JP2005248032A - Flame retardant aliphatic polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in mechanical strength and further flame retardance by using a resin effectively utilizing a natural resource. <P>SOLUTION: This flame retardant aliphatic polyester resin composition is obtained by blending (A) 100 pts. wt. aliphatic polyester resin, (B) 5-40 pts. wt. phosphorus-based compound, (C) 1-40 pts. wt. carbonization-accelerating compound, (D) 0.1-10 pts. wt. hydrolysis inhibitor and (E) 0.01-5 pts. wt. drip inhibitor. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a resin composition having excellent mechanical strength and flame retardancy using a resin that effectively utilizes natural resources.

  In recent years, biodegradable resins have been developed and put into practical use. Biodegradable resins are more effective use of resources using renewable natural raw materials, and even when discarded in the natural environment, they are easily biochemically decomposed into carbon dioxide and water by microorganisms. It is said that reducing the molecular weight further reduces the burden on the environment. Organic polymer compounds constituting such biodegradable resins include those obtained by chemically modifying natural polymers such as cellulose and starch, and aliphatic polyesters such as polylactic acid, polyhydroxybutyric acid, and polyhydroxyvaleric acid. It has been known.

  The biodegradable resin as described above can effectively use resources by using natural raw materials. However, in recent years, the demand for flame retardant has been increasing as one of the safety when using the resin. Regarding the properties, these resins are not sufficient. In particular, for electrical products, there is a desire to make the case etc. with biodegradable resin and to facilitate the post-recovery process. It is necessary to satisfy the flame retardant standard defined in the above, and existing biodegradable resins cannot meet the flame retardant standard.

Conventionally, as a method for imparting flame retardancy to a biodegradable resin, for example, a technique of adding aluminum hydroxide powder or magnesium hydroxide powder to a biodegradable resin (for example, see Patent Document 1), silicon A method of adding an oxide (see, for example, Patent Document 2), a method of adding at least one compound selected from a hydroxide compound, a phosphorus compound, and a silica compound (for example, see Patent Document 3) are proposed. However, flame retardancy and mechanical strength are not sufficient.
JP-A-8-252823 (paragraph numbers 0014 to 0016) JP 2000-319532 A (paragraph numbers 0022 to 0027) JP 2003-192925 A (paragraph numbers 0051 to 0067)

  This invention is made | formed in view of the said situation, It aims at providing the resin composition which was excellent in mechanical strength and excellent in a flame retardance using resin which utilized natural resources effectively. .

  As a result of intensive studies to achieve the above object, the present inventors have found that an aliphatic polyester resin containing a phosphorus compound, a carbonization promoting compound, a hydrolysis inhibitor, and a dripping inhibitor is flame retardant, mechanical It has been found that the resin composition is excellent in mechanical strength and effectively uses natural resources, and has reached the present invention.

  That is, the present invention relates to phosphorus compound (B) 5 to 40 parts by weight, carbonization promoting compound (C) 1 to 40 parts by weight, hydrolysis inhibitor (D) with respect to 100 parts by weight of aliphatic polyester resin (A). ) 0.1 to 10 parts by weight, and by adding 0.01 to 5 parts by weight of the dripping inhibitor (E), a resin composition that is excellent in flame retardancy and mechanical strength and that effectively utilizes natural resources is obtained. As a result, the present invention was found.

  Since the resin composition of the present invention is excellent in flame retardancy and mechanical strength, it can be applied to various applications. For example, the present invention can be applied to a molded product such as a housing for an electric product such as a radio, a television, and a personal computer.

  As aliphatic polyester resin (A) in this invention, the aliphatic polyester resin which contains a lactic acid unit in a molecule | numerator is mentioned. Specifically, homopolymers of lactic acid, polylactic acid and copolymers of lactic acid and other aliphatic hydroxycarboxylic acids, polyfunctional polysaccharide units and aliphatic polyesters containing lactic acid units, aliphatic polycarboxylic acid units, Examples include aliphatic polyhydric alcohol units, aliphatic polyesters containing lactic acid units, and mixtures thereof.

  Lactic acid has an L-form and a D-form. In the present invention, the term lactic acid refers to both the L-form and the D-form unless otherwise specified. The polylactic acid used in the present invention includes poly (L-lactic acid) whose structural unit is composed only of L-lactic acid, poly (D-lactic acid) composed of only D-lactic acid, and L-lactic acid units and D-lactic acid units. Examples thereof include poly (DL-lactic acid) present in various proportions.

