US20050014870A1 - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
US20050014870A1
US20050014870A1 US10/494,007 US49400704A US2005014870A1 US 20050014870 A1 US20050014870 A1 US 20050014870A1 US 49400704 A US49400704 A US 49400704A US 2005014870 A1 US2005014870 A1 US 2005014870A1
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Prior art keywords
resin component
groups
component according
replaced
polyester
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Inventor
Noritaka Sato
Tsutomu Noguchi
Hiroyuki Mori
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Sony Corp
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Sony Corp
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Assigned to SONY CORPORATION reassignment SONY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MORI, HIROYUKI, NOGUCHI, TSUTOMU, SATO, NORITAKA
Publication of US20050014870A1 publication Critical patent/US20050014870A1/en
Priority to US11/830,276 priority Critical patent/US7671117B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/46—Iso-indoles; Hydrogenated iso-indoles with an oxygen atom in position 1
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Definitions

  • the present invention relates to, a resin component, a resin component for molding and a method for producing it, and more particularly to a resin component for molding including a biodegradable resin and a method for producing it.
  • a biodegradable resin decomposed in a natural atmosphere and the moldings thereof have been hitherto required in view of natural atmospheric protection.
  • the biodegradable resin such as an aliphatic polyester has been especially vigorously studied.
  • polylactic acid ordinarily has a high melting point (170 to 180° C.) and the moldings made of the polylactic acid are ordinarily transparent and they have commenced to be put into practice depending on their uses.
  • the moldings made of the polylactic acid are poor in their heat resistance and have glass transition temperature (Tg) of about 60° C. Accordingly, the moldings made of the polylactic acid are disadvantageously deformed when the temperature exceeds the above-described temperature.
  • the heat resistance referred to in this specification means a sufficiently high rigidity (modulus of elasticity) at about 80° C. as high as 100 MPa.
  • inorganic filler To increase the heat resistance of biodegradable polyester, for instance, the addition of inorganic filler has been studied.
  • the inorganic filler talc or mica or the like having the heat resistance has been studied.
  • a hard inorganic filler having the heat resistance is added to the resin, like what is called reinforcing steel embedded in concrete.
  • the mechanical characteristics are imperfectly improved only by adding the inorganic filler to the resin.
  • the polylactic acid as a typical example of the biodegradable polyester is a polymer capable of having a crystal structure.
  • the moldings of the polylactic acid is ordinarily amorphous, the moldings are apt to be thermally deformed.
  • a proposal has been provided that the polylactic acid is crystallized and hardened under a heat treatment, for instance, during molding or after molding to improve the heat resistance.
  • the polylactic acid is crystallized in such a method, it takes extremely much time to crystallize the polylactic acid. For example, a molding cycle of about one minute is ordinarily required in an injection molding. However, it unrealistically takes too much time to completely crystallize the moldings of the polylactic acid in a die.
  • the size of a crystal is of the order of micron to of the order of sub mm.
  • the crystals themselves of the polylactic acid inconveniently cause a factor of light scattering to become thick in white, so that a transparency is lost.
  • a nucleus agent In order to solve these problems, that is, to accelerate the crystallization, the addition of, what is called a nucleus agent begins to be studied.
  • the nucleus agent forms a primary crystal nucleus of a crystalline polymer to accelerate the growth of the crystal of the crystalline polymer.
  • the nucleus agent may be regarded as a material for accelerating the crystallization of the crystalline polymer. That is, a material for accelerating the crystallization speed of the polymer may be regarded as a nucleus agent.
  • the nucleus agent such as the former is added to a resin, the crystals of the polymer become fine, so that the rigidity of the resin is improved or the transparency is improved. Otherwise, when the polymer is crystallized during molding, the entire speed (time) of the crystallization is accelerated. Thus, a molding cycle can be advantageously shortened.
  • the above-described effects can be exhibited in other crystalline resins as examples.
  • the nucleus agent is added thereto, so that the rigidity or the transparency thereof is improved.
  • the PP whose materiality is improved has been put into practical use in many moldings.
  • the nucleus agent includes, for instance, a sorbitol material and its operational function is not completely clarified. However, a three-dimensional network formed by this material is considered to effectively operate. Further, a nucleus agent of metal salt type is also put into practical use for the PP.
  • nucleus agent for instance, hydroxy-di (t-butyl benzoate) aluminum, sodium bis (4-t-butylphenyl) phosphate, or sodium methylene bis (2,4-di-t-butylphenyl) phosphate, etc. may be exemplified.
  • talc functions also as a nucleus agent.
  • Talc may seem to be used as an effective nucleus agent depending on its use.
  • talc when an amount of addition thereof is not several ten %, a satisfactory effect cannot be obtained.
  • the amount of addition of talc when the amount of addition of talc is increased, the component of the resin inconveniently becomes brittle. In such an amount of addition, the component of the resin becomes white and the transparency thereof cannot be absolutely expected.
  • the nucleus agent for accelerating the crystallization has been studied so far.
  • the use of sorbitol material is disclosed in Japanese Patent Application Laid-Open No. hei 10-158369.
  • This publication discloses that the sorbitol material has satisfactory results as a nucleus agent for crystallization in the PP and the sorbitol material is added to polylactic acid to effectively act thereon.
  • methods for adding a nucleus agent to polyester to accelerate the crystallization thereof are disclosed in Japanese Patent Application Laid-Open No. hei 9-278991, Japanese Patent Application laid-Open No. hei 11-5849 and Japanese patent Application Laid-Open No. hei 11-116783.
  • a cyclic compound represented by a following formula A1-B-A2 was added to polyester capable of having a crystal structure (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material.) to accelerate the crystallization thereof.
  • the inventors recognized that the cyclic compound was preferably an isoindolinone compound. More specifically, they had a knowledge that the cyclic compound was more preferably 3,3′-2-methyl-1,3-phenylene) diimino-bis-4,5,6,7-tetrachloro-1H-isoindole-1-one (Pigment Yellow 109) or 3,3′-(1,4-phenylene diimino) bis-4,5,6,7-tetrachloro-1H-isoindole-1-one (Pigment Yellow 110). Further, they found that the particle diameter of the cyclic compound was preferably 10 ⁇ m or smaller, more preferably 1 ⁇ m or smaller and most preferably 0.1 ⁇ m or smaller.
  • the amount of addition of the cyclic compound to the resin component was preferably located within a range of 0.001 to 10 parts by weight relative to polyester of 100 parts by weight capable of having a crystal structure, and more preferably located within a range of 0.01 to 1 parts by weight.
  • the inventors of the present invention understood that the polyester capable of the crystal structure was suitably biodegradable polyester, and further, polylactic acid was preferable in the biodegradable polyester. Further, they found that inorganic filler, preferably talc was added to the polyester in addition to the cyclic compound to accelerate the crystallization of the polyester without canceling their effects with each other. They understood that the amount of addition of the inorganic filler was suitably located within 1 to 50 parts by weight relative to the polyester of 100 parts by weight capable of having the crystal structure. Further, they found that a hydrolysis inhibitor was added to the resin component for molding so that the hydrolysis of the polyester could be suppressed without lowering its crystalline property.
