JP2023110903A - Plasticized composite material and method for producing plasticized composite material - Google Patents

Abstract

To provide a material which is suitable for producing a vegetable food residue-containing composition that is excellent in moldability and is also excellent in functional characteristics such as a color and odor.SOLUTION: A plasticized composite material contains a vegetable food residue, and plasticized starch, in which the starch contained in the vegetable food residue is plasticized. There is also provided a method for producing a plasticized composite material containing a vegetable food residue, and plasticized starch. The production method includes a plasticization step of plasticizing a mixture of a vegetable food residue and a starch material, in which the vegetable food residue is plasticized in a wet state.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a plasticized composite material and a method for producing the plasticized composite material, and more particularly to a plasticized composite material containing vegetable food residue and a method for producing the plasticized composite material.

Plastic molded products manufactured using petroleum resources as raw materials are used in a wide range of applications such as containers for eating and drinking, various packaging materials such as sheets and films, cushioning materials, daily necessities, agricultural supplies, and other industrial materials. On the other hand, global warming due to greenhouse gases caused by mass consumption of plastic materials and depletion of petroleum resources are important issues to be tackled on a global scale in the long term.

Therefore, utilization of biomass materials is being studied in order to reduce the amount of plastic materials used. For example, US Pat. 25-50% by weight of the total composition of a thermoplastic synthetic polymer; 1-10% by weight of the total composition of a plasticizer; and 1-5% by weight of the total composition of a coupling agent. wherein said blending is carried out at a first temperature above room temperature.

Japanese Patent Publication No. 2015-511648

One of the biomass materials is vegetable food residue. As one method of utilization of vegetable food residues, it is conceivable to mix them with thermoplastic resins such as polyesters and polyolefins to produce thermoplastic compositions. However, a composition containing vegetable food residue and a thermoplastic resin may have poor moldability. Such compositions often also have problems such as color or odor.

An object of the present invention is to provide a material suitable for producing a vegetable food residue-containing composition which is excellent in moldability and sensory properties such as color and odor.

The present invention provides the following.
[1] vegetable food residue;
a plasticized starch;
A plasticized composite material comprising
The starch contained in the vegetable food residue is plasticized,
Said plasticized composite material.
[2] The plasticized composite material according to [1], wherein the total content of the vegetable food residue and the plasticized starch is 60% by mass or more relative to the weight of the plasticized composite material.
[3] The plasticized composite material according to [1] or [2], wherein the plasticized composite material further contains a polyhydric alcohol.
[4] The plasticized composite material according to [3], wherein the content of the polyhydric alcohol is 10% by mass or more with respect to the mass of the plasticized composite material.
[5] According to [3] or [4], wherein the total content of the vegetable food residue, the plasticized starch and the polyhydric alcohol is 80% by mass or more relative to the mass of the plasticized composite material. of plasticized composites.
[6] The plasticized composite according to any one of [1] to [5], wherein the vegetable food residue is a food material residue selected from vegetables, fruits, grains, coffee, and tea. material.
[7] Any of [1] to [6], wherein the vegetable food residue is a starch extraction residue derived from vegetables or grains, a fruit juice extraction residue derived from fruit, a coffee or tea beverage extraction residue, or a grain polishing residue. The plasticized composite material according to claim 1.
[8] The plasticized composite material according to any one of [1] to [7], wherein the vegetable food residue is mainly composed of residue pieces having a size of 5 mm or less.
[9] The plasticized composite material according to any one of [1] to [8], wherein the plant food residue comprises ground food residue.
[10] The plasticizing according to any one of [1] to [9], wherein the content of the thermoplastic resin in the plasticized composite material is 5% by mass or less with respect to the mass of the plasticized composite material. composite material.
[11] The plasticized composite material according to any one of [1] to [10], wherein the plasticized composite material is mixed with a thermoplastic resin and used to produce a composition for producing a molded article. .
[12] A method for producing a plasticized composite material containing vegetable food residue and plasticized starch,
The manufacturing method includes a plasticizing step of plasticizing a mixture of vegetable food residue and starch material,
The vegetable food residue is subjected to the plasticizing treatment in a wet state.
The manufacturing method.
[13] The production method according to [12], wherein the vegetable food residue is subjected to the plasticizing treatment in a state where the moisture content is 5% by mass or more.

Compositions obtained by mixing the plasticized composite material according to the present invention with a thermoplastic resin have good moldability and good organoleptic properties such as color and odor. Therefore, the composite material according to the invention is suitable for developing the utilization of plant food residues. In addition, the present invention also allows for a reduction in the amount of thermoplastic resins such as polyesters and polyolefins utilized. That is, the present invention can greatly advance the upcycling of vegetable food residues and contribute to the achievement of SDGs.

SEM pictures to show the plasticization of starch in vegetable food residue. SEM pictures to show the plasticization of starch in vegetable food residue. It is a figure for demonstrating extrusion pressure difference (DELTA)P. FIG. 2 is a schematic diagram of a pressurization tester used for measuring the extrusion pressure difference ΔP. It is a schematic diagram for demonstrating press molding.

Preferred embodiments for carrying out the present invention will be described below. The embodiments described below are representative embodiments of the present invention, and the scope of the present invention is not limited only to these embodiments.

The present invention will be described in the following order.
1. First embodiment (plasticized composite material)
2. Second Embodiment (Method for Manufacturing Plasticized Composite Material)
3. Example

1. First embodiment (plasticized composite material)

As described above, compositions containing vegetable food residues and thermoplastic resins may have problems in moldability, color, odor, and the like. Such problems tend to occur particularly when the content of vegetable food residue is increased.

The inventors have found that certain plasticized composite materials can improve moldability and organoleptic properties such as color or odor in compositions obtained in combination with thermoplastic resins. In one embodiment, the plasticized composite material of the present invention comprises plant food residue and plasticized starch, wherein the starch contained in the plant food residue is plasticized. The plasticized composite material is suitable for use in combination with thermoplastic resins. For example, a composition (especially a thermoplastic composition) comprising the plasticized composite material and a thermoplastic resin has excellent moldability and also excellent sensory properties.

The composition of the present invention will be described in more detail below.

(1) Composition

(1-1) Vegetable Food Residue The plasticized composite material of the present invention contains vegetable food residue. The vegetable food residue may be a residue containing plant fibers. For example, the vegetable food residue may contain dietary fiber, for example, 10 g or more, preferably 15 g or more, more preferably 20 g or more, more preferably 30 g or more, 40 g or more, per 100 g of the dry weight of the residue. , or 50 g or more, or even 60 g or more, or 70 g or more. The dietary fiber content may be, for example, 99g or less, 97g or less, or 95g or less, or even 90g or less, 85g or less, or 80g or less per 100g dry weight of the residue. Food residues with high dietary fiber content are often difficult to mix with thermoplastic resins. The quality of the composition containing is improved.

The content of dietary fiber contained in vegetable food residue per 100 g of dry weight is the product obtained by freeze-drying the vegetable food residue, grinding it with a mill, and passing the ground product through a 0.8 mm mesh. , the dietary fiber was extracted according to the Prosky method (Prosky L et al., Determination of total dietary fiber in foods and food products, Collaborative study. J Assoc Off Anal Chem. 58:677-679, 1985.) and measured.

Said vegetable food residue may be, for example, a food material residue selected from among vegetables, fruits, cereals, coffee and tea. A variety of plant food residues may be utilized in the present invention.

In one embodiment, the vegetable food residue may be a vegetable food residue. The vegetable residue may be, for example, the residue of potatoes, root vegetables, legumes, leafy stem vegetables, fruit vegetables, cruciferous vegetables, or leafy vegetables.
Potatoes, sweet potatoes, taros, and yams can be mentioned as the potatoes. Examples of root vegetables include beets, radishes, carrots, and turnips. Examples of the legumes include soybeans, adzuki beans, broad beans, and green soybeans. Thus, the present invention can be applied to various vegetable food residues.

In another embodiment, the vegetable food residue may be a fruit food residue. The fruit may be the residue of citrus, pome, stone fruit, or berries.
Examples of the citrus fruits include tangerines, grapefruits, and oranges. Examples of the pome fruits include apples and pears. Examples of the stone fruits include peach and Japanese apricot. The berries include grapes and blueberries. Thus, the present invention can be applied to various fruit food residues.

In yet another embodiment, the plant food residue may be grain residue. The cereal residue may be rice, corn, barley (such as wheat, barley, or rye), or buckwheat residue. An example of the grain residue is rice bran.
In yet another embodiment, the plant food residue may be coffee or tea residue. For example, the residue may be coffee liquid extraction residue (eg coffee grounds) or tea beverage extraction residue (eg tea grounds).
Thus, the present invention can also be applied to vegetable food residues other than vegetables or fruits.