  Examples of other aliphatic hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and the like.

  Examples of the method for producing polylactic acid include a method of directly dehydrating and condensing L-lactic acid, D-lactic acid, or DL-lactic acid, a method of ring-opening polymerization of lactide, which is a cyclic dimer of these lactic acids, and the like. In addition, polylactic acid and a method for producing lactic acid and other aliphatic hydroxycarboxylic acid copolymer include dehydration polycondensation of each lactic acid and hydroxycarboxylic acid, lactide which is a cyclic dimer of each lactic acid, and hydroxy Examples include a method of ring-opening copolymerization of a carboxylic acid ring. It may be produced by any method.

  Examples of polyfunctional polysaccharides used in the production of aliphatic polyesters containing polyfunctional polysaccharide units and lactic acid units include cellulose, cellulose nitrate, methyl cellulose, ethyl cellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, and copper ammonia. Examples include rayon, cuprophane, bemberg, hemicellulose, starch, acropectin, dextrin, dextran, glycogen, pectin, chitin, chitosan, gum arabic, guar gum, locust bean gum, acacia gum, and mixtures thereof, and derivatives thereof. It is done.

  As a method for producing an aliphatic polyester containing a polyfunctional polysaccharide unit and a lactic acid unit, a method of reacting the polyfunctional polysaccharide with the polylactic acid, lactic acid and another aliphatic hydroxycarboxylic acid copolymer, etc., and the polyfunctional polysaccharide The method etc. which react each said lactic acid, cyclic ester, etc. are mentioned.

  Examples of the aliphatic polycarboxylic acid used for the production of the aliphatic polyester containing an aliphatic polycarboxylic acid unit, an aliphatic polyhydric alcohol unit and a lactic acid unit include oxalic acid, succinic acid, malonic acid, glutaric acid, adipine Examples include acids, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, and the like, and anhydrides thereof. These may be a mixture with an acid anhydride. Examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 3-methyl-1,5- Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol and the like can be mentioned.

  As a method for producing an aliphatic polyester containing an aliphatic polycarboxylic acid unit, an aliphatic polyhydric alcohol unit and a lactic acid unit, the aliphatic polycarboxylic acid and the aliphatic polyhydric alcohol, the polylactic acid, lactic acid and others And a method of reacting the above aliphatic polycarboxylic acid copolymer and the above aliphatic polycarboxylic acid and the above aliphatic polyhydric alcohol with each of the above lactic acid and cyclic esters.

  Examples of the phosphorus compound (B) in the present invention include triaryl phosphate esters, diaryl phosphate esters, monoaryl phosphate esters, aryl phosphonate compounds, aryl phosphine oxide compounds, condensed aryl phosphate esters, and phosphazene compounds. be able to.

  Specific examples are trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trithiophenyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate and the like. Arylphosphonic acid compounds such as Lille phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, phenylphosphonic acid, aryl such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Phosphine oxide compounds, 1,3-phenylene bis (2,6-dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (di Phenyl phosphate), bisphenol-A bis (diphenyl phosphate), resorcinol bis (dixyl phosphate), hydroquinone bis (dixyl phosphate), bisphenol-A bis (ditolyl phosphate), biphenol-A bis (dixyl phosphate), bisphenol Examples thereof include condensed aryl phosphates such as -S bis (dixyl phosphate) and phosphazene compounds such as phenoxy phosphazene oligomers.

  It is preferable that the addition amount of a phosphorus compound (B) is the range of 5-40 weight part with respect to 100 weight part of aliphatic polyester resin (A). When the addition amount is less than 5 parts by weight, the effect of imparting flame retardancy to the resin composition is insufficient, and when it exceeds 40 parts by weight, the mechanical properties of the resin composition are adversely affected.

  A phosphorus compound (B) may be used individually by 1 type, and may be used together 2 or more types as needed.

  The carbonization promoting compound (C) referred to in the present invention is a compound that delays the start of combustion of the resin composition and promotes carbonization to improve combustibility, and promotes carbonization of the resin by moving to the surface layer during combustion. It refers to a compound that has the effect of a flame retardant aid that improves flammability. However, the above properties may be duplicated.

