JP2005162872A - Resin composition, molded product, electrical product, and method for producing the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition enabling such high flame retardancy and storability as to be required for e.g. electrical product casing materials to be made compatible with each other. <P>SOLUTION: The resin composition comprises at least one biodegradable organic macromolecular compound, a flame-retardant additive comprising a phosphorus-containing compound and hydroxide(s), and at least one hydrolysis inhibitor for the biodegradable organic macromolecular compound. In this resin composition, the biodegradable organic macromolecular compound(s) is an aliphatic polyester resin and/or a polysaccharide, wherein the aliphatic polyester resin is selected from polylactic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, microorganism-synthesized polyester and copolymers containing at least one of them mentioned above, and the polysaccharide is selected from cellulose, starch, chitin, chitosan, dextran, one of derivatives thereof and copolymers containing at least one of them mentioned above. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a biodegradable resin composition, molded article, electrical product, and method for producing a resin composition.

  Conventionally, various synthetic resin materials have been developed and provided, and the amount of use in various industrial fields increases year by year, and the production amount reaches nearly 10 million tons per year. As a result, the amount of synthetic resin discarded has increased, and its treatment has become a major social problem. If the discarded resin is incinerated as it is, harmful gas may be generated or the incinerator may be damaged by a large amount of combustion heat, which places a heavy load on the environment.

  As a disposal method of the waste resin known so far, for example, there is a method of incinerating or landfilling a resin whose molecular weight is reduced by thermal decomposition or chemical decomposition. However, since the incineration process involves the discharge of carbon dioxide, there is a risk of causing global warming. In addition, when sulfur, nitrogen, halogen, or the like is contained in the incineration resin, incineration treatment contributes to air pollution due to harmful exhaust gas. On the other hand, when the resin is landfilled, most of the currently used resins remain as they are without being decomposed for a long time, which causes soil contamination.

  Therefore, in order to deal with such problems, bio-degradable natural materials such as biocellulose and starch-based plastics, low-substituted cellulose esters, natural polyesters by microorganisms, aliphatic polyester resins by chemical synthesis, etc. As a plastic, its manufacture and use are being studied. Since biodegradable resins are biochemically decomposed into carbon dioxide and water by microorganisms, etc., even when discarded into the natural environment, they are easily decomposed to lower molecular weight and become harmless to the environment. Change. Therefore, by using a biodegradable resin, it is possible to reduce adverse effects on the global environment due to disposal. For these reasons, practical use has been promoted for disposable products mainly made up of daily miscellaneous goods, sanitary goods, play goods and the like.

  As mentioned above, conventional biodegradable resins are superior in terms of safety to the natural environment, but the flame retardance is increasing as one of the safety when actually using the resin The existing biodegradable resin is not enough. In particular, for electrical products, there is a desire to facilitate the post-recovery process by forming the housing etc. with a biodegradable resin. ) And UL (Underwriter Laboratory) standards, it is necessary to satisfy the flame retardant standard, and existing biodegradable resins cannot meet the flame retardant standard.

  In addition, when the biodegradable resin is applied to a practical product such as a casing of, for example, an electric product or an electronic device, storage characteristics (durability under high temperature and high humidity conditions) are required in addition to the flame retardancy. For example, in a portable audio product, it is necessary to maintain physical properties such as strength for 3 to 7 years under conditions of 30 ° C. and 80% relative humidity.

In view of this, various studies have been conducted to impart biodegradable resins with physical properties suitable for practical molded products. For example, a method for improving biodegradability and moldability by blending an appropriate amount of a biodegradable resin exhibiting rubber-like properties having a low glass transition point with an aliphatic polyester resin that is a typical example of a biodegradable polymer (for example, , See Patent Document 1), a method of improving mechanical strength by adding calcium carbonate and / or magnesium carbonate to an aliphatic polyester resin (see, for example, Patent Document 2), melting poly-3-hydroxybutyric acid Thereafter, a method for improving the biodegradability by rapidly solidifying and forming a molded body having a crystallinity of less than 50% (for example, see Patent Document 3) has been proposed.
JP-A-3-290461 JP-A-4-146852 JP-A-4-325526

  However, it is assumed that the molded article made of the biodegradable resin described in Patent Documents 1 to 3 described above is mainly used for a film, a packaging material, and the like, and the flame retardancy and storage characteristics are not sufficient. There's a problem.

  Therefore, the present invention has been proposed in view of such a conventional situation, for example, a resin composition that can achieve both high flame retardancy and storage characteristics required for a casing material of an electrical product, for example. It is an object of the present invention to provide a product, a method for producing the product, a molded product of the resin composition, and an electrical product using the molded product.

  As a result of various studies on improving the physical properties of biodegradable resins, the present inventors have found that flame retardancy can be improved by adding flame retardant additives to biodegradable resins. It was. The flame retardant additive is typically a halogen flame retardant additive. However, when a biodegradable resin containing a halogen flame retardant additive is incinerated, a halogen gas is generated. There is an inconvenience that a complicated process is required to make it harmless.

  Therefore, as a result of intensive studies on a novel flame retardant additive, the present inventors have found that a phosphorus-containing compound having a phosphorus atom in the molecule is an excellent flame retardant additive when combined with a biodegradable resin. It can be used as a flame retardant additive that acts on the environment and is environmentally friendly. Further, it has been found that the storage characteristics can be improved by adding a hydrolysis inhibitor, and the present invention has been completed. It was.

  That is, the resin composition according to the present invention includes at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and hydrolysis of at least one organic polymer compound. It contains the hydrolysis inhibitor which suppresses.

  The molded product according to the present invention includes at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and hydrolysis of at least one organic polymer compound. It is characterized by molding a resin composition containing a hydrolysis inhibitor that suppresses the above.

  The electrical product according to the present invention includes at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and hydrolysis of at least one organic polymer compound. A molded article formed by molding a resin composition containing a hydrolysis inhibitor that suppresses odor is included as a constituent element.

  The method for producing a resin composition according to the present invention includes at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and at least one organic polymer compound. It is characterized in that it is combined with a hydrolysis inhibitor that suppresses hydrolysis of the compound.