In one embodiment, the vegetable food residue is starch extraction residue from vegetables or grains, juice extraction residue from fruit, coffee or tea beverage extraction residue, or grain polishing residue (e.g. rice or wheat polishing residue). It's okay. In this embodiment, the vegetables may be any of the vegetables mentioned above, in particular potatoes, root vegetables or legumes. In this embodiment, the cereal may be rice, corn, or wheat, among others. In this embodiment, the fruit may be citrus, pome fruit, stone fruit or berry, in particular apple or grape.
Said residue may comprise, for example, skin parts. For example, when the residue is potato residue, the residue may or may not contain potato skin. The said residue may contain the protein which arises at the time of juicing of potatoes. Moreover, the said residue may contain components other than the protein produced at the time of the said squeezing.
Moreover, when the residue is a root vegetable, the residue may contain root skin of the root vegetable and/or juice residue of the root vegetable. For example, carrot peels or pomace may be included in the residue. The residue may contain proteins produced during squeezing of root vegetables. Moreover, the said residue may contain components other than the protein produced at the time of the said squeezing.
In addition, when the residue is beans, the residue may contain bean skins of the beans and/or juice residue of the beans. Such skins include, for example, sheaths and pellicles. For example, the residue may include green soybean skins or pomace. The residue may contain proteins produced during juicing of legumes. Moreover, the said residue may contain components other than the protein produced at the time of the said squeezing.
Moreover, when the residue is a fruit, the residue may or may not contain the pericarp. For example, the residue may include apple or grape skins or pomace.
Thus, the residue may be a residue resulting from the processing of the plant food, such as the peel of the plant food or the extraction residue (eg, pomace). In addition, the residue may contain components such as protein produced during juicing or processing of the plant food.
These residues are particularly abundant in food manufacturing processes. The compositions of the present invention are particularly suitable from an upcycling point of view since such residues can be utilized.

Preferably, the plant food residue may be a residue mainly composed of residue pieces having a size of 5 mm or less. The use of residue whose main component is residue pieces having such a size contributes to the improvement of the physical properties of the composition obtained in combination with the thermoplastic resin. In this specification, the residue mainly composed of the residue pieces is, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more with respect to the total mass , having a size of 5 mm or less.
The residue containing the residue pieces as a main component may be obtained, for example, by pulverizing the residue raw material. The type of pulverization treatment may be appropriately selected by a person skilled in the art according to, for example, the type of residual raw material. That is, the plant food residue may contain a pulverized plant food residue. Grinding may result in a residue based on residue pieces having a size of 5 mm or less, as described above.

Particularly preferably, the vegetable food residue may be a ground vegetable food residue. The ground material may be a ground material having a fiber diameter of, for example, 1000 μm or less, preferably 200 μm or less, more preferably a ground material having a fiber diameter of 150 μm or less, and particularly preferably a fiber diameter of 100 μm or less. It may be a ground product that is Moldability is improved by using the above-mentioned vegetable food residue as such a ground product. In addition, by using the ground product, the quality of the molded body, such as surface roughness and/or elongation, is improved.
The ground product is obtained, for example, by grinding the residue with a stone grinder.
The fiber diameter of the ground material is measured by microscope imaging.

Said plant food residue may preferably be a residue that has not been dried. The moisture content of the residue may be, for example, 5% by weight or more, in particular 10% by weight or more, 20% by weight or more, or 30% by weight or more, and in a particular embodiment said water content is It may be 50% by mass or more. The moisture content may be, for example, 90% by weight or less or 80% by weight or less. Moisture content is measured by the loss-on-drying method. A composite material suitable for improving the moldability and organoleptic properties of the composition by using the vegetable residue in such a wet state to produce a plasticized composite material (also called a masterbatch). is obtained. That is, the plant food residue may be used wet to produce the masterbatch.
Vegetable food residues with too low a water content may be used for the production of said masterbatch in the form of a mixture of water and said residue. Moreover, when a dried residue is used, water may be added to the dried residue as appropriate.

In a preferred embodiment, the starch contained in the plant food residue in the composite material of the invention may be in a plasticized state. The plasticization of the starch derived from vegetable food residues contributes to the improvement of the moldability of the composition containing the composite material and the thermoplastic resin. The plasticized state may be achieved, for example, in a plasticizing process for producing said composite material from vegetable food residues and plasticized starch.
In a preferred embodiment, the vegetable food residue and the starch material forming the plasticized starch described below are plasticized together. Particularly preferably, the vegetable food residue and the starch material are extruded (kneaded) together and plasticized in an extruder. Composites obtained by plasticizing these two components in this manner are particularly suitable for combination with thermoplastic resins.
A scanning electron microscope (SEM), for example, can confirm that the starch contained in the composite material is plasticized. A SEM photograph is shown in FIG. 1A. The center of the figure is an SEM photograph of the vegetable food residue (residue obtained by starch extraction from potatoes) before plasticization treatment. The left side of the figure is an SEM photograph of a product obtained by mixing the residue with glycerin and heat-treating the mixture. The right side of the figure is an SEM photograph of a product obtained by mixing the residue with glycerin and maleic acid and heat-treating the mixture. Starch granules can be seen in the photograph in the center of the figure, but no such granules can be seen in the photographs on the right side of the figure and in the enlargement. Thus, the starch in the vegetable food residue is plasticized by the plasticizing treatment. Also, as shown in FIG. 1B, in any case where propylene glycol, propylene glycol and acid (maleic acid), or propylene glycol and sugar (maltitol) were used instead of glycerin, of starch is plasticized. Thus, various plasticizers may be used for plasticizing the starch in the plant food residue.

(1-2) Plasticized starch

The plasticized composite material of the present invention comprises plasticized starch. The plasticized starch includes plasticized starch that is not starch derived from vegetable food residues. That is, the plasticized starch may be a plasticized starch material prepared separately from the vegetable food residue. Compositions made by blending a combination of plant food residue and plasticized starch into a thermoplastic resin have better moldability and are more compact than compositions made by blending only the plant food residue into a thermoplastic resin. Excellent in sensory properties.

The plasticized starch is a starch material that is in a plasticized state. For example, by plasticizing a mixture of the plant food residue and the starch material, the starch material in the mixture becomes plasticized starch. The composition obtained by mixing the composite material thus plasticized with the thermoplastic resin has excellent moldability and sensory properties.

Raw starch can be used as the starch material to be subjected to the plasticizing treatment, and examples thereof include underground starch and ground starch. The plasticized starch may be a plasticized underground starch or a plasticized ground based starch or a combination thereof.
Subterranean starch is starch accumulated underground, for example, starch accumulated in rhizomes or roots. Examples of underground starch include, but are not limited to, tapioca starch (cassava starch), potato starch, sweet potato starch, arrowroot starch, and bracken starch.
Terrestrial starch is starch accumulated on the ground, for example, starch accumulated in seeds and the like. Ground-based starches include, but are not limited to, corn starch, wheat starch, sago starch, acorn starch, and rice starch.

The starch material may be a modified starch (ie modified starch), in particular a modified underground starch or a modified ground starch or a combination thereof. Such modifications include chemically modified starches that have been chemically modified. Examples of chemically modified starches include acetoacetic esterified starch, acetic esterified starch, hydroxymethyl-etherified starch, hydroxypropyl-etherified starch, carboxymethyl-etherified starch, allyl-etherified starch, methyl-etherified starch, succinic acid ester starch, xanthogen acetate esterified starch, nitrate esterified starch, urea phosphate esterified starch, phosphate esterified starch, phosphate crosslinked starch, formaldehyde crosslinked starch, acrolein crosslinked starch, epichlorohydrin crosslinked starch, and the like.

When the starch material is corn starch, its particle size is preferably 5 µm or more, more preferably 10 µm or more, and even more preferably 15 µm or more. Although the upper limit of the particle size is not particularly limited, it is preferably 50 µm or less, more preferably 40 µm or less, and still more preferably 30 µm or less.

When the starch material is tapioca starch, its particle size is preferably 2 µm or more, more preferably 10 µm or more, and still more preferably 15 µm or more. Although the upper limit of the particle size is not particularly limited, it is preferably 40 µm or less, more preferably 30 µm or less, and still more preferably 25 µm or less.

When the starch material is potato starch, its particle size is preferably 2 µm or more, more preferably 20 µm or more, and still more preferably 30 µm or more. Although the upper limit of the particle size is not particularly limited, it is preferably 80 µm or less, more preferably 60 µm or less, and still more preferably 40 µm or less.

The starch material may also preferably have an equilibrium moisture content. The amount of equilibrium moisture is, for example, preferably 10% to 15% by weight, more preferably 10% to 14% by weight, even more preferably 10% to 13% by weight, based on the starch material weight. and more preferably 11% to 13% by weight. When mixed with a thermoplastic resin, the starch may preferably have a moisture content of 3% or less.

