropriate MFR value, so it is possible to increase the mixing ratio of the diluent resin, making it possible to perform inflation molding. The quality was good in terms of ◎. It was confirmed that the biomass masterbatches of Examples 2 and 3 also had the same moldability as Example 1 because they had high starch blending ratios and appropriate MFR values.

On the other hand, the biomass masterbatch of the comparative example had a low blending ratio of starch and did not have an appropriate MFR value, so the inflation moldability was poor with XX to ○Δ.

Claims (15)

An additive containing starch, at least one resin selected from the group consisting of polyethylene, ionomer resins, and acrylate copolymers, a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and a glycerin fatty acid ester; , the MFR at 190°C and 10 kgf is 3.3 to 4.2 g/10 min, and the content ratio of starch is more than 60% by weight, a biomass masterbatch. The biomass masterbatch according to claim 1, wherein the starch is rice or derived therefrom. The biomass masterbatch according to claim 1, wherein the polyethylene is composed of at least two types. The biomass masterbatch according to claim 1, wherein at least one of the resins is biopolyethylene. starch and
At least one resin selected from the group consisting of polyethylene, ionomer resin, and acrylate copolymer;
an additive containing a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and a glycerin fatty acid ester;
The method for producing a biomass masterbatch according to claim 1, comprising kneading in a production apparatus. The manufacturing method according to claim 5 , wherein the starch is rice or rice-derived starch. The manufacturing method according to claim 5 , wherein at least one of the resins has a melting point of 110°C or less. MFR of at least one of the resins at 190° C. and 2.16 kgf is 15 g/10 min or more,
The manufacturing method according to claim 5 , wherein the MFR at 190° C. and 2.16 kgf of at least one of the resins is less than 15 g/10 min. The manufacturing method according to claim 5 , wherein at least one of the resins is biopolyethylene. The manufacturing method according to claim 5 , wherein gelatinization of the starch is started within the manufacturing apparatus. A resin mixture comprising the masterbatch according to claim 1 and a diluent resin, and having a starch content of 25% by weight or more. A molded article obtained by molding the resin mixture according to claim 11 . The molded article according to claim 12 , wherein the molding process is inflation molding. The molded article according to claim 12 , which is a film or a sheet. At least one selected from the group consisting of packaging materials, agricultural materials, electronic device casings, home appliance casings, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily necessities. The molded article according to claim 12 , which is used for one type of use.