Composite material, coating material using the same, and film material

Abstract

To provide a novel composite material.SOLUTION: The composite material of the present invention comprises an ion-crosslinkable polymer, an ion-crosslinking agent, and an environmentally degradable resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite material, a coating material using the same, and a film material. [Background technology]

[0002] Various developments have been made so far regarding methods for manufacturing composite materials. For example, the technique described in Patent Document 1 is known as this type of technique. Patent Document 1 describes that a marine biodegradation accelerator is prepared by kneading hydrophobic alginate particles, the surfaces of which have been hydrophobized, into a biodegradable resin at 140°C, and then press-molding the mixture at 150°C to produce a film (a resin molded product) (paragraphs 0189, 0230, etc.). Patent Document 1 also describes that the resin or the resin and the marine biodegradation accelerator in the resin composition may be melted by heat, and then molding may be carried out (paragraph 0180, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-191810 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have investigated a new composite material that is different from the resin composition described in Patent Document 1 above. [Means for solving the problem]

[0005] As a result of further investigation, the present inventors have found that a composite material can be obtained by melt-kneading raw material components including an ionically cross-linkable polymer, an ionically cross-linking agent, and an environmentally degradable resin, and have thus completed the present invention.

[0006] According to one aspect of the present invention, there are provided the following composite material, coating material, and film material using the same. [Effects of the Invention]

[0007] According to the present invention, there are provided a novel composite material, and a coating material and a film material using the same. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an apparatus for evaluating sustained urea release. DETAILED DESCRIPTION OF THE INVENTION

[0009] The composite material of this embodiment will be described.

[0010] The composite material of this embodiment is a resin composition containing an ionically crosslinkable polymer, an ionically crosslinking agent, and an environmentally degradable resin.

[0011] The environmentally degradable resin can be any resin that is decomposed by the action of natural microorganisms such as bacteria, and partially or entirely becomes water, carbon dioxide, etc., and circulates back into nature, and is preferably a material that complies with the biodegradability test in accordance with ISO 14855-2 (JIS K 6953-2).Known environmentally degradable resins can be used.

[0012] The environmentally degradable resin includes an environmentally degradable resin A having a main chain but no side chains. The environmentally degradable resin A may contain one or more of the specific examples of environmentally degradable resins described below. Furthermore, the environmentally degradable resin may contain, in addition to the environmentally degradable resin A, an environmentally degradable resin B having a main chain and a side chain. In this specification, the main chain includes a structure in which one or more repeating units contained in the molecule of the environmentally degradable resin are bonded, and a hydroxyl group, a carboxyl group, an amino group, or the like may be bonded to each of both ends of the main chain. On the other hand, the side chain includes a structure branched from a part of the main chain other than both ends. The side chain has one or more specific functional groups in at least one repeating unit in the main chain. The functional group is bonded to the carbon skeleton (carbon chain) that constitutes the side chain, and in the case of a functional group containing carbon atoms, the carbon atoms in the functional group may constitute at least a part or all of the carbon skeleton. Specific examples of functional groups include hydrophobic groups and hydrophilic groups, but preferably include at least a hydrophobic group. Hydrophobic groups may include hydrocarbon groups such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Hydrophilic groups may include carboxylic acid groups, sulfonic acid groups, hydroxyl groups, and amino groups (however, groups consisting of "=O" directly bonded to carbon atoms in the main chain do not need to be included in the above-mentioned hydrophilic groups). An example of the environmentally degradable resin A may include an environmentally degradable resin having a main chain containing an ester structure but no side chain, and may be selected from, for example, aliphatic polyester resins other than polylactic acid, aromatic aliphatic polyester resins, etc. On the other hand, an example of the environmentally degradable resin B may include an environmentally degradable resin having a main chain and side chain containing an ester structure, and may be selected from, for example, polylactic acid, PHA resins, P3HB resins, etc. The environmentally degradable resin may contain other environmentally degradable resins than the environmentally degradable resin A and the environmentally degradable resin B, as long as the effect of the invention is not impaired.