  • the hydrolysis inhibitor a compound having a carbodiimide group was suitable.
  • the resin component preferably had a crystallization factor located within a range of 40 to 100%, preferably had crystallization time located within a range of 0 to 200 seconds and preferably had a modulus of elasticity at 80° C. located within a range of 50 to 5000 MPa.
  • the inventors of the present invention found that the crystallization of the resin component for molding according to the present invention was accelerated and the rigidity of the moldings formed by using it was improved so that the resin component for molding was suitable for forming the moldings. They found that the moldings were preferably casings of electric or electronic devices.
  • the inventors found that the cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) was mixed with polyester capable of having the crystal structure, and then, the mixture was heated and kneaded to produce the resin component whose crystallization was improved.
  • A1-B-A2 in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material
  • nucleus agent including the cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) outstandingly accelerated the crystallization of the polyester capable of having the crystal structure.
  • the above-described cyclic compound could be used as the nucleus agent for the polyester capable of having the crystal structure.
  • the present invention concerns a resin component with its crystallization improved comprising: a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) and polyester capable of having a crystal structure.
  • a resin component with its crystallization improved comprising: a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) and polyester capable of having a crystal structure.
  • cyclic compound forming the resin component according to the present invention 3,3′-(2-methyl-1,3-phenylene) diimino-bis-4,5,6,7-tetrachloro-1H-isoindole-1-one (Pigment Yellow 109) or 3,3′-(1,4-phenylene diimino) bis-4,5,6,7-tetrachloro-1H-isoindole-1-one (Pigment Yellow 110) is used.
  • the cyclic compound is preferably a particle whose particle diameter is 10 ⁇ m or smaller.
  • the polyester capable of having the crystal structure is biodegradable polyester and the biodegradable polyester is polylactic acid.
  • the resin component according to the present invention is used as a resin molding material.
  • the mixing ratio of the cyclic compound is located within a range of 0.001 to 10 parts by weight relative to the polyester capable of having the crystal structure of 100 parts by weight.
  • the mixing ratio of the cyclic compound is located within a range of 0.01 to 1 parts by weight relative to the polyester capable of having the crystal structure of 100 parts by weight.
  • inorganic filler is further added.
  • talc can be used as the inorganic filler.
  • the mixing ratio of the inorganic filler is located within a range of 1 to 50 parts by weight relative to the resin component of 100 parts by weight.
  • hydrolysis inhibitor is further included in the resin component according to the present invention.
  • the hydrolysis inhibitor includes a compound having a carbodiimide group.
  • the crystallization rate is located within a range of 40 to 100% and crystallization time is located within a range of 0 to 200 seconds.
  • modulus of elasticity at 80° C. is located within a range of 50 to 5000 MPa.
  • the present invention concerns the moldings made of a resin and the moldings is made of the resin component with its crystallization improved comprising: a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) and polyester capable of having a crystal structure.
  • a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) and polyester capable of having a crystal structure.
  • the present invention concerns casings of electric and electronic devices.
  • the casings are made of the resin component with its crystallization improved comprising: a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) and polyester capable of having a crystal structure.
  • the present invention concerns a method for producing a resin component comprising the steps of: mixing a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) with polyester capable of having a crystal structure and heating and kneading the mixture.
  • A1-B-A2 in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material
  • the present invention concerns a nucleus agent for polyester capable of having a crystal structure which is represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material).
  • a phthalocyanine crystal which might be replaced by a material
  • a phthalocyanine compound which might include one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium, indium, thallium, tin, lead, antimony, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver
  • the inventors of the present invention understood that the cyclic compound was preferably a copper phthalocyanine crystal, a chlorophyll compound or a haemin compound. They found that the copper phthalocyanine crystal was preferably a beta type or an epsilon type crystal. Further, they found that the cyclic compound was a particle whose particle diameter was 10 ⁇ m or smaller.
  • the polyester capable of having the crystal structure was preferably biodegradable polyester
  • the biodegradable polyester was preferably polylactic acid
  • the resin component was preferably used for molding.
  • the amount of addition of the cyclic compound for the resin component was suitably located within a range of 0.001 to 10 parts by weight relative to the polyester capable of having the crystal structure of 100 parts by weight and preferably located within a range of 0.01 to 1 parts by weight.
  • inorganic filler preferably talc, as well as the cyclic compound was added to the polyester so that the crystallization of the polyester could be accelerated without canceling their effects with each other.
  • the amount of addition of the inorganic filler was suitably located within a range of 1 to 50 parts by weight relative to the polyester capable of having the crystal structure of 100 parts by weight.
  • a hydrolysis inhibitor was further added to the resin component for molding to suppress the hydrolysis of the polyester without lowering its crystallization.
  • the hydrolysis inhibitor suitably included a compound having a carbodiimide group.
  • the crystallization rate was preferably located within a range of 40 to 100%
  • crystallization time was preferably located within a range of 0 to 200 seconds
  • modulus of elasticity at 80° C. was preferably located within a range of 50 to 5000 MPa.
  • the inventors of the present invention recognized that the resin component for molding according to the present invention had its crystallization improved, the moldings formed by using it had rigidity improved and the resin component was suitable for producing the moldings. They found that the moldings were preferably the casings of electric or electronic devices.
  • the resin component of the present invention could be produced by mixing one or more cyclic compounds selected from between a copper phthalocyanine crystal (a) which might be replaced by a material, a phthalocyanine compound (b) which might include one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium, indium, thallium, tin, lead, antimony, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver,
  • a nucleus agent which comprised one or more cyclic compounds selected from between a copper phthalocyanine crystal (a) which might be replaced by a material, a phthalocyanine compound (b) which might include one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium, indium, thallium, tin, lead, antimony, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium,
  • FIG. 1 is a diagram showing a graph of luminance and time and showing a way to obtain crystallization time.
  • a resin component according to the present invention is a resin component whose crystallization is improved that comprises a cyclic compound represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) and polyester capable of having a crystal structure.
  • any of cyclic compounds represented by a following formula A1-B-A2 (in the formula, A1 and A2 are the same or different and show groups represented by a below-described formula, P shows a benzene ring which may be replaced by a material, and B shows a bivalent hydrocarbon group which may be replaced by a material) may be employed.
  • Well-known cyclic compounds may be used.
  • a benzene ring which may be replaced by a material for instance, a benzene ring which is replaced by the one to four same or different substituent groups or a benzene ring which is not replaced by the substituent groups or the like may be exemplified.
  • substituent groups such substituent groups as described below may be exemplified.
  • halogen atoms for instance, fluorine, bromine, iodine, etc.