(1-3) other components

The composite material of the present invention may further contain other components. Such other ingredients may include, for example, polyhydric alcohols, low-melting additives, and high-melting additives.

In one embodiment, the composite material comprises at least one polyhydric alcohol. That is, the composite material may comprise a vegetable food residue, a plasticized starch, a thermoplastic resin and a polyhydric alcohol. Polyhydric alcohols may be used to facilitate the plasticization of starch, ie, function as starch plasticizers. In the present invention, plasticizers other than polyhydric alcohols may be used.

In the present invention, polyhydric alcohol refers to alcohol having two or more hydroxyl groups in the molecule. Such polyhydric alcohols are preferably polyhydric alcohols having 2 to 5 carbon atoms, and more preferably polyhydric alcohols having 2 to 4 carbon atoms. The polyhydric alcohol preferably has 2 to 5 hydroxyl groups (OH groups), more preferably 2 to 4 hydroxyl groups (OH groups).
Said polyhydric alcohols may include, for example, glycerin and glycol. Examples of such glycols include ethylene glycol and propylene glycol.
Said polyhydric alcohol may preferably comprise one or a combination of two or more selected from glycerin, ethylene glycol and propylene glycol. The composite material may contain, for example, preferably 10 to 40 parts by mass, more preferably 20 to 35 parts by mass, of the polyhydric alcohol with respect to 100 parts by mass of the plasticized starch. Also, the content of the polyhydric alcohol in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.

The composite material of the present invention may contain additives. Such additives include low-melting additives that have a melting point temperature lower than the melting temperature of the thermoplastic resin and melt at a relatively low temperature. Such a low-melting-point additive preferably melts at 100°C or less, more preferably melts at 60 to 100°C. Ester compounds that are liquid or solid at room temperature are preferably used as such low-melting-point additives. Specifically, low-melting-point additives include monoglycerides, diglycerides, triglycerides, acetylated monoglycerides, organic acid monoglycerides, medium-chain fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, special fatty acid esters, and higher alcohols. and fatty acid esters. Preferably, a glycerin-based fatty acid ester or the like is used. A low melting point additive melts at a relatively low temperature and is viscous, so it can act to entangle and stick to plant food residue.

The low melting point additive is, for example, preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass per 100 parts by mass of the total amount of vegetable food residue and plasticized starch. It may be blended at the content ratio.

The composite material may also include a high melting point additive having a higher melting point than the low melting point additive. Such high-melting additives have a melting point higher than that of the low-melting additive, preferably in the range of 100 to 150° C., and solidify before the low-melting additive to form a thermoplastic resin. may have a melting point lower than the melting temperature of Examples of such high-melting-point additives include fatty acid metal salts, hydrocarbons, higher alcohols, fatty amides, fatty acid esters, etc. Specific examples include magnesium stearate, zinc stearate, calcium stearate, stearin. Aluminum acid, sodium lauryl sulfate, magnesium lauryl sulfate, potassium benzoate, sodium benzoate, sodium stearyl fumarate and the like are used.

The high melting point additive is, for example, preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of vegetable food residue and plasticized starch. It may be blended at the content ratio.

As other additives, in order to improve the affinity between the composite material (particularly vegetable food residues and plasticized starch in the composite material) and the thermoplastic resin, a compatibilizer is used for the composite material of the present invention or the composite It may be included in the composition obtained by combining the material and the thermoplastic resin. The compatibilizer may be selected according to the type of thermoplastic resin. Examples of such compatibilizers include acid-modified polyolefin, acid-modified nylon, acid-modified polystyrene, acid-modified EVA, acid-modified ethylene copolymer, acid-modified acrylate, acrylic acid-modified EVA, and modified ethylene acrylate. can be done.

When the thermoplastic resin is a polyolefin-based resin, the compatibilizer is preferably an acid-modified polyolefin, and in particular can be a carboxylic anhydride-modified polyolefin or an olefin-based comonomer.

The carboxylic anhydride constituting the carboxylic anhydride-modified polyolefin may preferably be maleic anhydride. The compatibilizer is, for example, a maleic anhydride-grafted polyolefin resin, more particularly selected from the group consisting of maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified ethylene-propylene copolymer1 It may be one or a combination of two or more. The rubber component may be dispersed in the compatibilizer.

The compatibilizer is added to the composite material at a content ratio of, for example, 0.1% by mass to 10% by mass, more preferably 1.0% by mass to 5.0% by mass, relative to the mass of the composite material. may be included.

In one embodiment, the compatibilizer may be used as a component in making the composite material and also as a component in making the composition of the present invention from the composite material and the thermoplastic resin. may be used as an ingredient. As such, it may be used in each of these two manufacturing processes.

A coloring agent can be used as another additive.

The coloring agent can be used to color the biomass material-containing thermoplastic resin composition. Colorants include, for example, titanium oxide, carbon black, dyes, and pigments.

Further, as the other components, for example, an antioxidant, a cross-linking agent, an ultraviolet absorber, a foaming agent, an impact-resistant agent, and the like may be used. Commercially available products may be used as these additives.

(1-4) Content ratio The total content ratio of the vegetable food residue and the plasticized starch is, for example, 60% by mass or more, preferably 62% by mass or more, relative to the mass of the plasticized composite material, or It may be 64% by mass or more, particularly 70% by mass or more, preferably 72% by mass or more, 74% by mass or more, 76% by mass or more, 78% by mass or more, or 80% by mass or more. The total content of the vegetable food residue and the plasticized starch may be, for example, 99% by mass or less, preferably 98% by mass or less, 96% by mass or less, 94% by mass or less, relative to the mass of the plasticized composite material. It may be 92% by mass or less, or 90% by mass or less.

The content of the polyhydric alcohol is, for example, 10% by mass or more, preferably 12% by mass or more, more preferably 14% by mass or more, 16% by mass or more, or 18% by mass, relative to the mass of the plasticized composite material. % or more, or 20% by mass or more. Also, the content of the polyhydric alcohol may be, for example, 30% by mass or less, preferably 28% by mass or less, and more preferably 26% by mass or less, relative to the mass of the plasticized composite material.

The total content of the vegetable food residue, the plasticized starch, and the polyhydric alcohol is, for example, 80% by mass or more, preferably 82% by mass or more, and 84% by mass, based on the mass of the plasticized composite material. 86% by mass or more, 88% by mass or more, 90% by mass or more, 92% by mass or more, or 94% by mass or more. The total content of the vegetable food residue, the plasticized starch and the polyhydric alcohol is, for example, 100% by mass or less, 99% by mass or less, or 98% by mass or less with respect to the mass of the plasticized composite material. you can

The composite material may or may not contain a thermoplastic resin. When the composite material contains a thermoplastic resin, the content of the thermoplastic resin in the plasticized composite material is 5% by mass or less, 4% by mass or less, or 3% by mass or less with respect to the mass of the plasticized composite material. can be For example, a polyolefin-based resin or a polyester-based resin may be included at a content ratio within this numerical range. The content of the thermoplastic resin in the plasticized composite material may be, for example, 0% by mass or more, or may be 0% by mass with respect to the mass of the plasticized composite material. The description in (3) below also applies to the polyolefin-based resin and the polyester-based resin contained in the composite material. For example, the thermoplastic resin used for producing the composition described in (3) below and the thermoplastic resin contained in the composite material may be the same or different, preferably the same is. For example, if the former is a polyolefin resin, the latter may also be a polyolefin resin. When the former is a polyester-based resin, the latter may also be a polyester-based resin.

2. Second Embodiment (Method for Manufacturing Plastic Composite Material)
(2) Manufacturing method

The composite material of the present invention may be produced by mixing and heating the plant food residue and starch material. In one embodiment, said mixing and said heating may be performed stepwise, ie said mixing may be performed followed by said heating. In other embodiments, said mixing and said heating may occur simultaneously.
That is, the present invention also provides a method for producing a plasticized composite material comprising vegetable food residue and plasticized starch. The manufacturing method may include a plasticizing step of subjecting a mixture of plant food residue and starch material to a plasticizing treatment, wherein the plant food residue may be subjected to the plasticizing treatment in a wet state. The vegetable food residue may be subjected to the plasticizing treatment in a state where the moisture content is 5% by mass or more.

The vegetable food residue and starch material and other ingredients are mixed. The mixing may be performed at ambient temperature. Other components used in the mixing include the polyhydric alcohols. In addition, the other component may further include water and/or a modifier (maleic acid or maleic anhydride). The mixing may be performed, for example, using mixers commonly used in the art.