[0013] Specific examples of environmentally degradable resins include biodegradable plastics, such as polyester resins such as aliphatic polyester resins, aromatic aliphatic polyester resins, and polyhydroxyalkanol (PHA) resins, and non-polyester resins such as natural polymers. These may be used alone or in combination of two or more. The aliphatic polyester resin, aromatic aliphatic polyester resin, and PHA resin may each be partially or entirely derived from biomass or petroleum-derived raw materials. The environmentally degradable resin may contain either a biomass-derived resin or a natural polymer alone, or may contain two or more of these, for example, a biomass-derived resin and a petroleum-derived resin. The aliphatic polyester resin may contain one or more of, for example, polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxybutyrate, polycaprolactone (PCL), polybutylene succinate / adipate (PBSA), polymalic acid, polyglycolic acid (PGA), polydioxanone, poly(2-oxetanone), etc. The aliphatic polyester resin may contain any of these alone or may contain a copolymer containing two or more of these. The aromatic aliphatic polyester resin is a polyester resin having both an aromatic moiety and an aliphatic moiety, and may include, for example, one or more of polybutylene succinate / terephthalate (PBST), polybutylene adipate / terephthalate (PBAT), polytetramethylene adipate / terephthalate, polyethylene adipate terephthalate (PEAT), and the like. The PHA-based resin may include, for example, a P3HB-based resin containing polyhydroxyalkanoate and / or 3-hydroxybutyrate units. The P3HB-based resin may be a polymer containing only 3-hydroxybutyrate units, or may be a copolymer containing repeating units other than 3-hydroxybutyrate units. Specific examples of P3HB-based resins include poly3-hydroxybutyrate (PHB), poly(3-hydroxybutyrate / 3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB3HV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). The poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (PHB4HB), poly(3-hydroxybutyrate-co-3-hydroxyoctadecanoate) (PHB3HO), poly(3-hydroxybutyrate-co-3-hydroxyoctadecanoate) (PHB3HOD), poly(3-hydroxybutyrate-co-3-hydroxydecanoate) (PHB3HD), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (PHB3HV3HH), and the like may be contained in one or more thereof. The natural polymer may include, for example, one or more of starch, cellulose, cellulose acetate, cellulose ester resin, starch, esterified starch, chitin, chitosan, gluten, gelatin, zein, soy protein, collagen, keratin, and the like. Without being limited thereto, the environmentally degradable resin may include, in addition to the above-mentioned polyester-based resins, polyamides having an ester structure in the main chain as environmentally degradable resins having a main chain containing an ester structure, and in addition to the above-mentioned natural polymers, non-polyester-based resins may include polyvinyl alcohol (PVA), polyamide 4 (PA4), biodegradable polycarbonates (PC) such as aliphatic polycarbonates, and the like.

[0014] Here, the environmentally degradable resin may contain the same type of aliphatic polyester resin, aromatic-aliphatic polyester resin, and PHA resin, or two or more different types. When containing different types, the environmentally degradable resin may include a combination of an aliphatic polyester resin and an aromatic-aliphatic polyester resin, a combination of an aliphatic polyester resin and a PHA resin, a combination of an aromatic-aliphatic polyester resin and a PHA resin, or a combination of an aliphatic polyester resin, an aromatic-aliphatic polyester resin, and a PHA resin. In this case, the PHA resin may include at least a P3HB resin, or may include only a P3HB resin. The environmentally degradable resin may contain the above-mentioned polyester resin alone, or may contain a polyester resin and a non-polyester resin, or a copolymer of a polyester resin and a non-polyester resin.

[0015] The lower limit of the content of the environmentally degradable resin contained in the composite material is, for example, 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more, based on 100% by mass of the total content of the ionically crosslinkable polymer, the ionically crosslinking agent, and the environmentally degradable resin. On the other hand, the upper limit of the content of the environmentally degradable resin is not particularly limited, but may be 99.9% by mass or less, 99.7% by mass or less, or 99.5% by mass or less, based on 100% by mass of the total content of the ionically crosslinkable polymer, ionically crosslinking agent, and environmentally degradable resin.

[0016] An ionically crosslinkable polymer is a polymer that has ionically crosslinking groups. The ionic crosslinking agent is an agent that itself serves as a crosslinking point for an ionic crosslinking reaction. The ionically crosslinkable polymer and the ionically crosslinking agent may each be contained in one kind or in two or more kinds.

[0017] The ionically crosslinkable polymer to be supplied may be in the form of a solid or liquid. The ionic crosslinking agent may be supplied in the form of a solid or liquid. The forms of the ionically crosslinkable polymer and the ionically crosslinking agent can be used in any combination, but a solid ionically crosslinkable polymer and a solid ionically crosslinking agent may be used, or a solid ionically crosslinkable polymer and a liquid ionically crosslinking agent may be used.

[0018] The shape of at least one of the solid ionically cross-linkable polymer and the solid ionically cross-linking agent may include, for example, one or more selected from the group consisting of granular, flat, fibrous, polyhedral, and irregular shapes. By using such granular shapes, dispersibility in the environmentally degradable resin can be improved. In this embodiment, the shapes of the ionically cross-linkable polymer and the ionically cross-linking agent can be measured by observing SEM images.

[0019] The ionically crosslinkable polymer preferably contains at least one of the following components (A) and (B). On the other hand, the ionic crosslinker is When the ionically crosslinkable polymer contains the following component (A), it is preferable that it contains one or more selected from the group consisting of the following components (B), (C), and (D): When the ionically crosslinkable polymer contains the following component (B), it preferably contains one or more selected from the group consisting of the following components (A), (C), and (D). (A) a polyanion having a monovalent or divalent or higher anionic group, or a salt containing the polyanion (B) A polycation having a monovalent or divalent or higher cationic group, or a salt containing the polycation (C) Inorganic cations having monovalent or divalent or higher cations, or salts containing one or more of the inorganic cations (D) An anionic monomer having a monovalent or divalent or higher anionic group, or an acid containing such an anionic monomer