  By adding a phosphorus-containing compound to a biodegradable organic polymer compound, when high heat is applied to the biodegradable organic polymer compound, the dehydration action and the heat shielding effect due to char formation are synergistic. Thus, high flame retardancy can be imparted to an organic polymer compound that functions and exhibits biodegradability.

  In addition, by adding a hydrolysis inhibitor that suppresses hydrolysis, the hydrolysis rate of the organic polymer compound exhibiting biodegradability is delayed, and as a result, compared with the case where no hydrolysis inhibitor is added, High mechanical strength can be maintained over a period of time. Thus, since the resin composition of the present invention contains a specific flame retardant additive (phosphorus-containing compound) and a hydrolysis inhibitor with respect to the organic polymer compound exhibiting biodegradability, flame retardancy and Both storage characteristics can be satisfied.

  According to the present invention, by including an organic polymer compound exhibiting biodegradability, a phosphorus-containing compound that exhibits a high flame retardancy when combined with this, and a hydrolysis inhibitor, for example, UL-standard V It has both extremely high flame resistance satisfying the range of -0 to V-1 and excellent storage characteristics that can be used, for example, as a housing for electrical products, and has little adverse effect on the natural environment when discarded. A resin composition can be provided.

  Further, according to the present invention, a resin composition comprising an organic polymer compound exhibiting biodegradability, a phosphorus-containing compound that exhibits a high flame retardancy when combined therewith, and a hydrolysis inhibitor is molded. Thus, for example, both extremely high flame resistance satisfying the UL standard V-0 to V-1 range and excellent storage characteristics that can be used, for example, as a housing of an electric product, and at the time of disposal It is possible to provide a molded product with less adverse effects on the natural environment.

  Further, according to the present invention, a molded article comprising an organic polymer compound exhibiting biodegradability, a phosphorus-containing compound that exhibits a high flame retardancy when combined therewith, and a hydrolysis inhibitor is used as a component. By making it a part, for example, it achieves both extremely high flame retardance satisfying the UL standard V-0 to V-1 range and excellent storage characteristics over a long period of time, and also to the natural environment at the time of disposal An electric product with few adverse effects can be provided.

  In addition, according to the present invention, there is provided a method for producing a resin composition that exhibits high flame retardancy and storage characteristics that can be used for, for example, a casing material of an electrical product, and that has little adverse effect on the natural environment when discarded. can do.

  Hereinafter, the resin composition of the present invention, the production method thereof, the molded product, and the electric product will be described in detail.

  The resin composition of the present invention comprises a biodegradable organic polymer compound, a phosphorus-containing compound that acts as a flame retardant additive, and a hydrolysis that regulates the hydrolysis rate of the biodegradable organic polymer compound. It contains an inhibitor. Here, the organic polymer compound exhibiting biodegradability (hereinafter sometimes referred to as “biodegradable polymer compound”) refers to a low molecular compound, that is, a low molecular compound that is ultimately associated with microorganisms in nature after use. It refers to a compound that decomposes into water and carbon dioxide (Biodegradable Plastics Research Society, ISO / TC-207 / SC3). The organic polymer compound exhibiting biodegradability is preferably a biodegradable resin, such as an aliphatic polyester resin exhibiting biodegradability, a polysaccharide, a peptide, polyvinyl alcohol, polyamide, polyalkylene glycol, or the like, or Examples thereof include a copolymer containing at least one of the compounds. As the organic polymer compound exhibiting biodegradability, these may be used alone, or they may be used in combination in order to obtain respective advantages.

  Among organic polymer compounds exhibiting biodegradability, it is preferable to use an aliphatic polyester resin exhibiting biodegradability that is excellent in mixing property and mass productivity. As the aliphatic polyester resin, polylactic acid such as poly-L-lactic acid (PLLA), a random copolymer of L-lactic acid and D-lactic acid, or a derivative thereof is more preferable. Of course, other aliphatic polyesters, for example, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, polyglycolic acid, polysuccinic acid ester, oxalic acid Esters, polybutylene diglycolates, polydioxanones, microbial synthetic polyesters, copolymers containing at least one of these, and the like can also be used. Here, examples of the microbial synthetic polyester include 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), or a copolymer thereof. As the aliphatic polyester resin, the above-described compounds may be used alone or in combination of two or more.

  In addition, as the organic polymer compound exhibiting biodegradability, polysaccharides having higher heat resistance than aliphatic polyester resins can be used. Examples of the polysaccharide contained in the resin composition include cellulose, starch, chitin, chitosan, dextran, or a derivative thereof, or a copolymer containing at least one of them. As the polysaccharide, the above-described compounds may be used alone, or two or more kinds may be used in combination. In addition, various plasticizers can be added to the polysaccharide to impart thermoplasticity.

  Examples of the cellulose derivatives include esterified cellulose. Specific esterified celluloses include organic acid esters such as cellulose acetate, cellulose butyrate, and cellulose propionate, cellulose nitrate, cellulose sulfate, and cellulose phosphate. A copolymer containing at least one of inorganic acid ester, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose nitrate acetate, and the like, and cellulose ester derivatives such as polycaprolactone-grafted cellulose acetate Etc. can be illustrated. These esterified celluloses may be used alone or in combination of two or more.

  The esterified cellulose used in the present invention can be produced according to a known method. Esterified cellulose can be produced by completely acetylating cellulose and then partially saponifying it. Furthermore, a plasticizer is added to the produced esterified cellulose in order to improve moldability. The plasticizer is not particularly limited as long as it has good biodegradability and an excellent plasticizing effect, but is preferably a low molecular weight ester plasticizer, and more preferably a phosphate ester or a carboxylate ester.

  Specific examples of the phosphate ester include triphenyl phosphate (TPP) and tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.

  Specific examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP) dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate, (DPP) and diethyl hexyl phthalate (DEHP). Examples of the citrate ester include triethyl O-acetylcitrate (OACTE), tributyl O-acetylcitrate (OACTB), acetyltriethyl citrate, acetyltributyl citrate and the like.