  As a compound having a flame retardant aid effect that delays the start of combustion and promotes carbonization to improve combustibility, and a compound that moves to the surface layer portion during combustion and promotes carbonization of the resin to improve combustibility. , Silicone compounds, novolac type phenol resins and the like.

  As the silicone compound, it is preferable to use a silicone compound in which the main chain has a branched structure and the organic functional group consists of an aromatic group, or consists of an aromatic group and a hydrocarbon group. As the novolac type phenol resin, known general-purpose ones can be used, but from the viewpoint of heat resistance, the free monomer component content in the novolac type phenol resin is less than 0.5% by weight and the free dimer component content is 2%. It is preferable to use less than%.

  The addition amount of the carbonization promoting compound (C) is preferably in the range of 1 to 40 parts by weight with respect to 100 parts by weight of the aliphatic polyester resin (A). When the addition amount is less than 1 part by weight, the effect of improving the combustibility becomes insufficient, and when it exceeds 40 parts by weight, the mechanical properties of the resin composition are adversely affected.

  The carbonization promoting compound (C) may be used alone or in combination of two or more as necessary.

  The hydrolysis inhibitor (D) in the present invention refers to an additive that reacts with a carboxyl group and a hydroxyl group, which are functional groups of an aliphatic polyester resin, to suppress hydrolysis. For example, an epoxy compound, A carbodiimide compound, an isocyanate compound, an oxazoline compound, and the like can be given.

  Examples of the epoxy compound include a bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, a bisphenol S-based epoxy resin, a phenol novolac resin, a cresol novolak resin, and a epichlorohydrin obtained by a reaction between bisphenol A and epichlorohydrin. Novolac epoxy resin, triglycidyl isocyanurate, tris (α-methylglycidyl) isocyanurate, tris (β-methylglycidyl) isocyanurate, tris (hydroxyphenyl) methane triglycidyl ether, 1,3,5-tri (glycidyloxy) ) Benzene, 1,3,5-trimesic acid triglycidyl ester, tetraglycidylxylylenediamine, tetraglycidyldiaminophenylmethane, teto Lakis (4-hydroxyphenyl) ethanetritetraglycidyl ether, neopentyl glycol diglycidyl ether, glycol diglycidyl ethers such as hexamethylene glycol diglycidyl ether, polyether such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Examples thereof include polyol polyglycidyl ethers such as diglycidyl ethers, glycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, and trimethylolpropane polyglycidyl ether.

  The carbodiimide compound is a compound having one or more carbodiimide groups in the molecule. For example, an organophosphorus compound or an organometallic compound is used as a catalyst, and various polyisocyanates are used in a solvent-free or non-solvent state at a temperature of about 70 ° C. or more. It can be synthesized by subjecting to a decarboxylation condensation reaction in an active solvent. 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 include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, 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-hexamethylene diisocyanate, dodecamethylene diisocyanate, trime Lehexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane Examples include diisocyanate or 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate.

  Examples of the oxazoline compound include 2,2′-o-phenylenebis (2-oxazoline), 2,2′-m-phenylenebis (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'-octamethylenebis (2-oxazoline), 2,2'-ethylenebis (4- Methyl-2 Oxazoline), or 2,2'- diphenylenebis (2-oxazoline).

  Examples of the dripping inhibitor (E) in the present invention include fluorine resins and silicone resins. For example, examples of the fluororesin include polydifluoroethylene, polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, perfluoromethanesulfonic acid sodium salt, perfluoro-n-butanesulfonic acid potassium salt, and perfluoro-t. -Perfluoroalkanesulfonic acid alkali metal salt compounds such as butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, or perfluoroalkanesulfonic acid alkaline earth metal salts It is done. Examples of silicone resins include polyorganosiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, silicone rubbers, and copolymer resins thereof. The modified silicone resin by which the terminal or side chain of this molecular structure was substituted by organic groups, such as a hydroxyl group, an amino group, an epoxy group, a carboxyl group, a mercapto group, can also be mentioned. The form of the silicone-based resin is arbitrary such as oil, varnish, gum, powder, and perit.

  As addition amount of a dripping inhibitor (E), 0.01-5 weight part is preferable with respect to 100 weight part of aliphatic polyester resin (A). If the addition amount is less than 0.01 parts by weight, the dripping suppression effect cannot be obtained, and if it exceeds 5 parts by weight, the moldability is adversely affected.