  • nitro groups for instance, cyano groups, hydroxy groups, thiol groups, sulfo groups, sulfino groups, mercapto groups, phosphono groups, alkyl groups (for instance, methyl groups, ethyl groups, isopropyl groups, n-propyl groups, n-butyl groups, isobutyl groups, secondary butyl groups, tertiary butyl groups or various kinds of other isomers such as pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octade
  • a bivalent hydrocarbon group which may be replaced by a material for example, a bivalent hydrocarbon group which is replaced by one or more same or different substituent groups or a bivalent hydrocarbon group which is not replaced by the substituent groups may be exemplified.
  • the substituent groups have the same meanings as described above.
  • the bivalent hydrocarbon groups such hydrocarbon groups as described below may be enumerated.
  • alkylene groups for instance, methylene, methyl methylene, dimethyl methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, butylene groups, 2-methyl propylene groups, pentamethylene groups, pentylene groups, 2-methyl tetramethylene groups, 2,2-dimethyl trimethylene groups, 2-ethyl trimethylene groups, hexamethylene groups, hexylene groups, 2-methyl pentamethylene groups, 3-methyl pentamethylene groups, heptamethylene groups, heptylene groups, octamethylene groups, octylene groups, 2-ethyl hexylene groups, nonamethylene groups, nonylene groups, decamethylene groups, decylene groups, cyclopropylene, 1,2-cyclobutylene, 1,3-cyclobutylene, cyclopentylene, 1,3-cyclopentylene, 1,3-cyclopen
  • cyclic compound following compounds may be exemplified. They include, for example, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, a compound represented by a below-described formula, and a compound represented by a below-described formula, (In the formula, D shows a formula or compounds obtained by replacing these compounds by materials as much as possible chemically permissible. Further, these bivalent hydrocarbon groups may exemplify the bivalent hydrocarbon groups represented by B.
  • the cyclic compound is preferably 3,3′-(2-methyl-1,3-phenylene) diimino-bis-4,5,6,7-tetrachloro-1H-isoindole-1-one which is represented by a below-described formula.
  • the yellow pigment having various kinds of particle size is marketed.
  • the pigment preferably has the particle size as small as possible. More specifically, the particle size of the particle is preferably about 10 ⁇ m or smaller, more preferably about 1 ⁇ m or smaller and most preferably about 0.1 ⁇ m or smaller.
  • the cyclic compound is preferably 3,3′-(1,4-phenylene diimino) bis-4,5,6,7-tetrachloro-1H-isoindole-1-one which is represented by a below-described formula.
  • the yellow pigment having various kinds of particle size is marketed.
  • the pigment preferably has the particle size as small as possible. More specifically, the particle size of the particle is preferably about 10 ⁇ m or smaller, more preferably about 1 ⁇ m or smaller and most preferably about 0.1 ⁇ m or smaller.
  • cyclic compound an isomer of the above-described cyclic compound (for instance, a tautomer of the above-described cyclic compound, etc.) or the like can be employed.
  • a group represented by a below-described formula includes a group as its tautomer represented by a below-described formula
  • A1-B-A2 one of A1 and A2 shows a group represented by a below-described formula (in the formula, P shows the same meaning as described above) and the other includes a group represented by a below-described formula (in the formula, P shows the same meaning as described above).
  • At least one of A1 and A2 includes a group represented by a below-described formula (P shows the same meaning as described above). More specifically, at least one of A1 and A2 includes, as an isomer of the cyclic compound, for example, a compound represented by a below-described formula, a compound represented by a below-described formula, or a compound represented by a below-described formula.
  • the cyclic compound used in the present invention preferably has the particle size as small as possible. More specifically, the particle size of the particle is preferably about 10 ⁇ m or smaller, more preferably about 1 ⁇ m or smaller and most preferably about 0.1 ⁇ m or smaller.
  • the cyclic compound is preferably used as a nucleus agent for polyester capable of having a crystal structure.
  • the polyester capable of having the crystal structure is a polymer compound having at least one ester bond. Any of polyesters capable of having the crystal structures may be employed and well-known polyesters may be employed. Polyester “capable of having a crystal structure” may be polyester capable of partly having a crystal structure without a special limitation. In the polyester, all molecule chains cannot be necessarily regularly arranged. Even in case all the molecule chains do not have regularity in the polyester, when at least two molecule chain segments can be oriented, any polyester may be used. Accordingly, the polyester capable of having the crystal structure preferably has straight chains, however, may have branches. Further, in the present invention, the polyester capable of having the crystal structure is preferably biodegradable polyester.
  • biodegradable polyesters for example, polyesters subjected to a metabolic action by microorganisms may be exemplified.
  • Aliphatic polyester having a moldability, a heat resistance and a shock resistance with good balance is preferably used among them.
  • polyoxalic acid, polysuccinic acid, polyhydroxy butyric acid, butylene polydiglycolic acid, polycaprolactone, polydioxanone, polylactic acid based aliphatic polyester, etc. may be exemplified.
  • the polylactic acid based aliphatic polyester is more preferably used among them.
  • polymers of hydroxy acid such as lactic acid, malic acid, glycolic acid, etc. or copolymers of them may be specifically exemplified.
  • Hydroxy carboxylic acid based aliphatic polyester that typically includes polylactic acid is especially preferably used among them.
  • polylactic acid is most preferable among the hydroxy carboxylic acid based aliphatic polyesters.
  • the biodegradable polyester used in the present invention can be produced in accordance with a known method.
  • the biodegradable polyester can be produced by methods such as a lactide method, a polycondensation of polyhydric alcohol and polybasic acid, or an intermolecular polycondensation of hydroxy carboxylic acid having a hydroxyl group and a carboxyl group in molecules.
  • the polylactic acid based aliphatic polyester can be ordinarily obtained by a method in accordance with a ring-opening polymerization of lactide as cyclic diester and corresponding lactones, what is called a lactide method, or a direct dehydration condensation method of lactic acid except the lactide method.
  • a catalyst for producing the polylactic acid based aliphatic polyester tin, antimony, zinc, titanium, iron, aluminum compounds, etc. may be exemplified. Tin catalyst and aluminum catalyst are preferably used among them and tin octylate and aluminum acetylacetonate are more preferably employed.
  • Poly L-lactic acid obtained by the lactide ring-opening polymerization is most preferable among the polylactic acid based aliphatic polyesters.
  • the poly L-lactic acid is hydrolyzed to have L-lactic acid and its safety is recognized.
  • the polylactic acid based aliphatic polyester employed in the present invention is not limited thereto. Accordingly, the lactide used for producing the polylactic acid based aliphatic polyester is not also limited to L forms.
  • a marketed product such as the name of a product H100J (produced by Mitsui Chemicals, Inc.) may be used.
  • polyester having not necessarily crystal structure or other biodegradable resins may be further included as resin constituents.
  • biodegradable resins below-described materials may be exemplified and there are many kinds of materials that can be employed in the present invention.
  • biodegradable polymers are organic materials decomposed and assimilated by the actions of the natural world and vital materials and any of ideal materials adapted to an environment that do not injure the objects of the present invention may be employed.
  • the biodegradable resin used in the present invention can be produced in accordance with the known methods. Further, as the biodegradable resin, a marketed product may be used. For example, Lacty (produced by Shimadzu Corporation), Lacea (produced by Mitsui Chemicals, Inc.) or Nature Works (produced by Cargill Dow Polymers LLC) etc. may be exemplified.
  • one kind of the above-described biodegradable resins may be included and two or more kinds of the biodegradable resins may be included.
  • these resins may form copolymers or may be mixed together.
  • resins except the above-described biodegradable resins may be included.
  • synthetic resins having no biodegradable property or the like may be included.
  • resins for example, polylactic acid, polybutylene succinate, etc. which moderates decomposition speed may be exemplified.
  • inorganic filler may be added.
  • well-known fillers may be used.
  • talc, alumina, silica, magnesia, mica, kaolin, etc. may be exemplified. Since talc among them is used together with the cyclic compound employed in the present invention to effectively accelerate the crystallization without canceling their effects with each other, talc is more preferably employed.
  • the inorganic filler of about 1 to 50 parts by weight is preferably added relative to polyester capable of having a crystal structure of 100 parts by weight.
  • the amount of the inorganic filler is located within the above-described range, the obtained resin component can be avoided from being brittle.
  • a hydrolysis inhibitor is further preferably added to the resin component according to the present invention.
  • any of hydrolysis inhibitors that can suppress the hydrolysis of the biodegradable resin may be used without special limitation.
  • compounds having reactivity with active hydrogen in the biodegradable resin may be exemplified.
  • the above-described compound is added to the biodegradable resin to reduce the amount of active hydrogen in the biodegradable resin, so that the active hydrogen can be prevented from hydrolyzing polymer chains forming the biodegradable resin like a catalyst.
  • the active hydrogen indicates hydrogen in the bond of oxygen, nitrogen, etc.
  • the hydrolysis inhibitor for example, carbodiimide compounds, isocyanate compounds or oxazoline compounds may be applied thereto.
  • the carbodiimide compound can be melted and kneaded with a biodegradable polymer compound and can more suppress the hydrolysis of the biodegradable resin with a small amount of addition, the carbodiimide compound is preferable.
  • the carbodiimide compound is a compound having one or more carbodiimide groups in a molecule and includes a polycarbodiimide compound.
  • monocarbodiimide compounds included in the carbodiimide compounds dicyclohexyl carbodiimide, diisopropyl carbodiimide, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, diphenyl carbodiimide, naphthyl carbodiimide, etc. may be exemplified.
  • Dicyclohexyl carbodiimide or diisopropyl carbodiimide that is especially industrially available is preferable among them.
  • isocyanate compounds for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl methane diisocyanate, 2,4′-diphenyl methane diisocyanate, 2,2′-diphenyl methane 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-tetrahydro naphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethyl hexamethylene
  • hydrolysis inhibitors can be easily produced in accordance with well-known methods and marketed products may be suitably employed.
  • the biodegradation speed of the resin component of the present invention can be adjusted depending on the kinds or the amount of addition of the hydrolysis inhibitor used in the present invention, the kind and a quantity of mixing of the hydrolysis inhibitor to be mixed may be determined in accordance with a desired product.
  • the amount of addition of the hydrolysis inhibitor is not especially limited to a specific value, however, the amount of addition of the hydrolysis inhibitor is ordinarily 5 wt % or lower relative to all the weight of the resin component and preferably 1 wt %.
  • the hydrolysis inhibitor the above-described compounds may be independently used or two or more kinds of compounds may be used together.
  • addition agents such as an antioxidant, an optical stabilizer, an ultraviolet absorbent, pigment, a colorant, an antistatic agent, a mold releasing agent, perfume, lubricant, a flame retardant, a filler, an antibacterial or antifungal agent, etc. may be added as desired so as not to seriously interfere with a crystallization or a crystalline property.
  • the resin component according to the present invention is produced in such a way that the above-described cyclic compounds or the mixture thereof, polyester capable of having the crystal structure and further other constituents are mixed together as desired.
  • a specific method for producing the resin component according to the present invention from the respective constituents as raw materials thereof a method that the biodegradable resin as a raw material is mixed with the inorganic filler, the hydrolysis inhibitor or the like as desired and the mixture was melted and kneaded by using an extruder is exemplified.
  • a solution method As a method for producing the resin component as well as the above-described method, what is called a solution method may be employed.
  • the solution method is a method that arbitrary solution capable of dispersing and dissolving the respective constituents is used to completely agitate the constituents as raw materials and solvent, form slurry and dry and removed the solvent.
  • the method for producing the resin component according to the present invention is not limited to these methods and conventionally well-known methods except these methods may be employed.
  • the cyclic compound is preferably uniformly and finely dispersed in the biodegradable polyester.
  • a conventionally well-known method may be employed for this purpose.
  • a method for dispersing pigment in the resin and coloring the resin may be used.
  • a method that three rolls are used may be exemplified.
  • a method that the cyclic compound is mixed with polyester, and then, the mixture is repeatedly heated and kneaded a plurality of times is exemplified.
  • a method that the mixture of the cyclic compound and the polyester is supplied to a known melting and mixing machine such as a uniaxial or biaxial extruder, a Banbury mixer, a kneader, a mixing roll, etc. and kneaded at the temperature of about 170 to 380° C. may be exemplified.
  • a known melting and mixing machine such as a uniaxial or biaxial extruder, a Banbury mixer, a kneader, a mixing roll, etc. and kneaded at the temperature of about 170 to 380° C.
  • the addition agent may be added thereto before molding.
  • the mixing ratio of the cyclic compound in the resin component is preferably located within a range of about 0.001 to 10 parts by weight relative to the polyester capable of having the crystal structure of 100 parts by weight, and more preferably located within a range of about 0.01 to 1 parts by weight.
  • the crystallization rate of the resin component is preferably located within a range of about 20 to 100%, and more preferably located within a range of about 40 to 100%.
  • the crystallization time of the resin component is preferably located within a range of about 0 to 1000 seconds, and more preferably located within a range of about 0 to 200 seconds.
  • the modulus of elasticity of the resin component at 80° C.
  • the crystallization rate and the crystallization time are respectively obtained by referring to below-described Examples.
  • the modulus of elasticity is obtained by a measuring method including a tensile elasticity measurement and a bending elasticity measurement.
  • Specimen length of 50 mm ⁇ width of 7 mm ⁇ thickness of 1 mm
  • Measuring device viscoelastic analyzer RSA-II (produced by Rheometric)
  • Measuring geometry Dual Cantilever Bending Frequency: 6.28 (rad/s)
  • the resin component according to the present invention can be widely used for various kinds of moldings. Since the crystalline property of the resin component is high, the moldings made of the resin component according to the present invention are excellent in their rigidity and the transparency thereof can be improved. Thus, the moldings can be preferably used as products that highly require such a rigidity and transparency. As the uses of the moldings using the resin component according to the present invention, such products as described below may be exemplified.