The vegetable food residue is as described in (1) above, and preferably may be a residue that has not been dried. The water content of the vegetable food residue may be, for example, 5% by mass or more, particularly 10% by mass or more, 20% by mass or more, 30% by mass or more, or 50% by mass or more. The moisture content may be, for example, 90% by weight or less or 80% by weight or less. Moisture content is measured by the loss-on-drying method. It is particularly preferable to use the vegetable residue in such a state containing water for producing a residue-containing plasticized composite material (masterbatch) in order to improve sensory properties. That is, the plant food residue may be used wet to produce the masterbatch.
Vegetable food residues with too low a water content may be used for the production of said masterbatch in the form of a mixture of water and said residue. Moreover, when a dried residue is used, water may be added to the dried residue as appropriate.

The mixture produced as described above is subjected to heat treatment. The heat treatment may be performed as the kneading treatment by the extruder described above. The extruder may be a twin screw extruder or a single screw extruder. The cylinder temperature of the extruder may be set to effect plasticization of the starch material and the starch in the residue, for example 60°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher. good. If the cylinder temperature is too high, the composite material may be discolored, so it is preferably 200° C. or less, more preferably 190° C. or less, 170° C. or less, or 150° C. or less, and particularly preferably 130° C. or less. Furthermore, it may be 120° C. or lower.

A residue-containing plasticized composite material is discharged from the extruder. The composite material may, for example, have a columnar shape (especially a columnar shape). The cross-sectional dimension of the columnar shape (especially the cross-sectional diameter of the columnar shape) may be, for example, 2 mm to 10 mm, particularly 3 mm to 8 mm, and more particularly 4 mm to 6 mm. For example, the composite material may be stranded. The composite material may be transparent or translucent, for example. The columnar composite material may be cut into pellets by, for example, a pelletizer. That is, the composite material may have a pellet shape.
Alternatively, the composite does not necessarily have a columnar shape, but may for example have a cake shape, in particular a wet cake shape.
The composite material may also optionally be ground to produce a composition in combination with a thermoplastic resin.

(3) How to use the composite material

The composites of the present invention may be used to produce compositions in combination with thermoplastic resins. The thermoplastic resin may contain at least a polyester-based resin or a polyolefin-based resin. That is, the composition may contain a polyester-based resin, a polyolefin-based resin, or both. Also, the thermoplastic resin may be a polystyrene-based resin. In addition, the thermoplastic resin may contain a biodegradable material so as not to reduce biodegradability.

The composition may contain the thermoplastic resin in a proportion of, for example, 90% by mass or less, preferably 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the mass of the composition. It may be contained in a ratio of mass % or less. Further, the composition may contain the thermoplastic resin in a proportion of, for example, 10% by mass or more, preferably 15% by mass or more, 20% by mass or more, and 25% by mass or more, relative to the mass of the composition. , or at a rate of 30% by mass or more.

The polyolefin resin is a polymer obtained by polymerization using olefins (eg, α-olefins) as main monomers. The polyolefin resin may be, for example, polyethylene (PE) resin, polypropylene (PP) resin, or a combination thereof.

Examples of the polyethylene resin include low density polyethylene resin (LDPE: Low Density Polyethylene), high density polyethylene resin (HDPE: High Density Polyethylene), very low density polyethylene resin (VLDPE: Very Low Density Polyethylene), linear low density polyethylene resin ( LLDPE: Linear Low Density Polyethylene), ethylene-vinyl acetate copolymer (EVA resin) and other ethylene copolymers, or ultra-high molecular weight polyethylene resins (UHMW-PE: Ultra High Molecular Weight-Polyethylene), or combinations thereof good.

The polyolefin-based resin may preferably be a biomass-derived polyolefin-based resin (for example, a biomass-derived polyethylene resin), for example, a biomass polyethylene resin. Biomass polyethylene resins can be, for example, LDPE, LLDPE, or HDPE. This makes it possible to reduce CO2 emissions.

The polyolefin resin may be a polyolefin resin produced using a metallocene catalyst. That is, the thermoplastic resin may be, for example, a metallocene-catalyzed polyethylene resin or polypropylene resin, or a combination thereof.
The polystyrene-based resin may be a metallocene-catalyzed polystyrene-based resin.

The polyester-based resin is a polymer obtained by polymerizing monomers through ester bonds. Polyester-based resins include, for example, polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PEN), polybutylene terephthalate resin (PBT), polylactic acid resin (PLA), polycarbonate resin (PC), polybutylene adipate terephthalate resin ( PBAT), polybutylene succinate resin (PBS), polyhydroxyalkanoate resin (PHA), or a combination of two or more of these. In a preferred embodiment, the polyester resin may contain PLA and PBAT.

A polystyrene-based resin is a polymer obtained by polymerizing a styrene-based monomer. Polystyrene resins include, for example, polystyrene resins, rubber-reinforced polystyrene resins (impact-resistant polystyrene resins, HIPS), acrylonitrile/styrene copolymers (AS resins), methacrylic acid ester/styrene copolymers, acrylonitrile/acrylic rubber/styrene Copolymers, acrylonitrile-ethylene-propylene-styrene copolymers, etc., or combinations of two or more thereof may also be used.

In the present embodiment, the type of thermoplastic resin may be appropriately selected by those skilled in the art according to, for example, the use of the molded article, and thermoplastic resins with low processing temperatures are preferred. For example, in the case of sheets used for food packaging containers, the thermoplastic resin may be, for example, preferably a polyolefin resin, more preferably a polyethylene resin or a polypropylene resin.

In this embodiment, the melting point of the thermoplastic resin is preferably 170° C. or lower, more preferably 165° C. or lower. By employing a thermoplastic resin with a lower melting point, the molding temperature can be lowered. Also, the melting point of the thermoplastic resin is preferably 90° C. or higher, more preferably 95° C. or higher.

The composition containing the composite material of the present invention and a thermoplastic resin preferably has a difference ΔP between the extrusion start pressure and the extrusion end pressure measured when the composition is measured with a pressurization tester under the following conditions: It may be 20 bar or less, more preferably 18 bar or less, even more preferably 14 bar or less, 12 bar or less, or 10 bar or less, particularly preferably 8 bar or less, 6 bar or less, or 4 bar or less. Said difference ΔP may for example be −1 bar or more, −0.5 bar or more, −0.3 bar or more, or 0 bar or more.

The method for the measurement will be described below.
<Conditions for measurement by the boost tester>
Extruder diameter: 25 mm
Temperature: 200°C
Mesh: 100 mesh Amount of composition subjected to test: 200 g

Extrusion pressure is measured for the composition using a pressurization tester as described below, and a graph such as that shown in FIG. 2 is obtained. The graph is a schematic example of a graph in which pressure is plotted against time.
The extrusion pressure difference ΔP measured for the composition means that the extrusion pressure of the base thermoplastic resin (Prime Polypro J106, Prime Polymer Co., Ltd.) is in an equilibrium state (the pressure change in the last 5 minutes is ± 0.5% or less. An index that represents the pressure difference between the extrusion start pressure P _start at the time of reaching an equilibrium state (a state in which the pressure change in the last 5 minutes was ± 0.5% or less) and the extrusion end pressure P _end Say. A unit is bar. In other words, it can be used as an indicator of the degree of presence of grains and the like contained in the composition. A lower value means that mesh clogging is less likely to occur.

The extrusion pressure difference ΔP is measured using a pressurization tester “LFT44-GP” (manufactured by Labotech).

The extrusion pressure difference ΔP is measured by the following procedure. FIG. 3 is a schematic diagram showing an example of a pressurization tester used when measuring the extrusion pressure difference ΔP for the starch-containing material according to this embodiment. A pressurization tester 40 shown in FIG. 3 includes a single screw extruder 43 , a gear pump 42 and a mesh 41 . In the boost tester 40, the gear pump inlet pressure P1 and the gear pump outlet pressure P2 are measured. When measuring the extrusion pressure difference ΔP, the rotation speed of the gear pump 42 was set to be constant at 30 RPM, the gear pump inlet pressure P1 was set to 50 bar, and the single screw extruder 43 was operated so that P1 was maintained at 50 bar. The gear pump outlet side pressure P2 is measured while the rotational speed is interlocked and controlled. The extrusion pressure difference ΔP is measured by the following procedure.
(1) As shown in FIG. 3, a mesh 41 of 100 mesh (opening 0.154 mm (nominal), void ratio 37%) is installed, and using a pressurization tester 40 capable of monitoring the extrusion pressure, the heat of the base The plastic resin is extruded, and after the extrusion pressure reaches an equilibrium state (a state in which the pressure change in the last 5 minutes is ±0.5% or less) at the pressure P2 on the outlet side of the gear pump of the pressurization tester 40, the extrusion pressure Extrusion of 200 g of the composition is started using a pressurization tester 40 with a set temperature of 200°C.
(2) The extrusion start pressure at the time when the extrusion pressure is in an equilibrium state (a state in which the pressure change in the last 5 minutes is ±0.5% or less) at the gear pump outlet side pressure P2 of the pressurization tester 40 shown in FIG. Measure P _start .
(3) After extruding 200 g of the composition from the pressurization tester 40, switch to the base thermoplastic resin, and the pressure is in equilibrium at the gear pump outlet pressure P2 (the pressure change in the most recent minute is ±0.5% Measure the extrusion end pressure P _end at the time of reaching the state below. (4) Calculate the extrusion pressure difference ΔP from the following formula.
Extrusion pressure difference ΔP = P _end - P _start

The composition may be a composition capable of forming a film or sheet. In particular, the composition may be a thermoplastic composition, ie a composition that is moldable under heat. The composition may be molded into, for example, a film or sheet. The composition may also be in pellet form.
The composition may also be used for press molding. In this case, the composition may be placed in a molding machine as a gel-like melt and then press-molded to obtain a molded body.