[0020] In this specification, the valence in (A), (B), and (D) refers to the valence per ionic functional group (ionically dissociating group) contained in the monomer or polymer. Taking the example of an ionic functional group in the side chain of a polymer (macromolecule), carboxylic acid is monovalent, and dicarboxylic acid (oxalic acid, fumaric acid, etc.) is divalent. Meanwhile, in the case of (C), sodium ions are monovalent, and calcium ions are divalent. To give a specific example, polyacrylic acid polymers are classified as "polyanions having monovalent anionic groups," and alkylphosphonic acid polymers are classified as "polyanions having divalent anionic groups." In addition, in polyacrylic acid or a polymer containing acrylic acid as a component, when acrylic acid forms a calcium salt, it is classified as a "salt containing a polyanion" in which the monovalent anion group forms a salt with a divalent cation. Furthermore, in a polymer containing phosphonic acid as a constituent element, when the phosphonic acid forms a sodium salt, the polymer is classified as a "salt containing a polyanion" in which the divalent anion group forms a salt with a monovalent cation. Basically, a polymer whose main chain has a repeating structural unit α with an anionic group is called a "polyanion" (polymeric anion). On the other hand, a polymer whose main chain has a repeating structural unit β with a cationic group is called a "polycation" (polymeric cation). However, when the main chain of a polymer contains repeating structural units α and β, a polymer whose molecule contains the same or more repeating structural units α than the number of repeating structural units β is called a "polyanion," and conversely, a polymer whose molecule contains more repeating structural units β than the number of repeating structural units α is called a "polycation." A monomer that has an anionic group but does not have a repeating structural unit α having an anionic group is referred to as an "anionic monomer."

[0021] (A) "Polyanion having monovalent or divalent or higher anionic groups" preferably includes one or more polyanions A1 selected from the group consisting of polysaccharides containing at least one of carboxylic acid, sulfonic acid, and phosphoric acid in the molecule, and complex carbohydrates containing polysaccharides. The polyanion A1 preferably includes at least one of carboxylic acid and sulfonic acid.

[0022] As used herein, a monosaccharide is a sugar composed of one type of sugar. Examples of sugars include glucose, mannose, galactose, glucosamine, galactosamine, xylose, sialic acid, glucuronic acid, iduronic acid, fucose, maltose, trehalose, and lactose. In this specification, a polysaccharide is a saccharide formed by glycosidic bonds between two or more monosaccharides. A polysaccharide may be a homopolysaccharide, which has only one type of monosaccharide, or a heteropolysaccharide (sometimes called a complex polysaccharide), which has two or more types of monosaccharides. Furthermore, the polysaccharide may be any polysaccharide as long as it has a sugar chain (main chain) consisting of a repeating structure of structural units derived from monosaccharides, and functional groups may or may not be formed on the side chains of the sugar chain. Examples of functional groups formed on the side chains include polar functional groups such as a carboxyl group, a sulfonic acid group, an amide group, an acetyl group, an acetylamide group, and an amino group. As used herein, a glycoconjugate is a complex in which a polysaccharide is covalently bonded to other biological compounds other than sugars, such as proteins, lipids, peptides, etc. Examples of glycoconjugates include biopolymers such as glycoproteins, proteoglycans, and glycolipids.

[0023] The polysaccharide in the polyanion A1 may include, for example, one or more selected from the group consisting of alginic acid, carboxymethylcellulose, carrageenan, homogalacturonan, and glycosaminoglycan. Furthermore, the complex carbohydrate in the polyanion A1 may contain, for example, one or more selected from the group consisting of hyaluronic acid and chondroitin sulfate.

[0024] In another embodiment, (A) "a polyanion having a monovalent or divalent or higher anionic group" may include one or more polyanions A2 selected from the group consisting of lignosulfonic acid and polyglutamic acid. That is, (A) may include polyanion A1 alone, polyanion A2 alone, or both polyanion A1 and polyanion A2. Furthermore, the salt containing (A) a "polyanion having a monovalent or divalent or higher anionic group" may include a salt of the polyanion with a monovalent cation, i.e., an anionic compound in which an anionic group of the polyanion forms a salt with a monovalent cation, or may include a salt of a polyanion having at least one of polyanion A1 and polyanion A2 with a monovalent cation. (A) The salt containing the polyanion may include, as the monovalent cation, one or more ions selected from the group consisting of sodium ions, potassium ions, ammonium ions, and phosphonium ions.

[0025] (B) "Polycations having monovalent or divalent or higher cationic groups" include, for example, polylysine and chitosan. Furthermore, the salt containing (B) a "polycation having a monovalent or divalent or higher cationic group" may include a salt of the polycation with a monovalent anion, i.e., a cationic compound formed by the cationic group of the polycation and a monovalent anion. The salt containing (B) the polycation may include, as the monovalent anion, one or more ions selected from the group consisting of chloride ions, hydroxide ions, fluoride ions, bromide ions, iodide ions, acetate ions, and nitrate ions.

[0026] The inorganic cation having a monovalent cation may include, for example, one or more selected from the group consisting of sodium ions, potassium ions, and ammonium ions. (C) The inorganic cation having a valence of two or more may include, for example, one or more ions selected from the group consisting of calcium ions, magnesium ions, and aluminum ions. The salt containing one or more of (C) "inorganic cations having a monovalent or divalent or higher cation" may include a salt of one or more of the inorganic cations with a monovalent or divalent or higher inorganic anion, and specifically may include an ionic compound containing (C) an inorganic cation having a monovalent cation and / or (C) a divalent or higher inorganic anion and one or more inorganic anions selected from the group consisting of sulfate ions, chloride ions, hydroxide ions, phosphate ions, carbonate ions, fluoride ions, bromide ions, iodide ions, nitrate ions, and acetate ions.

[0027] (D) The anionic monomer having a monovalent, divalent or higher anionic group may include an anionic monomer having one or more carboxyl groups, or may include an anionic monomer having a carboxylate group. (D) The acid containing an anionic monomer having a monovalent, divalent or higher anionic group may contain an acid in which a proton is bonded to the anionic group of the anionic monomer. (D) Examples of the acid containing the anionic monomer include anionic monomers having one or more carboxyl groups, such as oxalic acid, fumaric acid, ethylenediaminetetraacetic acid (EDTA), citric acid, adipic acid, etc. These may be used alone or in combination of two or more.

[0028] The weight average molecular weight of at least one of component (A) and component (B) may be, for example, 1,000 or more and 10,000,000 or less. The molecular weight of the raw material monomer of component (A), the raw material monomer of component (B), and / or the anionic monomer or acid containing the anionic monomer of component (D) may be, for example, 1 to less than 1,000. In this specification, the weight average molecular weight is a value calculated in terms of polystyrene.

[0029] The composite material may also contain one or more selected from the group consisting of (X) hydrates of the ionic crosslinkers described above, (Y) inorganic hydrates other than (X), and (Z) sodium silicate. The (Y) inorganic hydrate is not limited as long as it is an inorganic hydrate other than the (X) ionic crosslinker, but it is preferable that it does not include a hydrate of a salt containing any ion selected from the group consisting of calcium ions, magnesium ions, and aluminum ions. Specific examples of (Y) inorganic hydrates that can be used include sodium carbonate decahydrate, sodium acetate trihydrate, sodium thiosulfate pentahydrate, disodium hydrogen phosphate dihydrate, disodium hydrogen phosphate heptahydrate, disodium hydrogen phosphate octahydrate, disodium hydrogen phosphate dodecahydrate, sodium dihydrogen phosphate monohydrate, sodium dihydrogen phosphate dihydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, copper(II) sulfate pentahydrate, cobalt(II) iodide hexahydrate, tin(II) chloride dihydrate, and iron(III) oxide hydrate.

[0030] Additionally, the composite material may or may not include an ionically cross-linked material having at least ionic cross-links within its molecules.

[0031] The ionically cross-linked material preferably comprises an ionically cross-linked water-absorbing polymer. Compared to conventional composite materials such as polyolefin resins, ionically cross-linked water-absorbing polymers are able to absorb water and swell. Even when an ionically cross-linked water-absorbing polymer that has absorbed water gels, it is believed that the fertilizer inside dissolves in the water in the gel and is released to the outside. It is sufficient for the ionically cross-linked water-absorbing polymer to be able to absorb water, and it does not matter whether it can absorb oils other than water or not. The weight average molecular weight of the ionically cross-linked material and the ionically cross-linked water-absorbent polymer may each be, for example, 1,000 or more and 10,000,000 or less.

[0032] The ionically crosslinked water-absorbing polymer preferably contains at least one of the following (i) to (vi) as a polymer salt containing at least two of the following (A') to (D'). (i) (A') and (C'), (ii) (A'), (C') and (D') (iii) (A'), (B'), and (C') (iv) (A') and (B') (v) (B') and (D') (vi) (A'), (B'), (C') and (D') (A') Polyanion having monovalent or divalent or higher anionic groups (B') Polycation having monovalent or divalent or higher cationic groups (C') Polyvalent inorganic cations having monovalent or divalent or higher cations (D') Anionic monomer having a monovalent or divalent or higher anionic group

[0033] The composite material can improve its seawater decomposition ability by containing the above polymer salt as the ionically cross-linked water-absorbent polymer. The term "seawater decomposability" refers to a change in the properties of the polymer salt that makes it more soluble in aqueous solvents due to an ion exchange reaction between ions present in seawater and ions in the polymer salt. When composite materials are dissolved and fragmented in seawater, the increased surface area increases the number of microorganisms that come into contact with the surface, which is expected to accelerate the decomposition of the environmentally degradable resin.

[0034] The mechanism of seawater decomposition will be explained using an example in which the ionically cross-linked water-absorbent polymer contains the polymer salts (A') and (C') as the combination (i) above. However, the ionically cross-linked water-absorbent polymer is not limited to this. Ionically cross-linked polymers of alginate polymers (polyanions with monovalent anionic groups) and calcium ions (polyvalent inorganic cations) form ionic cross-linked structures in water, but in salt water (seawater), the calcium ions are exchanged for sodium, dissociating the cross-links, making the polymer soluble in salt water.

[0035] In another embodiment, the ionically crosslinked water-absorbing polymer is preferably a polymer salt containing at least one of (A') a polyanion having a monovalent or divalent or higher anionic group and (D') an anionic monomer having a monovalent or divalent or higher anion. More specifically, it is more preferable to use a polymer salt containing at least one of the above (i) and (ii).

[0036] The composite material may or may not contain, as the ionically crosslinked water-absorbent polymer, an ionically crosslinked material obtained by reacting the above-mentioned ionically crosslinkable polymer with the above-mentioned ionically crosslinking agent.