  • a power generator an electric motor, a transformer, a current transformer, a voltage regulator, a rectifier, an inverter, a relay, a contact for power, a switch, a machine circuit breaker, a knife switch, a rod for other electrode, an electric machine parts cabinet, a light socket, various kinds of terminal boards, electric device parts such as a plug or a power module, a sensor, an LED lamp, a connector, a resistor, a relay case, a small switch, a coil bobbin, a capacitor, a variable condenser case, an optical pick-up, an oscillator, a transformer, a printed circuit board, a tuner, a speaker, a microphone, a headphone, a storage device such as a floppy (registered trade mark) disc or an MO disc, a small motor, a magnetic head base, a semiconductor, a liquid crystal, an FDD carriage, an FDD chassis, a printer such as an ink jet printer or
  • the moldings are preferably employed among them as the casings of electric or electronic devices such as televisions or personal computers that are mass-produced. After these products are used, they may be subjected to a biodegradation process and disposed. An excessive energy is not advantageously consumed for disposal of the products.
  • the resin component according to the present invention comprises one or more cyclic compounds selected from between a copper phthalocyanine crystal (a) which may be replaced by a material, a phthalocyanine compound (b) which may include one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium, indium, thallium, tin, lead, antimony, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, silicon and cerium which may be replaced by a material and a por
  • a compound which may be replaced by a material means a compound in which substituent groups may be included.
  • substituent groups such substituent groups as described below may be exemplified. They include, for instance, halogen atoms (for instance, fluorine, chlorine, bromine, iodine, etc.), nitro groups, cyano groups, hydroxy groups, thiol groups, sulfo groups, sulfino groups, mercapto groups, phosphono groups, alkyl groups (for instance, methyl groups, ethyl groups, isopropyl groups, n-propyl groups, n-butyl groups, isobutyl groups, secondary butyl groups, tertiary butyl groups or various kinds of other isomers such as pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecy
  • any of crystals of phthalocyanine compounds including copper may be used without special limitation in the present invention.
  • Well-known materials called copper phthalocyanine crystals may be employed.
  • a crystal of a compound represented by a below-described formula is exemplified.
  • the crystal of a copper phthalocyanine substituent by which the above-described compound is replaced as much as chemically permissible may be also used as the copper phthalocyanine crystal.
  • halogenated copper phthalocyanine or the like may be exemplified.
  • halogenated copper phthalocyanine a material obtained by replacing hydrogen of a benzene ring of copper phthalocyanine by chlorine is exemplified.
  • halogen may be bromine, fluorine or iodine.
  • alkyl groups such as methyl, ethyl, etc.
  • alkoxy groups such as methoxy, ethoxy, etc.
  • hydroxyl groups amino groups, etc.
  • phthalocyanine compound shown in (b) which may include one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium, indium, thallium, tin, lead, antimony, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, silicon and cerium which may be replaced by a material, any of compounds including phthalocyanine groups having no metal or compounds including phthalocyanine groups having one kind of metal selected from between zinc, cadmium, mercury
  • phthalocyanine groups having one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium, indium, thallium, tin, lead, antimony, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, silicon and cerium”, for example, a phthalocyanine compound represented by a below-described formula (in the formula, M designates one kind of metal selected from between zinc, cadmium, mercury, aluminum, germanium, gallium,
  • phthalocyanine compounds well-known compounds referred to as phthalocyanine compounds may be employed.
  • metal free phthalocyanine, titanyl phthalocyanine, aluminum phthalocyanine, vanadium phthalocyanine, cadmium phthalocyanine, antimony phthalocyanine, chromium phthalocyanine, germanium phthalocyanine, iron phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine, dialkyl phthalocyanine, tetramethyl phthalocyanine, tetraphenyl phthalocyanine, etc. may be employed.
  • marketed products having the products names of metal free phthalocyanine, aluminum phthalocyanine, titanyl phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, tin phthalocyanine (produced by Sanyo Color Works, Ltd,) may be employed.
  • an uranium complex (super phthalocyanine) having five isoindole rings or a boron complex having three isoindole rings can be also used as the phthalocyanine compounds.
  • Phthalocyanine substituents by which the phthalocyanine compounds are replaced as much as chemically permissible can be also preferably used as the phthalocyanine compounds.
  • halogenated phthalocyanine or the like is frequently used as a green pigment and a marketed product can be used.
  • Halogen may be chlorine, bromine, fluorine, iodine, etc.
  • substituent groups except the halogen for example, alkyl groups such as methyl, ethyl, etc., alkoxy groups such as methoxy, ethoxy, etc, hydroxyl groups, amino groups, etc. may be exemplified.
  • copper phthalocyanine and phthalocyanine compounds are capable of forming crystals by a regular molecular arrangement. They may have some crystal forms depending on forming conditions.
  • molecules may be arranged in one direction so as to stack cards and rows may form bundles to form crystals.
  • the ways of stacks (inclination angles of planes of molecules relative to an axis and distances between molecules) and the ways of arrangements of rows are different so that many kinds of crystals may be formed.
  • the copper phthalocyanine crystal may take crystal forms such as an alpha type, a beta type, a gamma type, a delta type, a sigma type, an epsilon type, a pie type, a rho type, a tau type, a xi type or an R type.
  • the copper phthalocyanine crystal preferably has a crystal called the beta type or the epsilon type from the reason why the capability of the nucleus agent of crystalline polyester is high.
  • the above-described copper phthalocyanine crystal is frequently used as a blue pigment and the copper phthalocyanine crystals of various crystal types are available from marketed products.
  • porphyrin compound which may be replaced by a material shown in (c)
  • any of compounds including porphyrin groups may be employed without a special limitation in the present invention.
  • compounds called porphyrin compounds may be employed.
  • a haemin compound represented by a below-described formula in the formula, X, Y and Z are the same or different and show hydrocarbon groups, hydrogens, etc. which may be replaced by materials.
  • esters in carboxyl groups thereof may be exemplified.
  • hydrocarbon groups which may be replaced by materials any of the hydrocarbon groups which are replaced by one or more of the above-described substituent groups or hydrocarbon groups which are not replaced by materials may be employed without a special limitation.
  • hydrocarbon groups for instance, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, allyl groups, cross-linked hydrocarbon groups, etc. may be exemplified.
  • alkyl groups straight chain type or branch type alkyl groups (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, tert-amyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, n-docosyl, n-tetracosyl etc.) may be exed alky
  • alkenyl groups for example, straight chain type or branch type alkenyl groups such as vinyl, propenyl (1-, 2-), butenyl (1-, 2-, 3-), pentenyl, octenyl, butadienyl (1,3-) etc. may be exemplified.
  • alkynyl groups for example, straight chain type or branch type alkynyl groups such as ethynyl, propynyl (1-, 2-), butynyl (1-, 2-, 3-), pentynyl, octynyl, decynyl, etc. may be exemplified.
  • cycloalkyl groups for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. may be exemplified.
  • allyl groups for example, monocyclic or polycyclic groups such as phenyl, biphenyl, naphthyl, anthryl, phenanthryl, acenaphthylenyl, etc. may be exemplified.