  Other examples of the carboxylic acid ester include various trimellitic esters such as butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Glycolic acid esters can also be used. Specific examples include triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate. Of these, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl hexyl phthalate, triacetin, ethyl phthalyl ethyl glycolate and the like are preferable. These plasticizers may be used alone or in combination of two or more.

  The starch-substituted derivative which is a modified starch can be produced according to a known method. The basic method for producing a starch-substituted derivative, which is a modified starch, is esterification, and the starch ester produced by these reactions has been known as an aqueous reaction esterified starch (starch ester) having a low substitution degree. It has been. ("Starch Science Handbook" (July 20, 1997) Asakura Shoten Co., Ltd. p550) In addition, regarding starch esters with a high degree of substitution, acid anhydrides are reacted in pyridine using dimethylaminopyridine or an alkali metal as a catalyst. Method ("Starch Chemistry & Technology" by Whistler, published by Academic Press, p332-336), a method in which an alkali metal hydroxide aqueous solution is used as a catalyst in an acid anhydride at a high temperature of 100 ° C or higher (special table) No. 5-508185, Die Starke 1972, March p73, etc.) and “Method of reacting in vinyl organic ester in non-aqueous organic solvent” (see JP-A-8-188601), etc. It has been known. Further, a natural fatty acid or the like may be added to starch as a raw material, followed by etherification or graft polymerization reaction to obtain a starch substituted derivative as a modified starch. Furthermore, in order to give these starch substituted derivatives (starch esters) moldability (for example, injection molding, extrusion molding, stretch molding, etc.) like ordinary thermoplastics (thermoplastic resins), a plasticizer is added. It may be added.

  Further, it may be a starch-substituted derivative (see, for example, JP 2000-159802 A) that can be thermoplasticized without adding a plasticizer or by using a small amount of plasticizer. The above contents are obtained by replacing the hydrogen of the reactive hydroxyl group on the same starch molecule with a long-chain hydrocarbon-containing group having 6 to 24 carbon atoms and a short-chain hydrocarbon-containing group (long-chain / short-chain hydrocarbon-containing group). ), And the substitution degree of the long-chain hydrocarbon-containing group and the short-chain hydrocarbon-containing group is adjusted, and the starch-substituted derivative having self-thermoplasticity while maintaining biodegradability. Is.

  As a plasticizer added to starch such as starch ester, a plasticizer highly compatible with starch ester is preferable, and the following various plasticizers (mainly ester type) can be used. For example, phthalate esters such as phthalates such as dimethyl, diethyl, and dibutyl, and ethyl phthaloyl ethyl glycolate and butyl phthaloyl butyl glycolate, and aliphatic esters such as oleic acid, adipic acid, and stearic acid. In the case of polyhydric alcohol esters such as methyl, ethyl, butyl, and isopropyl, sultrol acetate, diethyl glycol benzoate, triacetin (triacetyl glycerin), tripropionin (tripropionyl glycerin), acetyl diglycerin, etc. Methyl acid, acetyl triethyl citrate, etc., phosphate ester, tributyl phosphate, triphenyl phosphate, etc., epoxy plasticizer, epoxidized soybean oil, epoxidized castor oil, alkyl epoxy Among polymer plasticizers such as tearates, various liquid rubbers, terpenes, linear polyesters, etc. Among these, ester type plasticizers such as triethyl acetyl citrate, ethyl phthaloyl ethyl glycolate, triacetin, tripropionine, etc. Preferably used.

  Examples of the peptide include, but are not limited to, collagen, casein, fibrin, gelatin and the like.

  Examples of the polyamide include nylon 4, nylon 2 / nylon 6 copolymer, and the like.

  In addition, organic polymer compounds that are biodegradable at low molecular weight but low biodegradability at high molecular weight can be biodegradable by graft copolymerization with the biodegradable polymer compounds exemplified above. If it comes to be obtained, this can be used in this invention. Specific examples of organic polymer compounds that are low in biodegradability at such high molecular weights include polyethylene, polyacrylic acid derivatives, polypropylene, and polyurethane. Further, the molecular weights and terminal groups of these resins are not particularly limited as long as mechanical strength can be obtained.

  The organic polymer compound exhibiting biodegradability used in the present invention can be produced according to a known method. For example, biodegradable aliphatic polyester is obtained by a method such as lactide method, polycondensation of polyhydric alcohol and polybasic acid, or intermolecular polycondensation of hydroxycarboxylic acid having a hydroxyl group and a carboxyl group in the molecule. Although it can manufacture, it is not limited to these.

  In the present invention, a phosphorus-containing compound having a phosphorus atom in the molecule is used as a flame retardant additive. The phosphorus-containing compound having a phosphorus atom in the molecule can be combined (added) to the material to be added mainly composed of a polymer material such as a resin by mixing or fixing. By adding a phosphorus-containing compound, the additive functions as a flame retardant / stabilizer / bulking agent. For example, flame retardant for an organic polymer compound exhibiting biodegradability, which is an addition target material of the present invention.・ Stability and weight gain can be added. For example, when high heat (for example, 500 ° C. or higher) is applied to the material to be added, the dehydration action and the heat shielding effect by char generation function in synergy to impart high flame retardancy to the material to be added. be able to. Specifically, for example, when evaluated in a UL94 flammability test, it is possible to impart high flame retardancy performance that satisfies the range of V-0 to V-1.

  By combining the phosphorus-containing compound and the biodegradable polymer compound, higher flame retardancy can be obtained as compared with the case where the phosphorus-containing compound and another resin are combined. The reason for this is considered to be that the temperature at which the biodegradable polymer compound is decomposed and the temperature at which the phosphorus-containing compound acts as a flame retardant are close, and the biodegradable polymer compound and the phosphorus-containing compound are easily mixed.

  In addition, since the phosphorus-containing compound is a compound containing phosphorus, which is a component of the living body, the impact on the ecosystem is minimal compared to existing flame retardant additives such as halogen flame retardant additives. There is also an advantage.