The composition is suitable for obtaining moldings with excellent surface conditions. For example, the composition is a molded body having a surface with a surface roughness (Ry) of, for example, 100 μm or less, preferably 90 μm or less, more preferably 80 μm or less, still more preferably 70 μm or less, and particularly preferably 60 μm or less. you can The surface roughness may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more. The surface may be, for example, the surface of the film or sheet when the molded article of the composition of the present invention is a film or sheet. The surface may also be the surface of a container when the molded article of the composition of the present invention is a container. According to the present invention, a composition (molded article) having such excellent surface conditions can be obtained.

In a particularly preferred embodiment, the composition has a surface roughness (Ry) of, for example, 50 μm or less, preferably 45 μm or less, more preferably 43 μm or less, even more preferably 42 μm or less, particularly preferably 41 μm or less, particularly preferably 40 μm. It may be a molded body having a surface that is: The surface roughness may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more. The surface may be, for example, the surface of the film or sheet when the molded article of the composition of the present invention is a film or sheet. Further, the surface may be the surface of a container when the molded article of the composition is a container.
The above-mentioned surface roughness of the composition in this embodiment can be easily achieved by using the ground material described above (especially ground material having the fiber diameter described above) as the vegetable food residue. The ground product is particularly suitable for obtaining a compact having such a particularly excellent surface condition.

The method for measuring the surface roughness (Ry) is as follows.
Equipment used: HANDYSURF+35 (manufactured by ACCRETECH)
Standard: JIS Z 1702
Measurement conditions: λc 2.5 mm, evaluation length 12.5 mm
Test piece: thickness 50 μm, width 50 mm, length 50 mm
That is, according to JIS Z 1702, for example, a film having a thickness of 50 μm is cut into a 50 mm square to prepare a sample, and the surface roughness of the sample is measured under the measurement conditions of λc 2.5 mm and an evaluation length of 12.5 mm. Then Ry is calculated. The device used for the measurement is HANDYSURF+35 (manufactured by ACCRETECH). In addition, the measurement object is not limited to the film, and the measurement may be performed on the surface of a sheet or other molded body in the same manner.

Said composition is suitable for obtaining moldings exhibiting excellent elongation properties. For example, when the composition is formed into a film having a thickness of 50 μm, the elongation at break of the film is, for example, 20% or more, preferably 30% or more, and more preferably 40% or more. The elongation at break may be, for example, 1000% or less, particularly 800% or less, or 600% or less, and more particularly 500% or less, 400% or less, or 300% or less. .

In a particularly preferred embodiment, when the composition is formed into a film having a thickness of 50 μm, the elongation at break of the film is, for example, 50% or more, and in some embodiments 80% or more. It may be 90% or more, 100% or more, or even 200% or more. The elongation at break may be, for example, 1500% or less, particularly 1200% or less, more particularly 900% or less, 800% or less, or 600% or less.
The elongation at break of the composition in the particularly preferred embodiment is achieved by using the ground material described above (especially the ground material having the fiber diameter described above) as the vegetable food residue. It's easy to do. The ground product is particularly suitable for obtaining a molded body having such particularly excellent elongation properties.

The method for measuring the elongation at break is as follows.
Tensile test (maximum stress, elongation at break)
Equipment used: STROGRAPH VE20D (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
Standard: JIS B 0601:2013
Measurement conditions: 300 mm/min Specimen: thickness 50 μm, width 15 mm, length 200 mm
That is, according to JIS B 0601: 2013, a film having a thickness of 50 μm was cut into a width of 15 mm and a length of 200 mm to prepare a sample, and the sample was subjected to a tensile test at a speed of 300 mm / min. Point stress and elongation at break are calculated (STROGRAPH VE20D: manufactured by Toyo Seiki Seisakusho Co., Ltd.).

The composition may be manufactured by performing a composition manufacturing process as follows. By using the composite material of the present invention, a composition having a pressure difference ΔP within the numerical range mentioned above can be obtained. When carrying out the above two steps, first the residue-containing plasticized composite material is obtained using the vegetable food residue and the starch material, and then the composite material is mixed with the thermoplastic resin to form the composition of the present invention. can get.

In the composition manufacturing step, the plasticized composite material and the thermoplastic resin are kneaded to manufacture the composition. In the kneading process, a compatibilizer may also be kneaded together.

The kneading process can be performed by an extruder. The extruder may be a twin screw extruder or a single screw extruder. The cylinder temperature in the extruder may be higher than, for example, the heating temperature (kneading temperature) in the composite material manufacturing process, and can be set so as to achieve the melting point of the thermoplastic resin. The cylinder temperature may be, for example, 100° C. or higher, 110° C. or higher, or 120° C. or higher. Also, the cylinder temperature may be, for example, 210° C. or lower, particularly 200° C. or lower, 190° C. or lower, 180° C. or lower, 170° C. or lower, 160° C. or lower, or 150° C. or lower.

A composition is discharged from the extruder. The composition may have a strand shape. The composition may be cut into pellets, for example by a pelletizer, for subsequent molding steps.

Thus, the composition is not only used in the molding step described below as a strand-shaped or pellet-shaped composition, but also can be used without being molded into a strand-shaped or pellet-shaped shape. It may be used in the molding process described below. That is, the composition of the present invention obtained by kneading the residue-containing plasticized composite material and the thermoplastic resin may be used as it is in the molding step described below.

The composition may be subjected to a molding process. A molding technique employed in the molding step may be appropriately selected by those skilled in the art according to the desired shape or type of the molded article. For example, in the molding step, a treatment for obtaining a film- or sheet-like molding may be performed. Then, the film- or sheet-like molded article of the composition may be further molded into another shape, and the film- or sheet-like molded article may be used by the user (eg, consumer) as it is.
Moreover, in the molding step, the composition may be molded into a desired shape without forming a film or sheet-like molded body. Thus, for example, the melt of the composition may be directly molded into the desired shape. The melt may be a melt obtained by melting the strand-shaped or pellet-shaped composition described above, or a melt obtained by kneading the residue-containing plasticized composite material and the thermoplastic resin. It may also be a melt (that is, one that has not undergone a strand-like or pellet-like state).
In order to obtain the molded article, for example, inflation molding, injection molding, extrusion molding, press molding, stretch molding, or the like may be performed. A molding method may be appropriately selected by a person skilled in the art.

For the production of film- or sheet-like moldings, see also the examples below.
An example in which the melt of the composition is directly molded will be described below.

For the production of the shaped bodies, the composition can be melted. For example, the composition can be melted using a melter. The melter may be one known in the art, for example a batch melter, especially an agitator melter.

The composition in a molten state (hereinafter also referred to as "melt") is molded using a molding machine to obtain the molded article. The melt may be gel-like, for example. The melt can be fed into the molding machine, for example by a mechanical arm or manually. The type of molding machine may be appropriately selected by those skilled in the art according to the desired shape or desired molding method. An example of press molding will be described below with reference to FIG.

As shown in FIG. 1A, a composition 52 in a molten state is placed between dies 50 and 51 (particularly dies) of a press molding machine using, for example, a mechanical arm. For example, it may be placed on the lower mold 51 as shown in the figure.
Next, the molds 50 and 51 are clamped and pressed as shown in FIG. Thereby, the composition 52 is molded into a desired shape. While clamped, the composition may be cooled.
Next, as shown in FIG. 1C, the molds 50 and 51 are opened and the molded body 52' of the composition is removed from the molding machine. Thus, a shaped body of the composition may be obtained.
During the pressing, if the composition does not have fluidity, the mold will not be filled with the composition, resulting in a short circuit. The compositions of the present invention are suitable and capable of being filled into molds in molding machines.

The proportions of components in the composition may be, for example, as described below.

The ratio of the total content of the vegetable food residue and the plasticized starch contained in the composition may be, for example, 10% by mass or more, preferably 15% by mass, relative to the mass of the composition of the present invention. Above, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. In addition, the ratio of the total content of the vegetable food residue and the plasticized starch may be, for example, 90% by mass or less, preferably 85% by mass or less, or 80% by mass, relative to the mass of the composition of the present invention. % or less, 75 mass % or less, 70 mass % or less, 65 mass % or less, or 60 mass % or less.

Further, the composition may contain the thermoplastic resin in a proportion of, for example, 90% by mass or less, preferably 85% by mass or less, 80% by mass or less, or 75% by mass or less, relative to the mass of the composition. Alternatively, it may be contained at a rate of 70% by mass or less. Further, the composition may contain the thermoplastic resin in a proportion of, for example, 10% by mass or more, preferably 15% by mass or more, 20% by mass or more, and 25% by mass or more, relative to the mass of the composition. , or at a rate of 30% by mass or more.

In addition, the content of the vegetable food residue is, for example, 5 parts by mass or more or 10 parts by mass or more, preferably 15 parts by mass, with respect to 100 parts by mass of the total content of the vegetable food residue and the plasticized starch. parts or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, or 50 parts by mass or more. In addition, the content of the vegetable food residue is, for example, 95 parts by mass or less or 90 parts by mass or less, preferably 85 parts by mass, with respect to the total content of 100 parts by mass of the vegetable food residue and the plasticized starch. parts or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, or 50 parts by mass or more.
For example, the content of the vegetable food residue is preferably 15 parts by mass or more with respect to 100 parts by mass of the total content of the vegetable food residue and the plasticized starch, from the viewpoint of promoting the utilization of the residue.

In addition, the content of the plasticized starch is, for example, 95 parts by mass or less or 90 parts by mass or less, preferably 85 parts by mass, with respect to 100 parts by mass of the total content of the vegetable food residue and the plasticized starch. 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, or 50 parts by mass or less. In addition, the content of the plasticized starch is, for example, 5 parts by mass or more or 10 parts by mass or more, preferably 15 parts by mass, with respect to 100 parts by mass of the total content of the vegetable food residue and the plasticized starch. Above, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 parts by weight or more.
For example, if the content of the plasticized starch is 15 parts by mass or more with respect to the total content of 100 parts by mass of the vegetable food residue and the plasticized starch, it is possible to improve the moldability and / or improve the quality of the molded product. It is preferable from the viewpoint of improvement.

In addition, the content of the polyhydric alcohol is, for example, 10 parts by mass or more, preferably 12 parts by mass or more, more preferably 14 parts by mass with respect to 100 parts by mass of the total content of the vegetable food residue and the plasticized starch. parts or more, 16 parts by mass or more, 18 parts by mass or more, or 20 parts by mass or more. In addition, the content of the polyhydric alcohol is, for example, 30 parts by mass or less, preferably 28 parts by mass or less, more preferably 100 parts by mass of the total content of the vegetable food residue and the plasticized starch. It may be 26 parts by mass or less.

The content ratio of the plasticized composite material contained in the composition may be, for example, 10% by mass or more or 13% by mass or more, preferably 15% by mass or more, relative to the mass of the composition of the present invention. , 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. In addition, the content ratio of the plasticized composite material may be, for example, 90% by mass or less, preferably 85% by mass or less, 80% by mass or less, or 75% by mass, relative to the mass of the composition of the present invention. 70% by mass or less, 65% by mass or less, or 60% by mass or less.

Also, the composite material may be used for mixing with a thermoplastic resin as described below, but the application of the composite material is not limited to this. For example, the composite material may be used as an additive used to make paper. For example, the composite material may be added and mixed with the stock in a molten state. The stock containing the composite material can be made into paper to produce paper. Thereby, paper containing the residue can be produced. That is, plant food residue can be upcycled in paper.
Thus, the present invention also provides a paper comprising said composite material and a method for producing said paper. In the paper, the components that make up the composite material may be dispersed throughout the paper. That is, the paper may comprise the residue, the starch material, and paper components.
The paper may contain the residue at a content ratio of, for example, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more relative to the mass of the paper, and further 1% by mass. It may be included in the above content ratio. Moreover, the said content rate may be 20 mass % or less, 15 mass % or less, or 10 mass % or less, for example.
The paper contains the starch material in a content ratio of, for example, 0.05% by weight or more, preferably 0.1% by weight or more, 0.5% by weight or more, or 1% by weight or more, based on the weight of the paper. OK. Moreover, the said content rate may be 30 mass % or less, 20 mass % or less, or 10 mass % or less, for example.

Alternatively, the composition may be produced by mixing the vegetable food residue, the starch material, and the thermoplastic resin in one step.

The composition may be made by mixing and heating the plant food residue, the starch material, and the thermoplastic resin. That is, the composition may be produced from these three materials without producing the residue-containing plasticized composite material (particularly pellets of the composite material) described above.
For example, in one kneader, these three materials may be introduced, heated and mixed. For example, the plant food residue, the starch material, and the thermoplastic resin may be added to the kneading device, and the three materials heated and mixed simultaneously. The composition can thus be obtained.
Alternatively, the plant food residue and the starch material are introduced into the kneading device, the two materials are heated and mixed, and the thermoplastic resin is introduced into the resulting melt. good. The composition can thus be obtained.
Alternatively, the starch material is added to the kneading device, the starch material is heated and melted, and then the vegetable food residue is added, heated and mixed, and then the thermoplastic resin is added. may be heated and mixed. The composition can thus be obtained.

Also in this method of manufacturing the composition, as described above, the other components (e.g., the polyhydric alcohol, and , water and/or modifiers) may be added. In addition, the vegetable food residue is as described above, preferably it may be a residue that has not been dried, and the water content of the vegetable food residue may be, for example, 5% by mass or more. , in particular 10% by mass or more, 20% by mass or more, 30% by mass or more, or 50% by mass or more. The moisture content may be, for example, 90% by weight or less or 80% by weight or less.

The heating temperature at which the plant food residue and the starch material are mixed and heated may be, for example, 60° C. or higher, 80° C. or higher, 90° C. or higher, or 100° C. or higher. If the temperature is too high, the composite material may be discolored, so it is preferably 130° C. or lower, more preferably 120° C. or lower.
Also, the temperature at which the thermoplastic resin is mixed and heated may be, for example, 100° C. or higher, 110° C. or higher, or 120° C. or higher. Also, the temperature may be, for example, 210° C. or lower, particularly 200° C. or lower, 190° C. or lower, 180° C. or lower, 170° C. or lower, 160° C. or lower, or 150° C. or lower.

3. Example

The present invention will now be described in more detail based on examples. It should be noted that the examples described below are examples of representative examples of the present invention, and the scope of the present invention is not limited only to these examples.

3-1. Examples 1 and 2
The evaluation methods used in the examples are described below, followed by a description of each composition.

(1) Evaluation method

(1-1) Pressure increase test Each composition was supplied to a pressure increase tester (LABTECH ENGINEERING, extruder diameter 25 mm, temperature 200°C) to conduct a pressure increase test. The pressurization test was performed at 200° C., using a mesh of 100, and measuring the pressure difference ΔP at the start and end of the measurement. The pressure difference ΔP is measured according to the above 1. was carried out as described in "(2) Physical properties".

(1-2) Moldability (inflation molding)
Each composition was supplied to an inflation molding machine (Placo Co., Ltd., die Φ65, extruder diameter 55 mm, temperature 150° C.) and inflation molding was performed. The inflation molding was performed at 150°C to 160°C. A film having a thickness of 50 μm was obtained by the inflation molding. The film obtained by the inflation molding was evaluated according to the following criteria.
<Evaluation Criteria>
A: It was blow-molded, and the resulting film had no tears and had a uniform appearance.
B: Inflation molding was possible, and the obtained film did not have any tear, but aggregates were confirmed in a part of the film.
C: Inflation molding could not be performed due to factors such as holes.

(1-3) Odor The odor of the film produced in the evaluation in (1-2) above was evaluated according to the following criteria.
<Evaluation Criteria>
A: Almost odorless B: Slightly odorous, acceptable C: Strong odor

(1-4) Color The color of the film produced in the evaluation in (1-2) above was evaluated according to the following criteria.
<Evaluation Criteria>
A: Yellow B: Light brown C: Brown

(1-5) Moldability (injection molding)
Injection molding was performed using each composition, and the injection moldability was evaluated.
Each composition was supplied to an injection molding machine (Sumitomo Heavy Industries Ltd., SH-125), and injection molding was performed. The injection molding was performed at 180-190°C. A dumbbell-shaped injection-molded product according to JIS7161 was obtained by the injection molding. The injection molded articles obtained by the injection molding were evaluated according to the following criteria.