[0037] The composite material may contain, in addition to the ionically crosslinkable polymer, the ionically crosslinking agent, and the environmentally degradable resin, other additives such as inorganic fillers, surfactants, sizing agents, hydrophobic substances, functional additives, etc. These may be contained alone or in any combination of two or more.

[0038] The composite material may or may not contain inorganic fillers. The inorganic filler may be any inorganic filler that is poorly soluble or insoluble in water, and may include, for example, one or more selected from the group consisting of silica, talc, magnesium oxide, calcium oxide, alumina, titanium oxide, calcium carbonate, clay, potassium titanate, mica, glass flakes, whiskers, ferrite, iron oxide, zeolite, and magnesium sulfate. Among these, silica, talc, calcium carbonate, clay, mica, etc. are preferred from the viewpoints of price and availability.

[0039] The upper limit of the content of the inorganic filler is, for example, 50% by mass or less, preferably 49% by mass or less, and more preferably 48% by mass or less, relative to 100% by mass of the composite material, which can improve the coating strength of the composite material. The lower limit of the content of the inorganic filler is, for example, 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more, based on 100% by mass of the composite material. This allows the moisture permeation rate to be controlled low due to the water blocking effect.

[0040] The composite material may contain at least one of a surfactant and a sizing agent, or may contain neither of them. The surfactant and the sizing agent can control the dispersion state of the ionically crosslinked material. Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. Among these, anionic surfactants and nonionic surfactants are preferred. Examples of sizing agents include natural sizing agents, synthetic sizing agents, reactive sizing agents, special sizing agents, etc. Among these, natural sizing agents and synthetic sizing agents are preferred. These may be contained alone or in any combination of two or more.

[0041] The composite material may include a hydrophobic material. The hydrophobic substance is any one of waxes, oils and fats, and fatty acids, or a mixture of two or more of the group consisting of these, and may include, for example, one or more selected from the group consisting of hydrocarbon waxes, fatty acid waxes, higher alcohol waxes, glycerin fatty acid esters, and fatty acids. The hydrophobic substance may also include polyester polyol or rosin resin. The addition of polyester polyol or rosin resin can control fluidity and moisture permeability. The polyester polyol may be biodegradable. The polyester polyol may be, for example, a copolymer of at least an organic acid and a glycol. The organic acid may include an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, and, if necessary, an aromatic dicarboxylic acid. The glycol may include, for example, ethylene glycol, butanediol, hexanediol, etc. Examples of rosin resins include rosin ester, hydrogenated rosin ester, modified rosin, maleated rosin, fumarated rosin, maleated rosin ester, disproportionated rosin ester, and polymerized rosin ester. Here, the wax may be any one of hydrocarbon waxes, fatty acid waxes, and higher alcohol waxes, or a mixture thereof. The fatty acid wax may contain, for example, one or more waxes selected from the group consisting of aliphatic esters, aliphatic ketones, aliphatic amides, and fatty acid metal soaps. The wax may be any of natural wax, synthetic wax, and modified wax. Natural waxes include those derived from plants, animals, minerals, and petroleum. Examples of fats and oils include glycerin fatty acid esters. The glycerin fatty acid esters may include any one of monoglycerin fatty acid esters, diglycerin fatty acid esters, and triglycerin fatty acid esters, or a mixture of two or more of these. The glycerin fatty acid esters may also include polyglycerin fatty acid esters, such as those in which one hydroxyl group of glycerin is dimerized via an ether bond. Examples of fatty acids include fatty acids having less than 10 carbon atoms and higher fatty acids having 10 or more carbon atoms. Fatty acids may include straight-chain fatty acids having a main chain and no side chains, branched fatty acids having a main chain and a side chain, and / or cyclic fatty acids having at least one ring structure. Fatty acids may also include fatty acid derivatives such as hydroxy fatty acids having at least one hydroxyl group and polymers of hydroxy fatty acids. These may be used alone or in combination of two or more. The fatty acids and aliphatic skeletons each contain saturated bonds and / or unsaturated bonds. The glycerin fatty acid esters may include highly purified products that have been purified by distillation or the like. The hydrophobic substance may include one or more of the following waxes and vegetable oils. Specific examples of waxes include natural waxes such as carnauba wax, beeswax, and rice wax; petroleum waxes such as paraffin wax and microcrystalline wax; and synthetic waxes such as Fischer-Tropsch wax and polyethylene wax. Specific examples of vegetable oils include palm oil, soybean oil, rapeseed oil, sunflower oil, palm kernel oil, cottonseed oil, peanut oil, olive oil, coconut oil, corn oil, sesame oil, linseed oil, safflower oil, rice oil, and perilla oil.

[0042] Here, a method for producing the above composite material will be described. An example of a method for producing a composite material may include a step of melt-kneading raw material components including the ionically cross-linkable polymer, the ionically cross-linking agent, and the environmentally degradable resin using a kneading device to obtain a solid composite material. The raw material components may also include one or more other additives.

[0043] The order in which the raw material components are supplied to the kneading device is not particularly limited, but after the addition of the environmentally degradable resin, the ionically crosslinkable polymer, the ionically crosslinking agent, and other additives may be added depending on various applications. If necessary, at least two or more components contained in the raw material ingredients may be mixed in advance before kneading the raw material ingredients.

[0044] The temperature during melt kneading can be adjusted depending on the melting point or softening point of the environmentally degradable resin used, and may be, for example, 50 to 300°C, preferably 70 to 290°C, and more preferably 90 to 280°C.

[0045] The raw material components may contain adsorbed water or crystal water as moisture contained in each component of the raw material components.

[0046] Another example of a method for producing a composite material may include a step of obtaining a liquid composite material containing raw material components including the ionically crosslinkable polymer, the ionically crosslinking agent, and the environmentally degradable resin, and a solvent. If necessary, the raw material components may contain other additives depending on the intended use.

[0047] The solvent may include a solvent having a boiling point of 30°C to 210°C. The solvent is preferably an organic solvent (non-aqueous solvent), and examples thereof include halogen-based solvents such as chloroform, trichloroethylene, dichloroethane, etc.; aromatic solvents such as toluene; aliphatic solvents such as hexane; alicyclic solvents such as cyclohexane; ketone-based solvents such as acetone and MEK; ester-based solvents such as ethyl acetate; and alcohol-based solvents such as methanol, ethanol, isopropanol, etc. These may be contained alone or in any combination of two or more.

[0048] In the process of obtaining a liquid composite material, the order in which the components contained in the raw material ingredients are mixed with the solvent is not particularly limited. Heating may or may not be performed at any stage during the mixing.

[0049] The liquid composite material may be a one-component liquid containing at least an ionic crosslinking agent, an ionic crosslinkable polymer, and a second liquid, or a two-component liquid containing a first liquid containing at least an ionic crosslinking agent and a second liquid containing at least an ionic crosslinkable polymer. In the case of a two-component liquid, the environmentally degradable resin is contained in at least one of the first and second liquids.

[0050] Additionally, the composite material of the present embodiment can be used as an intermediate product or a final product for a variety of applications. The composite material can be used, for example, as a coating material, a film material, etc. (hereinafter, these will be collectively referred to as application materials), but is not limited to these applications. The application fields of the composite materials are not particularly limited, but include agriculture, fishing, livestock farming, medicine, cosmetics, food, construction, and other industries.

[0051] The application materials may each contain at least one of the following resin compositions (J1) to (J4) as the solid content of the composite material. The resin composition (J1) contains an ionically crosslinkable polymer, an ionically crosslinking agent, and an environmentally degradable resin. The resin composition (J2) contains an ionically crosslinkable polymer, an ionically crosslinking agent, an ionically crosslinking material, and an environmentally degradable resin. The resin composition (J3) contains only one of an ionically crosslinkable polymer and an ionically crosslinking agent, and also contains an ionically crosslinkable material and an environmentally degradable resin. The resin composition (J4) does not contain either an ionically crosslinkable polymer or an ionically crosslinking agent, and contains an ionically crosslinkable material and an environmentally degradable resin. Furthermore, other additives than the resin compositions (J1) to (J4) may be contained, such as known additives used in various applications, inorganic fillers, surfactants, sizing agents, hydrophobic substances, functional additives, etc. These may be contained alone or in any combination of two or more. The solid content of the composite material does not substantially contain the solvent contained in the liquid composite material.

[0052] <Coating material> The coating material of this embodiment includes the above-described composite material. This coating material is preferably used to coat any of the following coating objects (a1) to (a4). (a1) Agricultural active ingredients (a2) Seeds (a3) Feed (a4)Fragrance

[0053] (a1) The agriculturally active ingredient may be any substance used to grow, promote, or protect agricultural crops, such as a fertilizer ingredient or a pesticide ingredient. These may be contained alone or in any combination of two or more. The coating material is not limited to agriculturally active ingredients, but may also contain other water-soluble ingredients, such as active ingredients used in pharmaceuticals, cosmetics, and foods.

[0054] (fertilizer ingredients) As the fertilizer component, known fertilizers can be used, for example, one or more of nitrogenous fertilizers, phosphorous fertilizers, and potassium fertilizers can be used. As nitrogenous fertilizers, for example, ammonium salts and nitrates are used, and specific examples include ammonium sulfate, ammonium chloride, urea, lime nitrogen, sodium nitrate, and ammonium nitrate. Examples of phosphorus fertilizers include calcium superphosphate, calcium triple superphosphate, fused phosphate fertilizer, and calcined phosphate fertilizer. Examples of potassium fertilizers include potassium chloride and potassium sulfate. In addition to the above three fertilizers, the fertilizer may also contain other fertilizers (calcareous fertilizers, silicate fertilizers, manganese fertilizers, boron fertilizers, etc.) and one or more known inorganic compounds containing inorganic nutrients.

[0055] The fertilizer components may contain other components as long as the effects of the present invention are not impaired. Other components may include, for example, carriers such as clay, kaolin, talc, bentonite, calcium carbonate, etc.; binders such as polyvinyl alcohol, sodium carboxymethyl cellulose, starches, etc.; and, if necessary, surfactants such as polyoxyethylene nonylphenyl ether, blackstrap molasses, animal oil, vegetable oil, hydrogenated oil, fatty acid, fatty acid metal salt, paraffin, wax, glycerin, etc. These may be used alone or in combination of two or more.