  As the phosphorus-containing compound, an organic phosphorus compound, a phosphorus simple substance, an inorganic phosphorus compound, or the like can be used. Organophosphorus compounds include monomeric organophosphorus compounds, polymeric organophosphorus compounds, etc., and monomeric organophosphorus compounds include organophosphonates, organophosphinates, organophosphates, phosphate esters, phosphorous esters. An acid ester, a phosphine oxide, a hypophosphite ester optionally substituted by an alkyl group and / or an aryl group (for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.), Examples include phosphonocarboxylic acid esters, nitrogen-containing phosphates, ammonium salts of acidic aliphatic phosphates, and amine-containing compound salts. Examples of the phosphate esters include aliphatic phosphate esters, aromatic phosphate esters (such as triphenyl phosphate), and aliphatic-aromatic phosphate esters. Examples of the phosphites include aromatic phosphites, aliphatic phosphites, and aliphatic-aromatic phosphites.

  Among the organophosphorus compounds, polymer-type organophosphorus compounds include condensates of the above monomer-type organophosphorus compounds, phosphate esters of polymers having a hydroxyl group (such as phenolic resins), polyphosphinicocarboxylic acid esters, polyphosphonic acid amides. And phosphazene compounds.

  Examples of the condensate include resorcinol phosphates, hydroquinone phosphates, biphenol phosphates, bisphenol phosphates, and the like.

  Specific examples of phosphorus alone include red phosphorus, and examples of inorganic phosphorus compounds include polyphosphates, phosphates, red phosphorus surface treatment compounds, and the like. Examples of phosphoric acid of phosphate include orthophosphoric acid, phosphorous acid, polyphosphoric acid, polyphosphorous acid (metaphosphorous acid, pyrophosphorous acid, etc.) and the like. Examples of phosphate salts include alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), aluminum salts, ammonium salts, amine salts, etc. Can do.

The organic phosphorus compound, phosphorus simple substance, and inorganic phosphorus compound include organic phosphoric acid or inorganic phosphoric acid and a salt of a metal or an amine-containing compound. The organic phosphoric acid or inorganic phosphoric acid may be substituted with an alkyl group and / or an aryl group. Moreover, as a phosphorus containing compound, any of the above-mentioned compounds can be used individually or in combination of 2 or more types.
The phosphorus-containing compound is added in the phosphorus-containing compound with respect to 100 parts by weight of the final composition in which the phosphorus-containing compound, other flame retardant additives, hydrolysis inhibitors, other additives, and the like are added to the resin. It is desirable that the proportion of phosphorus atoms is 20 parts by weight or less. If the amount added exceeds the upper limit, a problem that physical properties such as mechanical strength of the resin cannot be obtained occurs.

  The hydrolysis inhibitor used in the present invention is not particularly limited as long as it is an additive that suppresses hydrolysis of the biodegradable polymer compound. By containing a hydrolysis inhibitor that suppresses hydrolysis of the biodegradable polymer compound, the hydrolysis rate of the biodegradable polymer compound is delayed, resulting in high mechanical strength, impact strength, etc. over a long period of time. It exhibits high storage properties that can be maintained.

Specific examples of the hydrolysis inhibitor include compounds having reactivity with active hydrogen in a biodegradable polymer compound. By adding the above compound, the amount of active hydrogen in the biodegradable polymer compound can be reduced, and active hydrogen can be prevented from catalytically hydrolyzing the biodegradable polymer chain. Here, active hydrogen is hydrogen in a bond (N—H bond or O—H bond) of oxygen, nitrogen or the like and hydrogen, and such hydrogen is in a bond of carbon and hydrogen (C—H bond). Reactivity is higher than hydrogen. More specifically, for example, hydrogen in a carboxyl group: —COOH, a hydroxyl group: —OH, an amino group: —NH ₂ , an amide bond: —NHCO— or the like in the biodegradable polymer compound may be mentioned.

  As the compound having reactivity with active hydrogen in the biodegradable polymer compound, a carbodiimide compound, an isocyanate compound, an oxazoline compound, and the like are applicable. In particular, a carbodiimide compound is preferable because it can be melt-kneaded with a biodegradable polymer compound, and hydrolysis can be further suppressed with a small amount of addition.

  The carbodiimide compound is a compound having one or more carbodiimide groups in the molecule, and also includes a polycarbodiimide compound. As a method for producing the carbodiimide compound, for example, as a catalyst, for example, O, O-dimethyl-O- (3-methyl-4-nitrophenyl) phosphorothioate, O, O-dimethyl-O- (3-methyl-4) -(Methylthio) phenyl) phosphorothioate, organic phosphorus compounds such as O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate, or, for example, rhodium complex, titanium complex, tungsten complex, palladium complex A method for producing various polymer isocyanates by decarboxylation polycondensation in a solvent-free or inert solvent (for example, hexane, benzene, dioxane, chloroform, etc.) at a temperature of about 70 ° C. or higher using an organometallic compound such as be able to.

  Examples of the monocarbodiimide compound contained in this carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, naphthylcarbodiimide, and among them, particularly industrially available. Easy dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferred.

  Examples of the isocyanate compound that is reactive with active hydrogen in the biodegradable polymer compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, and p-phenylene diisocyanate. 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4 '-Biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexame Diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, Examples include 4,4′-dicyclohexylmethane diisocyanate or 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate.

  The said isocyanate compound can be easily manufactured by a well-known method, and a commercial item can be used suitably. As commercially available polyisocyanate compounds, aromatic isocyanate adducts such as coronate (manufactured by Nippon Polyurethane; hydrogenated diphenylmethane diisocyanate) or myrionate (manufactured by Nippon Polyurethane) can be used. In particular, when the composition according to the present invention is produced by melt-kneading, the use of a polyisocyanate compound in which a solid substance, for example, an isocyanate group is blocked with a masking agent (polyhydric aliphatic alcohol, aromatic polyol, etc.) from a liquid is used. preferable.

  Examples of the oxazoline-based compound that is reactive with active hydrogen in the biodegradable polymer compound include 2,2′-o-phenylenebis (2-oxazoline) and 2,2′-m-phenylene. Bis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-2) -Oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'- Octamethylene Bis (2-oxazoline), 2,2′-ethylenebis (4-methyl-2-oxazoline), 2,2′-diphenylenebis (2-oxazoline), or the like can be given. Moreover, a hydrolysis inhibitor may use the said compound individually or in combination of 2 or more types.