<Evaluation Criteria>
A: Molding is possible without defects in appearance such as black spots and burnt deposits, and molding defects such as sink marks, insufficient filling, and foaming.
B: Black spots and burnt deposits are observed, but can be molded without molding defects such as insufficient filling and foaming.
C: Black spots and burnt deposits are observed, and molding defects such as insufficient filling and foaming cannot be resolved.

(2) Production of composition

Each composition was prepared with the formulation shown in the table below. The manufacturing method for each composition is as described after these tables. In these tables, the unit of numerical values relating to composition is parts by weight, and the unit of ΔP is bar.

(Comparative example 1)
A potato residue was prepared. The potato residue is the pomace produced in the potato starch extraction process, that is, the potato-derived starch extraction residue. The potato residue was ground and dried to have a size of 5 mm or less. A dry powder of potato residue was thus prepared.

40 parts by mass of the potato residue dry powder, 1.5 parts by mass of magnesium stearate, 1 part by mass of zinc stearate, 0.5 parts by mass of monoglyceride, linear low density polyethylene resin (LLDPE: Linear Low Density Polyethylene, product name UF641) , Japan Polyethylene Co., Ltd.) and 3 parts by mass of a compatibilizing agent (maleic anhydride-modified polyethylene, manufactured by DuPont) were prepared. These ingredients were dry blended. The dry blending was done at ambient temperature.

The mixture obtained by the dry blending was fed into a twin-screw extruder (PCM30, Ikegai Co., Ltd.), and these components were kneaded. The cylinder temperature in the kneading process was 140° C. and the resin pressure was 9.5 MPa. During the kneading process, suction from the vent was performed. Through the kneading treatment, a composition (hereinafter also referred to as "composition of Comparative Example 1") was obtained.

(Comparative example 2)
A composition (hereinafter referred to as Also referred to as "composition of Comparative Example 2")) was prepared.

(Example 1-1)
The potato pomace used in Comparative Example 1 was pulverized to have a size of 5 mm or less, but unlike Comparative Example 1, it was not dried. In this way, a potato residue pulverized material that had only been pulverized was prepared. The potato residue grind was moist. The potato residue pulverized product had a wet state to the extent that moisture adhered to hands when touched.

70 parts by mass of corn starch, 16 parts by mass of glycerin, 8 parts by mass of ethylene glycol, 1 part by mass of formamide, 0.5 parts by mass of monoglyceride, 2 parts by mass of polyethylene, 2 parts by mass of modified polyethylene, and water and the ground potato residue A mixture (mass ratio 10:3) of 100 parts by mass was prepared. These ingredients were mixed in a mixer. The mixing was performed at ambient temperature. The glycerin, the ethylene glycol, the water, and the mixture of the water and ground potato residue were pre-mixed before being charged into the mixer. The mixture obtained by the mixing was a liquid mixture.

The mixture obtained by the mixing was fed into a twin-screw extruder (PCM30, Ikegai Co., Ltd.) and kneaded.

The cylinder temperature in the kneading process was 110°C. During the kneading process, suction from the vent was performed. After the kneading process, the mixture was extruded through the die of the extruder to obtain an elongated substantially cylindrical residue-containing plasticized composite material (also referred to as "masterbatch of Example 1-1").

50 parts by mass of the masterbatch of Example 1-1 and 50 parts by mass of polyethylene (LLDPE: Linear Low Density Polyethylene, product name UF641, manufactured by Japan Polyethylene Co., Ltd.), and acid-modified polyethylene (maleic anhydride-modified polyethylene, manufactured by DuPont) 3 parts by mass were fed into a twin-screw extruder (PCM30, Ikegai Co., Ltd.), and these components were kneaded. The cylinder temperature in the kneading process was 140° C. and the resin pressure was 4.4 MPa. During the kneading process, suction from the vent was performed. A composition (hereinafter also referred to as “composition of Example 1-1”) was obtained by the kneading treatment.

The composition of Example 1-1 was supplied to a pressurization tester (LABTECH ENGINEERING, extruder diameter 25 mm, temperature 200° C.), and the pressurization test was performed as described above to measure the pressure difference ΔP.
In addition, the composition of Example 1-1 was evaluated for moldability regarding film formation, odor and color as described above.

(Examples 1-2 and 1-3)
A masterbatch was produced in the same manner except that the formulation for producing the masterbatch was changed as shown in Table 2, and the composition (“Example 1-2 composition and "Compositions of Examples 1-3"). For each of the compositions produced, a pressurization test was performed as described above to measure the pressure difference ΔP. These compositions were also evaluated for moldability for film formation and for odor and color as described above.

(Example 2-1)
The potato pomace used in Comparative Example 1 was pulverized to have a size of 5 mm or less, but unlike Comparative Example 1, it was not dried. In this way, a potato residue pulverized material that had only been pulverized was prepared. The potato residue grind was moist.

Phosphate-crosslinked tapioca starch (T-1, Matsutani Chemical Industry Co., Ltd.) 67 parts by mass, glycerin 5 parts by mass, ethylene glycol 18 parts by mass, water 18 parts by mass, potato residue pulverized product 4.1 parts by mass and maleic anhydride 0 .5 parts by mass were prepared. These ingredients were mixed in a mixer. The mixing was performed at ambient temperature. The glycerin, the ethylene glycol, and the ground potato residue were pre-mixed prior to being charged into the mixer. The mixture obtained by the mixing was a powdery mixture.

The mixture obtained by the mixing was fed into a twin-screw extruder (PCM30, Ikegai Co., Ltd.) and kneaded.

The cylinder temperature in the kneading process was 110°C. During the kneading process, suction from the vent was performed. After the kneading process, the mixture was extruded through the die of the extruder to obtain an elongated substantially cylindrical residue-containing plasticized composite material (also referred to as "masterbatch of Example 2-1").

50 parts by mass of the masterbatch of Example 2-1 and 60 parts by mass of a mixed resin of PLA and PBAT (ECOVIO, manufactured by BASF) are fed into a twin-screw extruder (PCM30, Ikegai Co., Ltd.), and these The ingredients were subjected to a kneading process. The cylinder temperature in the kneading process was 140° C. and the resin pressure was 4.4 MPa. During the kneading process, suction from the vent was performed. A composition (hereinafter also referred to as “composition of Example 2-1”) was obtained by the kneading treatment.

The composition of Example 2-1 was supplied to a pressurization tester (LABTECH ENGINEERING, extruder diameter 25 mm, temperature 200° C.), and the pressurization test was performed as described above to measure the pressure difference ΔP.
In addition, the composition of Example 2-1 was evaluated for moldability regarding film formation, odor and color as described above.

(Examples 2-2 to 2-13)
A masterbatch was produced in the same manner except that the formulation for producing the masterbatch and the formulation for producing the composition were changed as shown in Table 3, and the composition was produced using the masterbatch. manufactured things.

The apple residue used in Examples 2-7 and 2-11 is the pomace produced in the apple juice extraction process, that is, the apple juice extraction residue. The apple residue was ground to have a size of 5 mm or less. The pulverized apple residue thus prepared was used in these examples.
The mixture of water and potato residue used in Examples 2-8 and 2-9 is the same as that used in Example 1-1.

For Examples 2-5 and 2-6, moldability in injection molding was evaluated instead of moldability in film molding.

(Examples 2-14 to 2-17)
A masterbatch was produced in the same manner except that carrot residue, grape residue, green soybean residue, or coffee residue was used as vegetable food residue and the formulation was changed as shown in Table 4, and the masterbatch was was used to prepare the composition.

The ginseng residue is a residue such as a pomace produced in the ginseng extract extraction process or a skin or cut off part produced during the processing of the ginseng into food. The ginseng residue was prepared by crushing or grinding to have a size of 5 mm or less.
The grape residue is the pomace produced in the grape juice extraction process, that is, the grape juice extraction residue. The grape residue was prepared by crushing or grinding to have a size of 5 mm or less.
The green soybean residue is a residue obtained by removing beans during food processing. The edamame residue was prepared by crushing or grinding to have a size of 5 mm or less.
The coffee residue is residue such as grounds generated in the coffee extraction process. The coffee residue was prepared by grinding or grinding to have a size of 5 mm or less.

(3) Evaluation Results Evaluation results for each composition are shown in Tables 1 to 3 above. As shown in the evaluation results for Comparative Example 1, the composition containing a thermoplastic resin and potato residue dry powder had poor moldability. Further, as shown in the evaluation results of Comparative Example 2, moldability was poor even when starch was further added to the thermoplastic resin and dried potato residue powder.
In addition, both Comparative Examples 1 and 2 gave bad evaluation results for odor.
In addition, the color evaluation results for both Comparative Examples 1 and 2 were brown.