  • cross-linked hydrocarbon groups for example, 1-adamantyl, 2-adamantyl, 2-norbornanyl, 5-norbornene-2-yl, etc. may be exemplified.
  • substituent groups may be introduced within a chemically permissible range.
  • the cyclic compounds may be, for example, halogenated materials or sulfonated materials.
  • the above-described cyclic compound preferably has a particle size of about 100 ⁇ m or smaller and more preferably has the particle size of the particle of about 10 ⁇ m or smaller.
  • the cyclic compound is also commercially valuable as a nucleus agent for polyester capable of having a crystal structure. In that case, the cyclic compound may be diluted by a diluting agent of suitable solvent.
  • the polyester capable of having the crystal structure is a polymer compound having at least one ester bond. Any of polyesters capable of having the crystal structures may be employed and well-known polyesters may be employed. Polyester “capable of having a crystal structure” may be polyester capable of partly having a crystal structure without a special limitation. In the polyester, all molecule chains cannot be necessarily regularly arranged. Even in case all the molecule chains do not have regularity in the polyester, when at least two molecule chain segments can be oriented, any polyester may be used. Accordingly, the polyester capable of having the crystal structure preferably has straight chains, however, may have branches. Further, in the present invention, the polyester capable of having the crystal structure is preferably biodegradable polyester.
  • biodegradable polyesters for example, polyesters subjected to a metabolic action by microorganisms may be exemplified.
  • Aliphatic polyester having a moldability, a heat resistance and a shock resistance with good balance is preferably used among them.
  • polyoxalic acid, polysuccinic acid, polyhydroxy butyric acid, polydiglycolic acid, polycaprolactone, polydioxanone, polylactic acid based aliphatic polyester, etc. may be exemplified.
  • the polylactic acid based aliphatic polyester is more preferably used among them.
  • polymers of hydroxy acid such as lactic acid, malic acid, glycolic acid, etc. or copolymers of them may be specifically exemplified.
  • Hydroxy carboxylic acid based aliphatic polyester that typically includes polylactic acid is especially preferably used among them. Further, polylactic acid is most preferable among the hydroxy carboxylic acid based aliphatic polyesters.
  • the biodegradable polyester used in the present invention can be produced in accordance with a known method.
  • the biodegradable polyester can be produced by methods such as a lactide method, a polycondensation of polyhydric alcohol and polybasic acid, or an intermolecular polycondensation of hydroxy carboxylic acid having a hydroxyl group and a carboxyl group in molecules.
  • the polylactic acid based aliphatic polyester can be ordinarily obtained by a method in accordance with a ring-opening polymerization of lactide as cyclic diester and corresponding lactones, what is called a lactide method, or a direct dehydration condensation method of lactic acid except the lactide method.
  • a catalyst for producing the polylactic acid based aliphatic polyester tin, antimony, zinc, titanium, iron, aluminum compounds, etc. may be exemplified. Tin catalyst and aluminum catalyst are preferably used among them and tin octylate and aluminum acetylacetonate are more preferably employed.
  • Poly L-lactic acid obtained by the lactide ring-opening polymerization is most preferable among the polylactic acid based aliphatic polyesters.
  • the poly L-lactic acid is hydrolyzed to have L-lactic acid and its safety is recognized.
  • the polylactic acid based aliphatic polyester employed in the present invention is not limited thereto. Accordingly, the lactide used for producing the polylactic acid based aliphatic polyester is not also limited to L forms.
  • a marketed product such as the name of a product H100J (produced by Mitsui Chemicals, Inc.) may be used.
  • polyester that does not necessarily have a crystal structure or other biodegradable resins may be further included as resin constituents.
  • biodegradable resins below-described materials may be exemplified and there are many kinds of materials that can be employed in the present invention.
  • biodegradable polymers are organic materials decomposed and assimilated by the actions of the natural world and vital materials and any of ideal materials adapted to an environment that do not injure the objects of the present invention may be employed.
  • the biodegradable resin used in the present invention can be produced in accordance with the known methods. Further, as the biodegradable resin, a marketed product may be used. For example, Lacty (produced by Shimadzu Corporation), Lacea (produced by Mitsui Chemicals, Inc.) or Nature Works (produced by Cargill Dow Polymers LLC) etc. may be exemplified.
  • one kind of the above-described biodegradable resins may be included and two or more kinds of the biodegradable resins may be included.
  • these resins may form copolymers or may be mixed together.
  • resins except the above-described biodegradable resins may be included.
  • synthetic resins having no biodegradable property or the like may be included.
  • resins for example, polylactic acid, polybutylene succinate, etc. which moderates decomposition speed may be exemplified.
  • inorganic filler may be added.
  • well-known fillers may be used.
  • talc, alumina, silica, magnesia, mica, kaolin, etc. may be exemplified. Since talc among them is used together with the cyclic compound employed in the present invention to effectively accelerate the crystallization without canceling their effects with each other, talc is more preferably employed.
  • the inorganic filler of about 1 to 50 parts by weight is preferably added relative to polyester capable of having a crystal structure of 100 parts by weight.
  • the amount of the inorganic filler is located within the above-described range, the obtained resin component can be avoided from being brittle.
  • a hydrolysis inhibitor is further preferably added to the resin component according to the present invention.
  • any of hydrolysis inhibitors that can suppress the hydrolysis of the biodegradable resin may be used without special limitation.
  • compounds having reactivity with active hydrogen in the biodegradable resin may be exemplified.
  • the above-described compound is added to the biodegradable resin to reduce the amount of active hydrogen in the biodegradable resin, so that the active hydrogen can be prevented from hydrolyzing polymer chains forming the biodegradable resin like a catalyst.
  • the active hydrogen indicates hydrogen in the bond of oxygen, nitrogen, etc.
  • the hydrolysis inhibitor for example, carbodiimide compounds, isocyanate compounds or oxazoline compounds may be applied thereto.
  • the carbodiimide compound can be melted and kneaded with a biodegradable polymer compound and can more suppress the hydrolysis of the biodegradable resin with a small amount of addition, the carbodiimide compound is preferable.
  • the carbodiimide compound is a compound having one or more carbodiimide groups in a molecule and includes a polycarbodiimide compound.
  • monocarbodiimide compounds included in the carbodiimide compounds dicyclohexyl carbodiimide, diisopropyl carbodiimide, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, diphenyl carbodiimide, naphthyl carbodiimide, etc. may be exemplified.
  • Dicyclohexyl carbodiimide or diisopropyl carbodiimide that is especially industrially available is preferable among them.
  • isocyanate compounds for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl methane diisocyanate, 2,4′-diphenyl methane diisocyanate, 2,2′-diphenyl methane 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-tetrahydro naphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethyl hexamethylene
  • hydrolysis inhibitors can be easily produced in accordance with well-known methods and marketed products may be suitably employed.
  • the biodegradation speed of the resin component of the present invention can be adjusted depending on the kinds or the amount of addition of the hydrolysis inhibitor used in the present invention
  • the kind and a quantity of mixing of the hydrolysis inhibitor to be mixed may be determined in accordance with a desired product.
  • the amount of addition of the hydrolysis inhibitor is about 5 wt % or lower relative to all the weight of the resin component and preferably about 1 wt %.
  • the hydrolysis inhibitor the above-described compounds may be independently used or two or more kinds of compounds may be used together.
  • addition agents such as an antioxidant, an optical stabilizer, an ultraviolet absorbent, a pigment, a colorant, an antistatic agent, a mold releasing agent, perfume, lubricant, a flame retardant, a filler, an antibacterial or antifungal agent, etc. may be added as desired so as not to seriously interfere with a crystallization or a crystalline property.
  • the resin component according to the present invention is produced in such a way that the above-described cyclic compounds or the mixture thereof, polyester capable of having the crystal structure and further other constituents are mixed together as desired.
  • a more preferable method for producing the resin component according to the present invention from the respective constituents as raw materials thereof a method that the biodegradable resin as a raw material is mixed with the inorganic filler, the hydrolysis inhibitor or the like as desired and the mixture was melted and kneaded by using an extruder is exemplified.
  • a solution method may be employed as a method for producing the resin component as well as the above-described method.
  • the solution method is a method that arbitrary solution capable of dispersing and dissolving the respective constituents is used to completely agitate the constituents as raw materials and solvent, form slurry and dry and removed the solvent.
  • the method for producing the resin component according to the present invention is not limited to these methods and conventionally well-known methods except these methods may be employed.
  • the cyclic compound is preferably uniformly and finely dispersed in the biodegradable polyester.
  • a conventionally well-known method may be employed for the uniform dispersion.
  • a method for dispersing pigment in the resin and coloring the resin may be used.
  • a method that three rolls are used may be exemplified. Otherwise, a method that simple heating and kneading operations are repeated a plurality of times is also exemplified.
  • the mixing ratio of the cyclic compound in the resin component is preferably located within a range of about 0.001 to 10 parts by weight relative to the polyester capable of having the crystal structure of 100 parts by weight and more preferably located within a range of about 0.01 to 1 parts by weight.
  • the crystallization rate of the resin component is preferably located within a range of about 40 to 100%.
  • the crystallization time of the resin component is preferably located within a range of about 0 to 200 seconds.
  • the modulus of elasticity of the resin component at 80° C. is preferably located within a range of about 50 to 5000 MPa.
  • the crystallization rate and the crystallization time are respectively obtained by referring to below-described Examples.
  • the modulus of elasticity is obtained by the same method as the above-described measuring method. Accordingly, a detailed explanation thereof is omitted.
  • the resin component can be also widely applied to various kinds of moldings similar to those of the above-described resin component. That is, since the crystalline property of the resin component is high, the moldings composed of the resin component according to the present invention are excellent in rigidity and sometimes high in transparency as described above. Accordingly, the moldings are preferably suitably used as products in which the rigidity and transparency are highly requested.
  • polyester capable of having a crystal structure H100J (produced by Mitsui Chemicals, Inc.) as polylactic acid was used.
  • the polylactic acid had molecular weight of 200,000.
  • Pigment Yellow 109 (produced by Chiba Fine Chemical Co., Ltd. IRGAZIN Yellow 2GLTE) was employed as a nucleus agent.
  • the specific surface area thereof was 30 m 2 /g.
  • the nucleus agent was mixed with the polylactic acid so as to have 0.5 parts by weight relative to the polylactic acid of 100 parts by weight.
  • the mixture was heated and kneaded, and then, pelletized to obtain a resin component for molding of the Example 1.
  • the crystalline property of this resin component for molding was evaluated by a differential scanning calorimetry (DSC) in accordance with a method disclosed in Japanese Patent Application Laid-Open No. hei 10-158369.
  • DSC differential scanning calorimetry
  • a sample of 3 to 4 mg was cut from a pellet and accommodated in an aluminum pan. The sample was temporarily heated to 200° C. and cooled to 0° C. at 50° C./minute, and then, the temperature of the sample was raised at 20° C./minute to carry out a measurement.
  • the general crystallization speed (crystallization time) was measured under a photographing operation by a polarizing microscope.
  • a small amount of resin component was mounted on a thin glass (about 0.1 mm), heated by a hot stage at 200° C., and further pressed and covered by a thin glass to have a sample to be observed.
  • the temperature of the sample heated to 200° C. was lowered at 90° C./minute and held and crystallized at 120° C.
  • the state thereof was observed by a crossed nicol. Since the crystal of polylactic acid has a double refraction, the growth of the crystal can be observed by the crossed nicol. As the crystal grows, a visual field to be observed gradually becomes light and the brightness of the visual field to be observed is saturated at a prescribed level.
  • the image of the visual field to be observed was recorded by an objective lens of 10 times and a black and white 1 ⁇ 3 inch CCD video camera and a range of about 600 ⁇ 450 ⁇ m was recorded (digitizing by 10 bits of about 640 ⁇ 480 pixels) and taken in an image capture board of a personal computer. Then, the average of the brightness of an area of about 378 ⁇ 283 ⁇ m in the center of the visual field was obtained (refer simply it to as brightness, hereinafter). The obtained average of brightness was plotted relative time. The time at 120° C. was determined to be 0 and a reference. Since the double refraction of the crystal is used, it is important to recognize many spherulites in all the visual field to be observed as observing conditions. When the number of spherulites is small within the visual field to be observed (when magnification is high or an area set for calculating the average brightness is small), the change of brightness may be possibly uneven relative to the time.
  • Crystallization time was obtained as described below. That is, as shown in FIG. 1 , the leading edge of the brightness in the vicinity of 1 ⁇ 2 as high as saturation is extrapolated 1 by a straight line. Further, a saturation level is horizontally extrapolated 2 by a straight line. The time 4 at the intersection of them is read to obtain the crystallization time 3 .
  • polyester capable of having a crystal structure H100J (produced by Mitsui Chemicals, Inc.) as polylactic acid was used.
  • the polylactic acid had molecular weight of 200,000.
  • Pigment Yellow 110 produced by Chiba Fine Chemical Co., Ltd. CROMOPHTAL Yellow 2RLP was employed.
  • the specific surface area thereof was 49 m 2 /g.
  • a nucleus agent was mixed with the polylactic acid so as to have 0.5 parts by weight relative to the polylactic acid of 100 parts by weight. The mixture was heated and kneaded, and then, pelletized to obtain a resin component for molding of the Example 2.
  • the resin component was evaluated in the same manner as that of the Example 1, and the results thereof are shown in the following Table 1.
  • a Comparative Example 1 the above-described H100J was used as polylactic acid and the polylactic acid was subjected to producing processes under the same conditions as those of the previous Examples. That is, the polylactic acid was heated and kneaded and pelletized to obtain a resin component composed of only the polylactic acid. The resin component was evaluated in the same manner as described above. The results thereof are shown in the following Table 1.