  The type and blending amount of the hydrolysis inhibitor are not particularly limited, but the biodegradation rate of the molded article and thus the mechanical strength can be adjusted by appropriately adjusting the type and blending amount of the hydrolysis inhibitor. Therefore, it may be determined according to the target product.

  The manufacturing method of the resin composition of this invention is not specifically limited, You may use a well-known method. For example, a method of producing the organic polymer compound exhibiting biodegradability by melting and kneading the above-mentioned flame retardant additive and hydrolysis inhibitor is a suitable example.

  The production method by melt kneading is performed by adding and mixing a flame retardant additive and a hydrolysis inhibitor before or when the organic polymer compound exhibiting biodegradability is melted. At this time, the flame retardant additive and the hydrolysis inhibitor may be added simultaneously or individually. Moreover, when adding individually, any may be added first. In addition, after melting the organic polymer compound exhibiting biodegradability, either a flame retardant additive or a hydrolysis inhibitor is added and mixed, and then the obtained composition is melted again to obtain a hydrolysis inhibitor. Alternatively, a method of adding and mixing any remaining component of the flame retardant additive may be used.

  In the resin composition according to the present invention, other additives for improving performance can be appropriately used as long as the object of the present invention is not impaired. Other additives include, for example, reinforcing materials, antioxidants, heat stabilizers, UV absorbers, etc., as well as lubricants, waxes, colorants, crystallization accelerators, anti-dripping agents, and degradability such as starch. The organic substance etc. which have this are mentioned, However, It is not limited to these. These additives may be used alone or in combination of two or more.

  Examples of the reinforcing material include fillers such as inorganic fillers and organic fillers. Examples of the inorganic filler include carbon, silicon dioxide, metal oxide fine particles such as alumina, silica, magnesia, or ferrite, silicates such as talc, mica, kaolin, zeolite, wollastonite, barium sulfate, calcium carbonate, Or fine particles, such as fullerene, etc. are mentioned. Examples of inorganic fillers include glass microbeads, carbon fibers, chalk, quartz such as novoculite, asbestos, feldspar, mica, and the like. Examples of the organic filler include an epoxy resin, a melamine resin, a urea resin, an acrylic resin, a phenol resin, a polyimide resin, a polyamide resin, a polyester resin, and a Teflon (registered trademark) resin. Of these, carbon and silicon dioxide are preferable. However, the reinforcing material is not limited to the above, and any generally used fillers such as inorganic fillers and organic fillers can be used. In addition, the reinforcing material may be the above material alone or in combination of two or more.

Examples of the antioxidant include phenol-based, amine-based, phosphorus-based, sulfur-based, hydroquinone-based, and quinoline-based antioxidants. Phenol antioxidants include hindered phenols such as 2,6-di-t-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris (3,5-di- -T-butyl-4-hydroxybenzyl) benzene, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4, C ₂₋ such as 4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ₁₀ alkylenediol - bis [3- (3,5-di - branched C _3-6 alkyl-4-hydroxyphenyl) propionate], for example, triethylene glycol - bis [3- (3-t-butyl - - methyl-4-hydroxyphenyl) propionate] and the like di- or Toriokishi C _2-4 alkylene diol - bis [3- (3,5-di - branched C _3-6 alkyl-4-hydroxyphenyl) propionate], such as glycerin C _3-8 alkanetriol-bis [3- (3,5-di-branched C _3-6 alkyl-4] such as tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] -Hydroxyphenyl) propionate], for example C _4-8 alkanetetraol tetrakis [3- (3,5-, 5-pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]). Di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate], for example n-octadecyl-3- (4 ′, 5′-di-t-butyl) Ruphenol) propionate, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenol) propionate, stearyl-2- (3,5-di-t-butyl-4-hydroxyphenol) ) Propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methyl Phenyl acrylate, N, N′-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocymamide), 3,9-bis {2- [3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4, Examples thereof include 4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane, and the like.

Examples of amine-based antioxidants include phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N′-diphenyl-1,4-phenylenediamine, or N-phenyl-N′-cyclohexyl-1,4- Examples include phenylenediamine.
Examples of phosphorus antioxidants include triisodecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 2,2-methylenebis (4,6-di-). t-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris ( 2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, bis (2-t-butylphenyl) ) Phenyl phosphite, tris [2- (1,1-dimethylpropyl) -phenyl ] Phosphite, tris [2,4- (1,1-dimethylpropyl) -phenyl] phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-phenylphenyl) phosphite, etc. Phosphite compounds: triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, triphenylphosphine, methylphenyl-p-anisylphosphine, p-anisyldiphenylphosphine, p-tolyl Diphenylphosphine, di-p-anisylphenylphosphine, di-p-tolylphenylphosphine, tri-m-aminophenylphosphine, tri-2,4-dimethylphenylphosphine, tri-2,4,6 Trimethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-o-anisylphosphine, tri-p-anisylphosphine, or 1,4-bis (diphenylphosphine) And phosphine compounds such as fino) butane.
Examples of the hydroquinone antioxidant include 2,5-di-t-butylhydroquinone, and examples of the quinoline antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2. -Dihydroquinoline etc. are mentioned, As a sulfur type antioxidant, dilauryl thiodipropionate, distearyl thiodipropionate etc. are mentioned, for example. Among them, preferable antioxidants include phenolic antioxidants (particularly hindered phenols), for example, polyol-poly [(branched C _3-6 alkyl group and hydroxy group-substituted phenyl) propionate] and the like. The antioxidants may be used alone or in combination of two or more.