When adding a biomass material such as potato residue dry powder to a thermoplastic resin, it is considered desirable to remove moisture as much as possible in consideration of the ease of mixing with the thermoplastic resin. be. However, as shown in Comparative Example 1, when the potato residue was used in the dry powder state, the moldability was poor. Further, as shown in Comparative Example 2, even if starch was added to improve the ease of mixing the thermoplastic resin and the dried potato residue powder, the moldability was still poor.

In Examples 1-1 to 1-3 and 2-1 to 2-13 (hereinafter collectively referred to as "example group"), first, residue-containing plasticized composite materials ( masterbatch) was produced. The vegetable food residue used in the production of the masterbatch was wet rather than dry processed. Tables 2 and 3 show the compositions obtained by mixing the masterbatch produced by plasticizing the mixture of the residue and starch in a wet state and the thermoplastic resin. As can be seen, both had excellent moldability.
As described above, it can be seen that the use of the plasticized composite material according to the present invention can improve the moldability of a composition containing vegetable food residue.
It can also be seen that the composition comprising vegetable food residue, plasticized starch and thermoplastic resin and having a low ΔP of the composition can improve moldability. The plasticized composite material according to the invention is suitable for reducing ΔP.

Moreover, the odor of the example group was odorless or permissible in all cases. Therefore, the odor can be reduced by the composition containing vegetable food residue, plasticized starch and thermoplastic resin as in the example group and by the low ΔP of the composition. It is also found that the use of the composite material contributes to the reduction of odor in the composition.

Moreover, the color of the example group was yellow or light brown. Therefore, by comprising a composition comprising vegetable food residue, plasticized starch and a thermoplastic resin as in the example group and lowering the ΔP of the composition, the brown tint can be reduced, i.e. a lighter color. A resin composition having a taste is obtained. In addition, it can be seen that the use of the composite material contributes to brightening the color of the composition.

There is a difference in pressure difference ΔP between the compositions of Comparative Examples 1 and 2 and the compositions of the example group, as shown in Tables 1-3. Therefore, the pressure difference ΔP measured for the composition is, for example, 20 bar or less, preferably 18 bar or less, more preferably 19 bar or less, even more preferably 17 bar or less, 16 bar or less, or 15 bar or less, for excellent moldability. presumably contributed to its performance.

Also, in order to control the pressure difference ΔP to such a low level, it is considered effective to combine the vegetable food residue with starch in a wet state for plasticization, as in the example group. The masterbatch obtained by the plasticizing treatment is suitable for obtaining a composition in combination with a thermoplastic resin.

As described above, the composite material of the present invention is useful for improving moldability and quality of a composition containing vegetable food residue. Also, the manufacturing method according to the present invention is suitable for manufacturing composite materials having such excellent functions.

In Example 1-1, a mixture of water and potato residue was used, and in Examples 1-2 and 1-3, potato residue was used without being mixed with water. It can be seen that moldability and composition quality properties are improved in any mode of residue utilization.

Further, in Examples 1-1 to 1-3, a polyolefin resin was used, in Examples 2-1 to 2-12, a polyester resin was used, and in Example 2-13, a polyolefin resin was used. . Also, various ratios of vegetable food residue and thermoplastic resin were used in these examples. It can be seen that the moldability and composition quality characteristics are improved regardless of the resin and ratio.

Further, from the evaluation results of the moldability in Examples 2-1 to 2-4, it is considered that the moldability improves as the ratio of the residue to the total amount of the residue and plasticized starch decreases. However, in Examples 2-10 and 2-11, the molded examples were very good even at such high proportions. Therefore, it can also be seen that moldability can be improved by, for example, the type of starch or the type of thermoplastic resin.

Further, as shown in Examples 2-14 to 2-17, in any case of using carrot residue, grape residue, edamame residue, and coffee residue as the types of vegetable food residue, the pressure difference ΔP was 20 bar. Good evaluation results were obtained by the following. Therefore, even when various kinds of vegetable food residues are used, it can be seen that good properties of the composition can be achieved by setting the pressure difference ΔP to 20 bar or less.

3-2. Example 3

A masterbatch was produced in the same manner, except that the formulation for producing the masterbatch was changed as shown in Table 5 below, and the composition was produced using the masterbatch.

Examples 3-1 and 3-5 are the same except that the vegetable food residue is ground or not ground potato residue. be. Similarly, for the three pairs of Examples 3-2 and 3-6, Examples 3-3 and 3-7, and Examples 3-4 and 3-8, other than the presence or absence of grinding are the same.
The non-ground residue was pulverized to have a size of 5 mm or less as in Examples 1 and 2 above, but was ground to make the fiber diameter 100 μm or less as described later. is not done. That is, the non-ground residue contains fibers with a fiber diameter of 100 μm or more and 5 mm or less. The non-ground residue may also contain fibers with a fiber diameter of 100 μm or less. That is, fibers having a fiber diameter of 100 μm or less may be present in the non-ground residue.
In addition, the ground residue may be substantially free of fibers with a fiber diameter of 100 μm or more and 5 mm or less, for example, 3% or less, 2% or less, or 1% of the total fibers in the microscope image. may be:
Any ground residue has a fiber diameter of 100 μm or less. The ground residue was obtained by further grinding the non-ground residue with a stone grinder (Masuko Sangyo Co., Ltd.) at 1500 rpm.
The pressure difference ΔP was measured by a pressurization test for the manufactured composition of each example. Further, each composition was evaluated for film formability as described above, and the surface roughness (Ry) and elongation at break were measured. These measurements were performed as described above.

As shown in Table 5, it was confirmed that inflation molding is possible when the pressure difference ΔP is 20 bar or less. It was also confirmed that the use of ground residue further improved moldability compared to the use of non-ground residue. In particular, the milling is believed to contribute to preventing agglomeration of residual components.
It can also be seen that the use of ground residue improves the surface roughness and elongation at break compared to the use of non-ground residue.
As described above, it can be seen that a composition having particularly excellent physical properties can be obtained by using ground vegetable food residue.

The configurations, methods, steps, shapes, materials, and values given in the above-described embodiments and examples are merely examples, and different configurations, methods, steps, shapes, materials, and values may be used. .

Also, the configurations, methods, steps, shapes, materials, numerical values, etc. of the above-described embodiments and examples can be combined with each other without departing from the gist of the present invention.

Further, in this specification, a numerical range indicated using "to" indicates a range including the numerical values before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range in one step may be replaced with the upper limit or lower limit of the numerical range in another step. The materials exemplified in this specification can be used singly or in combination of two or more unless otherwise specified.

Claims (13)

vegetable food residues;
a plasticized starch;
A plasticized composite material comprising
The starch contained in the vegetable food residue is plasticized,
Said plasticized composite material. The plasticized composite material according to claim 1, wherein the total content of the vegetable food residue and the plasticized starch is 60 mass% or more relative to the mass of the plasticized composite material. 3. The plasticized composite material of claim 1 or 2, wherein the plasticized composite material further comprises a polyhydric alcohol. The plasticized composite material according to claim 3, wherein the content of said polyhydric alcohol is 10% by mass or more with respect to the mass of said plasticized composite material. 4. The plasticized composite material according to claim 3, wherein the total content of said vegetable food residue, said plasticized starch and said polyhydric alcohol is 80 mass % or more relative to the mass of said plasticized composite material. 3. The plasticized composite material according to claim 1 or 2, wherein the vegetable food residue is a food material residue selected from among vegetables, fruits, grains, coffee and tea. 3. The plasticized composite material according to claim 1 or 2, wherein the vegetable food residue is a starch extraction residue derived from vegetables or grains, a fruit juice extraction residue derived from fruit, a coffee or tea beverage extraction residue, or a grain polishing residue. . 3. The plasticized composite material according to claim 1 or 2, wherein the vegetable food residue consists mainly of residue pieces having a size of 5 mm or less. 3. The plasticized composite material of claim 1 or 2, wherein the vegetable food residue comprises ground food residue. The plasticized composite material according to claim 1 or 2, wherein the content of the thermoplastic resin in the plasticized composite material is 5% by mass or less with respect to the mass of the plasticized composite material. 3. The plasticized composite material according to claim 1, wherein the plasticized composite material is mixed with a thermoplastic resin to produce a composition for producing a molded article. A method for producing a plasticized composite material comprising vegetable food residue and plasticized starch, comprising:
The manufacturing method includes a plasticizing step of plasticizing a mixture of vegetable food residue and starch material,
The vegetable food residue is subjected to the plasticizing treatment in a wet state.
The manufacturing method. 13. The production method according to claim 12, wherein the vegetable food residue is subjected to the plasticizing treatment in a state where the moisture content is 5% by mass or more.