[0056] The form of the fertilizer ingredients is not particularly limited as long as they are solid in the atmosphere at 25°C. The shape of the fertilizer components may be, for example, powder, granules, pellets, briquettes, or any other granular fertilizer having a predetermined shape. Among these, from the viewpoint of dispersibility, the shape of the fertilizer is preferably spherical.

[0057] The granular fertilizer can be produced by using a known granulation method such as a fluidized bed granulation method, a tumbling granulation method, a coating granulation method, an adsorption granulation method, or an agglomeration granulation method, but the method for producing the granular fertilizer is not limited to these.

[0058] The coating material that coats the fertilizer components may contain the following functional additives, if necessary. The functional additive is not particularly limited as long as it is used in the fertilizer composite material, and examples thereof include fillers other than the above-mentioned inorganic fillers, thickeners, adhesion promoters, surface modifiers, pH adjusters, crosslinking retarders (chelating agents), reinforcing materials, gas barrier agents, magnetic materials, decomposition inhibitors, etc. These may be used alone or in combination of two or more.

[0059] Here, the coating material may be used to form a resin shell structure that encapsulates one or more coating targets, or may be used to form a resin matrix structure in which multiple coating targets are arranged or dispersed, or may be used to form a resin bonded structure that acts as a binder between the coating targets.

[0060] The coating material can, for example, slowly release the coated object to the outside, and can also adjust the permeability of the coating material to the inside of the coated object, such as water, air, and / or carbon dioxide, depending on the requirements of the coated object.

[0061] In one form, the coating material may be used to form a coating layer that covers at least a part or the entire surface of an object to be coated. This form of coating has a coating layer containing the coating material and an object whose surface is covered with the coating layer.

[0062] The coating method may be any known method for coating the surface of solid particles, including, for example, chemical methods such as a non-aqueous wet method, an aqueous wet method, a gas phase reaction method, and a mechachemical method, and physical methods such as a mechanical surface treatment method, a laser ablation method, an air suspension coating method, and a spray drying method. When coating the granules with the composite material, it is preferable to use a fluidized bed granulation method or a rolling granulation method. When applying such a production method, it is preferable to use a liquid composite material. However, when using a solid composite material, it is not limited to this, and it is also possible to use a varnish made by dissolving it in a solvent.

[0063] (Pesticide ingredients) Pesticide ingredients include fungicides, insecticides, and other chemicals (including materials that use such chemicals as raw materials or ingredients and are used for such control) used to control bacteria, nematodes, mites, insects, rodents, and other plants and animals or viruses (hereinafter referred to as "pests") that harm crops (including trees and agricultural and forestry products; hereinafter referred to as "crops, etc."), as well as plant growth regulators, germination inhibitors, and other chemicals used to enhance or suppress the physiological functions of crops, etc. However, there are no particular restrictions on pesticides as long as they are chemicals used for agricultural purposes, and any chemical can be used, including insecticides, fungicides, and herbicides.

[0064] (a2) Seeds include, for example, plant seeds, preferably seeds used to cultivate crops. The seed may be a cereal (eg, wheat, oat, rice, maize (corn kernels), barley, sorghum, rye, millet), fruit, vegetable, legume or other type of seed. The coating material may be any material that covers at least a portion of the surface of a seed. By applying the coating material to the seed surface, properties such as seed protection, growth promotion, gas permeability, or water permeability can be imparted to the seed. The coating material may also contain one or more agriculturally active ingredients, such as fertilizers, pesticides, antimicrobial agents, and plant growth regulators. The seed coating material may also contain antifreeze agents, thickeners, antifoaming agents, pigments, preservatives, pH adjusters, fusing agents, stabilizers, and active ingredients, either alone or in combination of any two or more thereof. The coating material can be applied to the surface of the seeds by various methods, such as spraying or mixing.

[0065] (a3) Feed includes feed or feedstuffs used in the fields of aquaculture, livestock farming, pets, etc., i.e., food for living organisms. Examples of living things include fish, shellfish, and animals. The feed may contain ingredients such as meat, nutritional components, and drugs. Known meat ingredients can be used depending on the intended use of the feed, such as fish meat gel for seafood and meat chunks for pets. Examples of nutritional components include water-soluble nutritional components such as water-soluble proteins, amino acids, and water-soluble vitamins. The coating material may be any material that covers at least a portion of the surface of the feed. The coating material can be used to obtain a feed capsule in which granular feed is coated with the coating material. Furthermore, the coating material can be used as a binder to bind the feed together, thereby obtaining a shaped product (lump feed) containing the feed and the coating material.

[0066] (a4) Examples of fragrances include synthetic fragrances, natural essential oils, natural fragrances, animal and plant extracts, etc. The coating material may be any material that coats a portion of the surface of the fragrance. A fragrance capsule can be obtained in which the fragrance is encapsulated inside the coating material. An example of a fragrance capsule has a core portion encapsulated in a shell portion, and the core portion may contain the coating material as the shell portion and the fragrance as the core material. The fragrance may also contain an oil component and a solvent. The coating material allows the fragrance encapsulated in the fragrance capsule to be gradually released to the outside. The fragrance capsules can be used for a variety of purposes, including laundry applications such as fabric softeners, hair care compositions such as rinses, conditioners, and hair styling products, and day care applications such as cosmetic sheets, diapers, and masks.