  Examples of the heat stabilizer include nitrogen-containing compounds such as basic nitrogen-containing compounds such as polyamide, poly-β-alanine copolymer, polyacrylamide, polyurethane, melamine, cyanoguanidine, and melamine-formaldehyde condensate; organic carboxylic acid Metal salts (calcium stearate, calcium 12-hydroxystearate, etc.), metal oxides (magnesium oxide, calcium oxide, aluminum oxide, etc.), metal hydroxides (magnesium hydroxide, calcium hydroxide, aluminum hydroxide, etc.), metal carbonates Examples thereof include alkali or alkaline earth metal-containing compounds such as salts; zeolite; or hydrotalcite. In particular, alkali or alkaline earth metal-containing compounds (especially alkaline earth metal-containing compounds such as magnesium compounds and calcium compounds), zeolite, hydrotalcite and the like are preferable. The heat stabilizer may be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include conventionally known benzophenone, benzotriazole, cyanoacrylate, salicylate, and oxalic anilide. For example, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy -4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- ( Methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy-4- (Methacryloy Oxy) benzophenone] - methyl methacrylate copolymer, or [2,2'-dihydroxy-4- (methacryloyloxy-octoxybenzophenone) - methyl methacrylate copolymer, and the like. The ultraviolet absorbers may be used alone or in combination of two or more.

  Examples of the lubricant include petroleum-based lubricating oils such as liquid paraffin; synthetic lubricating oils such as halogenated hydrocarbons, diester oils, silicone oils, and fluorosilicones; various modified silicone oils (epoxy-modified, amino-modified, alkyl-modified, Ether-modified, etc .; Silicon-based lubricants such as copolymers of silicon and organic compounds such as polyoxyalkylene glycols; Silicon copolymers; Various fluorosurfactants such as fluoroalkyl compounds; Fluorine-based lubricating substances such as polymers; waxes such as paraffin wax and polyethylene wax; higher aliphatic alcohols, higher aliphatic amides, higher fatty acid esters, higher fatty acid salts, or molybdenum disulfide. Among these, it is particularly preferable to use a silicon copolymer (a resin obtained by polymerizing silicon by block or graft). Silicone copolymers include acrylic resins, polystyrene resins, polynitrile resins, polyamide resins, polyolefin resins, epoxy resins, polybutyral resins, melamine resins, vinyl chloride resins, polyurethane resins, or polyvinyl resins. What is necessary is just to block or graft-polymerize silicon to ether resin etc., It is preferable to use a silicon graft copolymer. These lubricating substances may be used alone or in combination of two or more. Examples of the waxes include olefin wax such as polypropylene wax and polyethylene wax, paraffin wax, Fischer-Tropsch wax, microcrystalline wax, montan wax, fatty acid amide wax, higher aliphatic alcohol wax, and higher fatty acid wax. , Fatty acid ester wax, carnauba wax, rice wax and the like. These waxes may be used alone or in combination of two or more.

Examples of the colorant include inorganic pigments, organic pigments, and dyes. Examples of inorganic pigments include chromium pigments, cadmium pigments, iron pigments, cobalt pigments, ultramarine blue, and bitumen. Specific examples of organic pigments and dyes include, for example, carbon black; phthalocyanine pigments such as phthalocyanine copper; quinacridone pigments such as quinacridone magenta and quinacridone red; Examples include azo pigments such as red and naphthol red; for example, spirit black SB, nigrosine base, nigrosine dyes such as oil black BW, oil blue, pigment yellow, pigment blue, pigment red, and alkali blue. The colorants may be used alone or in combination of two or more.
Examples of the crystallization accelerator include organic acid salts such as sodium pt-butylbenzoate, sodium montanate, calcium montanate, sodium palmitate, and calcium stearate; for example, calcium carbonate, calcium silicate, magnesium silicate, sulfuric acid Inorganic salts such as calcium, barium sulfate and talc; for example, metal oxides such as zinc oxide, magnesium oxide and titanium oxide. These crystallization accelerators may be used alone or in combination of two or more.

As the dripping inhibitor, for example, a thermosetting resin such as a fluororesin or a phenol resin can be used. Examples of the fluororesin include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and other fluorine-containing monomers, or copolymers; the above fluorine-containing monomers, ethylene, propylene, (meta ) Copolymers with copolymerizable monomers such as acrylates are included. These anti-dripping agents may be used alone or in combination of two or more.
You may perform a well-known process with respect to the resin composition concerning this invention. For example, in order to suppress hydrolysis of the biodegradable polymer compound in the resin composition according to the present invention, the resin composition according to the present invention may be irradiated with active energy rays.

  Examples of the active energy ray source include electromagnetic waves, electron beams, particle beams, and combinations thereof. Examples of the electromagnetic wave include ultraviolet rays (UV) and X-rays, and examples of the particle beam include rays of elementary particles such as protons and neutrons. Among these, electron beam irradiation by using an electron accelerator is particularly preferable.

  The active energy ray can be irradiated using a known apparatus. For example, a UV irradiation apparatus, an electron accelerator, etc. are mentioned. The irradiation dose and irradiation intensity are not particularly limited as long as the hydrolysis of the biodegradable polymer compound is effectively delayed in the resin composition according to the present invention. For example, in the case of an electron beam, the acceleration voltage is preferably about 100 to 5000 kV, and the irradiation dose is preferably about 1 kGy or more.

  The molded product obtained by molding the resin composition according to the present invention can be applied to various uses. Examples of the molding method of the molded product include pressure molding, film molding, extrusion molding, and injection molding. In particular, injection molding is preferable. More specifically, the extrusion molding can be performed according to a conventional method using a known extrusion molding machine such as a single-screw extruder, a multi-screw extruder, a tandem extruder, or the like. The injection molding can be performed according to a conventional method using a known injection molding machine such as an inline screw type injection molding machine, a multilayer injection molding machine, or a two-head injection molding machine. Moreover, it does not specifically limit as a method of shape | molding the resin composition of this invention, and manufacturing a molded article, All the well-known shaping | molding methods can be utilized.

  Thus, by including the organic high molecular compound which shows biodegradability, the phosphorus containing compound which expresses a high flame-retardant effect when combined with this, and a hydrolysis inhibitor, for example, in UL flammability test When evaluated, it is possible to achieve both extremely high flame retardancy satisfying the range of V0 to V1 and excellent storage characteristics that can be used, for example, as a housing for electrical products.