  In the flame-retardant resin composition of the present invention, other general-purpose resins can be used in combination as long as the purpose is not significantly impaired. For example, polyester resin, polycarbonate resin, polyurethane resin, acrylic resin, polyacetal resin, polyphenylene ether resin, polyethylene resin, polypropylene resin, polyamide resin, polyester elastomer resin, polyamide elastomer resin, melamine resin, urea resin, etc. can be blended It is.

  In addition, the flame retardant aliphatic polyester resin composition of the present invention includes a filler, a plasticizer, a lubricant, an antistatic agent, a filler, a nucleating agent, an antioxidant, a flame retardant, as long as the purpose is not significantly impaired. Thermal stabilizer, impact resistance improver, ultraviolet absorber, colorant, light stabilizer, antibacterial agent, release agent, tackifier, antifogging agent, surfactant, metal deactivator, dispersant, publicly known A coupling agent or the like may be added. These may be used alone or in combination.

  Examples of the filler include metal oxide fine particles such as carbon, silicon dioxide, alumina, silica, magnesia, or ferrite, silicates such as talc, mica, and zeolite, and fine particles such as barium sulfate, calcium carbonate, or fullerene. . Examples of the plasticizer include glycerin fatty acid esters such as glycerin monostearate, sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monooleate, polyglycerin fatty acid esters, and propylene glycol fatty acid esters. Lubricants include hydrocarbons such as liquid paraffin and polyethylene wax, fatty acids such as stearic acid, oxy fatty acids, fatty acid amides, alkylene bis fatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acids Examples include polyglycol esters, aliphatic alcohols, polyhydric alcohols, polyglycols, and metal soaps such as calcium stearate. Antistatic agents include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, aliphatic amines and aliphatic amide sulfates, aliphatic alcohol phosphate esters, dibasic fatty acid ester sulfonates , Aliphatic amide sulfonates, alkyl allyl sulfonates, aliphatic amine salts, quaternary ammonium salts, alkyl pyridium salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters Sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, imidazoline derivatives, higher alkyl amines, and the like. Examples of the filler include glass, carbon fiber, chalk, quartz, asbestos, feldspar, mica, silicate, kaolin and the like. Nucleating agents include: organic acid salts such as sodium pt-butylbenzoate, sodium montanate, calcium montanate, sodium palmitate, calcium stearate, calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, talc And inorganic salts such as zinc oxide, magnesium oxide, and metal oxides such as titanium oxide. As the antioxidant, a phenol-based antioxidant, an organic phosphite-based antioxidant, a thioether-based antioxidant, a hindered amine-based antioxidant, or the like can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not restrict | limited to the following description examples, unless the summary is exceeded.

<Examples 1-3, Comparative Examples 1-3>
The proportions (values represent parts by weight) described in Table 1 below were weighed and mixed with a blender. The obtained mixture was melt-kneaded at a cylinder temperature of 170 to 200 ° C. by a twin-screw extruder (manufactured by Ikekai Tekko Co., Ltd., model: PCM30) to obtain a pellet-shaped resin composition. After drying the obtained pellets at 90 ° C. for 4 hours or more, a test piece was prepared with an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS60B) at a cylinder temperature of 170 to 190 ° C. An evaluation test was conducted. The evaluation test results are shown in Table 1.

<Evaluation method>
(Izod) Impact strength: Measured according to JISK7110 (with V notch, 1/8 inch thickness).
Tensile strength: measured in accordance with JISK7113.
Flammability: Evaluation was performed according to the flammability standard UL94 using a test piece having a thickness of 1/16 inch.

As described above, the flame retardant aliphatic polyester resin composition of the present invention is excellent in flame retardancy and mechanical strength, such as a personal computer, radio, TV, keyboard, microphone, portable music player, etc. It can be applied to electrical product cases. Moreover, it can be used not only for electrical product casings but also for other uses such as packing materials, and has an extremely high industrial utility value.

Claims (1)

5 to 40 parts by weight of the phosphorus compound (B), 1 to 40 parts by weight of the carbonization promoting compound (C), and 0.1 to 10 of the hydrolysis inhibitor (D) with respect to 100 parts by weight of the aliphatic polyester resin (A). A flame-retardant aliphatic polyester resin composition obtained by blending 0.01 part by weight and 5 parts by weight of a dropping inhibitor (E).