  • a resin component including polylactic acid of 100 parts by weight and calcium stearate (produced by Kanto Kagaku) of 0.5 parts by weight was likewise produced.
  • the resin component was evaluated in the same manner as described above. The results thereof are shown in Table 1.
  • the salt of a long chain carboxylic acid has an effect as a nucleus agent relative to polylactic acid. Accordingly, the crystallization rate was certainly slightly improved.
  • polyester capable of having a crystal structure H100J (produced by Mitsui Chemicals, Inc.) as polylactic acid was used.
  • the polylactic acid had molecular weight of 200,000.
  • Pigment Blue 15:3 (produced by Chiba Fine Chemical Co., Ltd. IRGALITE Blue GBP) was employed.
  • the nucleus agent was mixed with the polylactic acid so as to have 0.5 parts by weight relative to the polylactic acid of 100 parts by weight.
  • the mixture was heated and kneaded, and then, pelletized to have a resin component for molding of Example 3A.
  • Resin components for molding of Examples 3B and 3C including the nucleus agent of 0.1 parts by weight and 0.05 parts by weight were obtained.
  • the crystalline property of the resin component for molding was evaluated by a differential scanning calorimetry (DSC) in accordance with a method disclosed in Japanese Patent Application Laid-Open No. hei 10-158369.
  • DSC differential scanning calorimetry
  • a sample of 3 to 4 mg was cut from a pellet and accommodated in an aluminum pan. The sample was temporarily heated to 200° C. and cooled to 0° C. at 50° C./minute, and then, the temperature of the sample was raised at 20° C./minute to carry out a measurement.
  • the general crystallization speed (crystallization time) was measured under a photographing operation by a polarizing microscope.
  • a small amount of resin component was mounted on a thin glass (about 0.1 mm), heated by a hot stage at 200° C., and further covered with a thin glass in a sandwiched state to have a sample to be observed.
  • a metallic ring of 0.1 mm was used as a spacer between the glasses as desired.
  • the temperature of the sample heated to 200° C. was lowered at 90° C./minute and held and crystallized at 120° C. The state thereof was observed by a crossed nicol.
  • the crystal of polylactic acid Since the crystal of polylactic acid has a double refraction, the growth of the crystal can be observed by the crossed nicol. As the crystal grows, a visual field to be observed gradually becomes light and the brightness of the visual field to be observed is saturated at a prescribed level.
  • the image of the visual field to be observed was recorded by an objective lens of 10 times and a black and white 1 ⁇ 3 inch CCD video camera and a range of about 600 ⁇ 450 ⁇ m was recorded (digitizing by 10 bits of about 640 ⁇ 480 pixels) and taken in an image capture board of a personal computer. Then, the average of the brightness of an area of about 378 ⁇ 283 ⁇ m in the center of the visual field was obtained (refer simply it to as brightness, hereinafter). The obtained average of brightness was plotted relative time. The time at 120° C. was determined to be 0 and a reference. Since the double refraction of the crystal is used, it is important to recognize many spherulites in all the visual field to be observed as observing conditions. When the number of spherulites is small within the visual field to be observed (when magnification is high or an area set for calculating the average brightness is small), the change of brightness may be possibly uneven relative to the time.
  • Crystallization time was obtained as described below. That is, as shown in FIG. 1 , the leading edge of the brightness in the vicinity of 1 ⁇ 2 as high as saturation is extrapolated 1 by a straight line. Further, a saturation level is horizontally extrapolated 2 by a straight line. The time 4 at the intersection of them is read to obtain the crystallization time 3 .
  • Example 4 a resin component for molding was obtained in the same manner as that of the Example 3A except that Pigment Blue 15 (produced by Chiba Fine Chemical Co., Ltd, IRGARITE Blue BLPO) of 0.5 parts by weight was used in place of IRGARITE Blue GBP of 0.5 parts by weight in the Example 3A.
  • Pigment Blue 15 produced by Chiba Fine Chemical Co., Ltd, IRGARITE Blue BLPO
  • Example 5 a resin component for molding was obtained in the same manner as that of the Example 3A except that Pigment Blue 15:6 (produced by Dainippon Ink and Chemicals Incorporated, FASTROGEN Blue EP-7) of 0.5 parts by weight was used in place of IRGARITE Blue GBP of 0.5 parts by weight in the Example 3A.
  • Pigment Blue 15:6 produced by Dainippon Ink and Chemicals Incorporated, FASTROGEN Blue EP-7
  • a Comparative Example 4 the above-described H100J was used as polylactic acid and the polylactic acid was subjected to producing processes under the same conditions as those of the Examples 3 to 5. That is, the polylactic acid was heated and kneaded and pelletized to obtain a resin component composed of only the polylactic acid. The resin component was evaluated in the same manner as described above. The results thereof are shown in the following Table 2.
  • a resin component including polylactic acid of 100 parts by weight and calcium stearate (produced by Kanto Kagaku) of 0.5 parts by weight was likewise produced.
  • the resin component was evaluated in the same manner as described above. The results thereof are shown in the Table 2.
  • the salt of a long chain carboxylic acid has an effect as a nucleus agent relative to polylactic acid. Accordingly, the crystallization rate was assuredly slightly improved.
  • a resin component including polylactic acid of 100 parts by weight and bis (p-methyl benzylidene) sorbitol (produced by New Japan Chemical Co., Ltd. Gel All MD) of 0.5 parts by weight was likewise produced.
  • the resin component was evaluated in the same manner as described above. The results thereof are shown in the following Table 2.
  • a resin component according to the present invention has a high degree of crystallization, the resin component is excellent in its rigidity and moldability. In the resin component according to the present invention, a transparency can be improved, the resin component can be applied to a wide range. Further, since the resin component according to the present invention is decomposed in a natural environment after its disposal, the resin component is also preferable in view of global atmospheric maintenance.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Polyesters Or Polycarbonates (AREA)
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US20090043018A1 (en) * 2007-08-06 2009-02-12 Canon Kabushiki Kaisha Resin composition and molded article
EP2096142A1 (en) * 2008-02-29 2009-09-02 Sony Corporation Resin composition
US20100240820A1 (en) * 2009-03-17 2010-09-23 Sony Corporation Resin composition and molded product thereof, and method for their production
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JP5360487B2 (ja) * 2009-09-28 2013-12-04 Ｄｉｃ株式会社 ポリアリーレンスルフィド樹脂成形体の製造方法
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JP6398404B2 (ja) * 2014-07-15 2018-10-03 富士ゼロックス株式会社 樹脂組成物および樹脂成形体
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US20090043018A1 (en) * 2007-08-06 2009-02-12 Canon Kabushiki Kaisha Resin composition and molded article
US7741389B2 (en) 2007-08-06 2010-06-22 Canon Kabushiki Kaisha Resin composition and molded article
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US11123905B2 (en) * 2016-03-31 2021-09-21 Dandelion Research Limited Polylactic acid moulding process

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CN1602341A (zh) 2005-03-30
JP5157039B2 (ja) 2013-03-06

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