  In addition, the molded product comprising the resin composition of the present invention is mainly composed of a biodegradable resin, which is a safe component for the living body, and is easily decomposed in the natural environment. The adverse effects on the environment can be reduced. In addition, the flame retardant additive used in the present invention exhibits high flame retardancy and decomposes into components that are safe for living bodies and the global environment such as phosphorus, water, carbon dioxide and the like after disposal. There is no risk of adversely affecting the human body. For this reason, by applying such a molded product to a casing or packaging material of an electric product, it is possible to realize sufficient environmental considerations compared to the case of using an existing synthetic resin or biodegradable resin. .

  The molded product formed by molding the resin composition of the present invention is suitable for application to some of the following electrical products, for which it has been difficult to apply biodegradable resins. Specific electrical products include, for example, DVD (digital versatile disc) players, CD (compact disc) players, MD (mini disc) players, stationary AV equipment such as amplifiers, speakers, in-vehicle AV / IT equipment, electronic PDAs including books, video decks, projectors, TV receivers, monitors, digital video cameras, digital still cameras, printers, radios, radio cassettes, system stereos, microphones, headphones, keyboards, headphone stereos, portable CD players, portables Portable music machines such as MD players, so-called silicon audio players, refrigerators, washing machines, air conditioners, personal computers and computer peripherals, stationary game machines, portable game machines, mobile phones, telephones, fax machines , Copiers, entertainment robots and the like, the molded article of the present invention can be utilized as a housing for these electrical products. In addition, the molded product of the present invention can be used not only for a housing of an electric product, but also for other components such as parts and structural materials constituting the electric product. By using a molded product formed by molding the resin composition of the present invention as a component of an electrical product, the electrical product exhibits sufficient flame retardancy and storage characteristics, and also exhibits biodegradability, and thus is a synthetic resin. Compared with, the adverse effect on the natural environment at the time of disposal and after disposal can be reduced.

  In addition, the use of the molded product comprising the resin composition of the present invention is not limited to this, and since it exhibits biodegradability, it is a packaging material as well as disposable products mainly used for daily goods, sanitary goods, play goods, etc. It can be applied to all uses such as automobile use and industrial product use.

  Examples of the present invention will be described in detail below, but it goes without saying that the present invention is not limited thereto.

<Experiment 1>
First, the case where an aliphatic polyester resin is used as the organic polymer compound exhibiting biodegradability will be examined.

(Sample preparation)
As an aliphatic polyester resin exhibiting biodegradability, (A1) Lacia belonging to polylactic acid (H100J, manufactured by Mitsui Chemicals), and (A2) Bionore belonging to polybutylene succinate (# 1020, manufactured by Showa Polymer Co., Ltd.), (B) Hydrolysis inhibitor (Carbodilite HMV-8CA, manufactured by Nisshinbo Co., Ltd.), various flame retardant additives (C1: triphenyl phosphate, Ajinomoto Fine Techno Co., Ltd., C2: condensed phosphate ester, eighth chemical industry C3; phosphinic acid salt, manufactured by Clariant Japan, C4; ammonium polyphosphate, manufactured by Clariant Japan). A melt kneading method was used for mixing A, B, and C.

As the kneading conditions, a minimax-mix loader (manufactured by Toyo Seiki Co., Ltd.) is used as a kneading machine, the nozzle temperature is 170 to 175 ° C., the torque is 4 to 6 kg, the residence time is within 3 seconds, and the resin is kneaded by kneading Additives were added. After the obtained resin composite was pulverized, it was pressed at 170 ° C. at 300 Kg / cm ² , formed into a plate material having a thickness of 1.0 mm, cut into a size of 12.7 mm × 127 mm, and used as a measurement test piece. The compositions of the test pieces of Examples 1 to 7 and Comparative Examples 1 to 5 are shown in Table 1 below.

  About the test pieces of Examples 1 to 7 and Comparative Examples 1 to 5 produced as described above, the combustion test and the storage test were performed as follows, and the flame retardancy and the storage characteristics were evaluated. .

(Combustion test)
The vertical combustion test was performed according to UL94 flammability tests V-0 to V-2 using the above test pieces. The method is described below.

  Each sample is held at 6.4 mm from the top with the vertical axis vertical, and held by a ring stand clamp, and the tip of the burner is 9.5 mm below the sample and the absorbent cotton is 305 mm below. To spread the horizontal layer. To make a horizontal layer, tear a piece of cotton about 12.7mm x 25.4mm from the lump of cotton with your thumb and forefinger, spread it thinly with your finger, 50.8mm square, and the natural thickness is 6.4mm. To be.

  Place the burner away from the sample, ignite, and adjust to produce a 19 mm high blue flame. For the flame, adjust the gas supply amount and the air outlet of the burner so that a yellow blue flame with a height of 19 mm will appear first, then adjust the amount of air so that the yellow flame will disappear. To do. Measure the flame height again and adjust as necessary.

  The test flame is centered on the lower end of the test sample and continued for 10 seconds. The flame is then separated by at least 152 mm and the time for the sample to burn and burn is recorded. As soon as the flame of the sample has disappeared, the test flame is again applied to the lower end of the sample. Then, after 10 seconds, the flame is released again and the burning time of flame and flameless is recorded. When it is difficult to distinguish between visually flaming and non-flaming, a surgical cotton is brought into contact with the questionable part. If cotton ignites, it is flaming. During each flame contact, when molten or flammable material is dripped from the sample, the burner is tilted to an angle of 45 degrees during the flame contact, and also slightly from one of the 12.7 mm faces of the sample. Keep away and avoid dripping material into the burner tube. If molten or flammable material is dripped from the sample or keeps burning during the test, hold the burner, and during flame contact, the distance between the lower end of the sample and the tip of the burner tube is 9.5 mm. Must hold. All dripping of molten material shall be negligible and shall be in contact with the center of the sample.

And the 94V-1 certified material, that is, the material certified as 94V-1 must meet the following conditions.
(A) All samples should be flamed for at least 30 seconds after being flamed and not burned.
(B) A total of 10 times of flame contact with each set of five samples, and the total time for burning and burning does not exceed 250 seconds.
(C) For all samples, flammable or flameless combustion shall not reach the support clamp.
(D) Do not ignite dry surgical absorbent cotton 305 mm below by dripping material from the sample.
(E) All samples must be kept flameless for more than 60 seconds after the second flame.