[0067] <Film materials> The film material of this embodiment includes the composite material described above. By utilizing the permeability of film materials to water and air and / or the ability to release functional components from the outside, film-like composite materials can be used in a variety of applications.

[0068] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0069] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the descriptions of these examples.

[0070] <Production of coating materials> Example 1 Sodium alginate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an ionically crosslinkable polymer and aluminum sulfate 14-18 hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an ionically crosslinking agent were pulverized and mixed in a mortar to obtain a mixture. The resulting mixture was mixed with polybutylene succinate (PBS) as an environmentally degradable resin under heating to obtain a coating material. The content of the ionically crosslinkable polymer in 100% by mass of the coating material was 3% by mass, and the content of the ionically crosslinking agent was 15% by mass relative to 100% by mass of the ionically crosslinkable polymer.

[0071] Example 2 A coating material was produced in the same manner as in Example 1, except that calcium carbonate was added to the mixture as an inorganic filler. The content of the ionically crosslinkable polymer was 10% by mass, the content of the inorganic filler was 25% by mass, and the content of the ionically crosslinking agent was 10% by mass relative to 100% by mass of the ionically crosslinkable polymer.

[0072] <Evaluation of urea sustained release> (Preparation of 50 evaluation samples) First, the covering material was formed into a film having a thickness of about 100 μm, and the obtained film was punched into a circle having a diameter of 15 mm to obtain a film-like test piece 10. Next, using a tablet molding machine, solid urea (specific gravity: approximately 1.3) was compressed into cylindrical tablets with a height of 1 mm, a diameter of 10 mm, and a volume of approximately 78 mm3, to obtain cylindrical urea tablets 20 with flat upper and lower surfaces 21. Next, the processed film-like test piece 10 was placed so that the inner surface 13 faced the upper and lower surfaces of the urea tablet 20, and these side surfaces 23 were fixed using ring-shaped silicone rubber (waterproof member 30) to produce an evaluation sample 50.

[0073] (Measurement of urea release amount) Standard solutions of known urea concentrations in the range of 1 mg / mL to 12 mg / mL were prepared, and a calibration curve showing the relationship between absorbance and urea concentration was prepared. The evaluation sample 50 was subjected to a water treatment by immersing it in distilled water (water 60) stored in a polypropylene container 70 at room temperature of 25°C and atmospheric pressure, as shown in Fig. 1. During the water treatment, the outer surface 11 of the film-like test piece 10 was kept in contact with the water 60. Immediately after the water treatment, the absorbance of the water 60 at a wavelength of 450 nm was measured over time using an absorbance meter, and the urea concentration was determined from a calibration curve. From the obtained results, the amount of urea in the urea tablet 20 that has moved into the external water 60 (urea dissolution rate) can be measured. 80 (days) was calculated. Similarly, instead of the coating materials of Examples 1 and 2, a 100 μm thick film of PBS alone was used. 80 was calculated.

[0074] According to the above <Evaluation of urea sustained release>, T 80 The results showed that the value of index T decreased in the order of PBS alone, the coating material of Example 1, and the coating material of Example 2. 80 The smaller the value, the higher the effect of the coating material in providing a sustained release rate. Therefore, by forming a composite of an ionically crosslinkable polymer and an ionically crosslinking agent with an environmentally degradable resin, a coating material with excellent controlled sustained release of urea can be realized.

[0075] Example 3 The pellet-like composite material obtained above was dissolved in a mixed solvent of toluene and MEK to produce a liquid composite material. The resulting liquid composite material was applied to a supporting substrate, and the solvent was removed by drying to form a film. It was confirmed that a film-like composite material could be produced by separating the formed film from the supporting substrate.

[0076] Example 4 Sodium alginate (Tokyo Chemical Industry Co., Ltd.) as an ionically cross-linkable polymer, aluminum sulfate 14-18 hydrate (Fujifilm Wako Pure Chemical Industries, Ltd.) as an ionically cross-linking agent, and polybutylene succinate (PBS) as an environmentally degradable resin were blended in a predetermined mass ratio and melt-kneaded using an extruder as a kneading machine, and the resulting melt-kneaded mixture was extruded through a die. The extruded strands were cut and formed into pellets. It was confirmed that by producing such a composite material, it was possible to produce a pellet-shaped composite material that was solid at room temperature. The pellet-shaped composite material was heat-pressed to obtain a film-shaped composite material. (Comparative Example 1) On the other hand, a film-like composite material containing sodium alginate and PBS was obtained in the same manner as in Example 4, but without adding an ionic crosslinking agent.

[0077] Example 4 showed a higher modulus of elasticity than Comparative Example 1, and therefore showed the result that a film with excellent mechanical properties was obtained. [Explanation of symbols]

[0078] 10 Film-shaped test piece 11 Exterior 13 Inner 20 urea tablets 23 Side 30 Waterproofing materials 50 evaluation samples 60 water 70 containers

Claims

1. A composite material comprising an ionically crosslinkable polymer, an ionically crosslinking agent, and an environmentally degradable resin.

2. A coating material comprising the composite material of claim 1, A coating material used to coat any of the following coating objects (a1) to (a4). (a1) Agricultural active ingredients (a2) Seeds (a3) Feed (a4) Fragrance

3. A film material comprising the composite material of claim 1.

Images