(Preservation test)
Although the molded product having high flame retardancy according to the present invention has biodegradability, it needs to have a certain degree of storage in order to be used as a molded product in a casing of an electrical device. As the evaluation, the storage stability under high temperature and high humidity was evaluated. The evaluation was performed by storing each sample for 100 hours at a temperature of 80 ° C. and a relative humidity of 80%, and then measuring the shape and the molecular weight of the polymer. The test pieces used were the same as those in the above-mentioned combustion test, and those having no problem in shape and having a molecular weight maintenance rate of 80% from before the evaluation were evaluated as ◯, and those that could not be secured as x. The molecular weight was evaluated by GPC (Gel Permeation Chromatography) method. The results of combustion tests and storage tests of Examples 1 to 7 and Comparative Examples 1 to 5 are shown in Table 1 below. In the table below, “UL94-V1; ◯” indicates that the material is 94V-1 certified, and “UL94-V1; ×” indicates that the material is not 94V-1 certified.

  From Table 1, the aliphatic polyester (A1 and A2) which shows biodegradability, a hydrolysis inhibitor (B), and the flame retardant additive (at least 1 type of C1-C4) which is a phosphorus containing compound are included. Examples 1 to 7 exhibited high flame retardancy satisfying the UL94V-1 standard, and also had good storage characteristics. On the other hand, the comparative example 1 which does not contain a phosphorus containing compound does not satisfy UL94V-1 specification, and the comparative example 2-comparative example 5 which does not contain (B) hydrolysis inhibitor compared with an Example. The characteristics were impaired. From the results of the above experiment 1, it was found that both flame retardancy and storage characteristics can be achieved by blending a phosphorus-containing compound and a hydrolysis inhibitor into an aliphatic polyester resin exhibiting biodegradability.

<Experiment 2>
Next, the case where a polysaccharide is used as an organic polymer compound exhibiting biodegradability will be examined.

(Sample preparation)
In Experiment 2, instead of the aliphatic polyester resin exhibiting biodegradability, (A3) acetylcellulose (360E-16, manufactured by Daicel FineChem), which is a polysaccharide, and (A4) esterified starch (CPR-3M, Japan) Cornstarch) was used. (B) The hydrolysis inhibitor and various flame retardant additives (C) are the same as those used in Experiment 1.
These raw materials were kneaded in the same manner as in Experiment 1 to prepare measurement test pieces of Example 8 to Example 21 and Comparative Example 6 to Comparative Example 13. The compositions of the test pieces of Examples 8 to 21 and Comparative Examples 6 to 13 are shown in Table 2 below.

  The test pieces of Examples 8 to 21 and Comparative Examples 6 to 13 were subjected to a combustion test and a storage test in the same manner as in Experiment 1. The results of the combustion test and the storage test are shown in Table 2 below.

  From Table 2, acetylcellulose (A3), which is a biodegradable polysaccharide, hydrolysis inhibitor (B), and flame retardant additive (at least one of C1 to C4) that is a phosphorus-containing compound. Including Examples 8 to 14 exhibited high flame retardancy satisfying the UL94V-1 standard, and also had good storage characteristics. On the other hand, Comparative Example 9 containing no phosphorus-containing compound does not satisfy the UL94V-1 standard, and (B) Comparative Examples 6 to 8 containing no hydrolysis inhibitor are Examples 8 to Compared to Example 14, the storage characteristics were impaired.

  Also, when esterified starch (A4) is used as a biodegradable polysaccharide, as with acetylcellulose (A3), esterified starch (A4), hydrolysis inhibitor (B), and phosphorus-containing compound are used. When including all of the flame retardant additive (at least one of C1 to C4) (Example 15 to Example 21), it exhibits high flame retardancy satisfying the UL94V-1 standard, and storage characteristics Was also good. On the other hand, Comparative Example 13 containing no phosphorus-containing compound does not satisfy the UL94V-1 standard, and (B) Comparative Examples 10 to 12 containing no hydrolysis inhibitor are Examples 15 to Compared to Example 21, the storage characteristics were impaired.

From the results of Experiment 2 above, it was found that both flame retardancy and storage characteristics can be achieved by blending a phosphorus-containing compound and a hydrolysis inhibitor into a biodegradable polysaccharide.

Claims (12)

  Contains at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and a hydrolysis inhibitor that suppresses hydrolysis of at least one organic polymer compound A resin composition characterized by comprising:   The organic polymer compound is an aliphatic polyester resin, polysaccharide, peptide, polyvinyl alcohol, polyamide, polyalkylene glycol, or a copolymer containing at least one of these. Resin composition.   The aliphatic polyester resin comprises polylactic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, polyethylene succinate, polybutylene succinate, polybutylene adipate, polymalic acid, microbial synthetic polyester, or at least one of these. The resin composition according to claim 2, wherein the resin composition is a copolymer.   3. The resin composition according to claim 2, wherein the polysaccharide is cellulose, starch, chitin, chitosan, dextran, a derivative thereof, or a copolymer containing at least one of them. .   The resin composition according to claim 4, wherein the cellulose derivative is esterified cellulose.   The resin composition according to claim 4, wherein the starch derivative is an esterified starch.   2. The resin composition according to claim 1, wherein the phosphorus-containing compound is at least one of an organic phosphorus compound, a single phosphorus, and an inorganic phosphorus compound.   The resin composition according to claim 1, wherein the hydrolysis inhibitor is a carbodiimide compound, an isocyanate compound, or an oxazoline compound.   Contains at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and a hydrolysis inhibitor that suppresses hydrolysis of at least one organic polymer compound A molded product obtained by molding a resin composition.   Contains at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and a hydrolysis inhibitor that suppresses hydrolysis of at least one organic polymer compound An electrical product comprising a molded product formed by molding a resin composition as a constituent element.   The electrical product according to claim 10, wherein the component is a housing.   Combining at least one organic polymer compound exhibiting biodegradability, a flame retardant additive containing a phosphorus-containing compound, and a hydrolysis inhibitor that suppresses hydrolysis of at least one organic polymer compound. A method for producing a resin composition, comprising: