WO2006054493A1 - 難燃性樹脂組成物、その製造方法およびその成形方法 - Google Patents
難燃性樹脂組成物、その製造方法およびその成形方法 Download PDFInfo
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- WO2006054493A1 WO2006054493A1 PCT/JP2005/020719 JP2005020719W WO2006054493A1 WO 2006054493 A1 WO2006054493 A1 WO 2006054493A1 JP 2005020719 W JP2005020719 W JP 2005020719W WO 2006054493 A1 WO2006054493 A1 WO 2006054493A1
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- catalyst
- resin
- flame retardant
- flame
- resin composition
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
Definitions
- the present invention relates to a resin composition imparted with flame retardancy, and in particular, a resin composition containing, as a resin component, biodegradable resin and Z or plant oils as a raw material.
- the present invention relates to a product, a manufacturing method thereof, and a molding method thereof.
- biodegradable fats or biodegradable plastics
- CO 2 carbon dioxide
- biodegradable resin has attracted attention from the viewpoint of measures to prevent global warming.
- Products using biodegradable coagulants may be convenient for users, for example, when used in the agricultural field, because it is not necessary to collect used plastic. For these reasons, the market for biodegradable fats and oils is expanding.
- Plant-derived rosin is also attracting attention in the fields of electronic equipment and automobiles.
- Plant-derived coconut oil is obtained by polymerizing or copolymerizing monomers obtained from plant raw materials. Plant-derived coconut oil is generally produced without relying on petroleum resources, and even when the plant as a raw material grows by absorbing carbon dioxide and is discarded by incineration, Small amount of generated CO
- Plant-derived fats and oils are generally biodegradable, but it is not always necessary to have biodegradability from the standpoint of preventing the depletion of petroleum resources.
- biodegradable soot that contributes to environmental protection
- plant-derived rosin that does not have biodegradability is also included. Therefore, in the present specification including the following explanation, in order to generically refer to biodegradable fats (including petroleum-derived and plant-derived) and non-biodegradable fats derived from plants.
- the term “environmental oil” is used.
- PHA polylactic acid
- PBS polybutylene succinate (copolymer resin of 1,4 butanediol and succinic acid).
- PET modified polyethylene terephthalate
- PLA corresponds to the plant-derived scabs described above.
- PLA can be produced by chemical synthesis using sugars produced by plants such as corn or sweet potato as raw materials, and has the potential for industrial production.
- plastics containing plant-derived rosin are also called bioplastics.
- PLA has attracted particular attention since mass production using corn as a raw material has started, and it is desired to develop technologies that can apply PLA to a wide variety of uses, not just those that require biodegradability. Yes.
- Table 2 shows the physical properties of polystyrene (PS), acrylo-tolyl-butadiene-styrene resin (hereinafter abbreviated as ABS), polylactic acid (PLA) and environmental resin, which are common resins.
- PS polystyrene
- ABS acrylo-tolyl-butadiene-styrene resin
- PLA polylactic acid
- environmental resin which are common resins.
- PBS polybutylene succinate
- “Bending elastic modulus” and “bending strength” represent rigidity. The larger the value, the higher the rigidity.
- Izod impact strength” indicates the fracture energy when a test piece breaks under impact load. The larger the value, the harder it is to crack when an impact is applied.
- Thermal deformation temperature is the temperature at which the deformation of the resin starts, and the higher the value, the higher the temperature that can be used.
- PLA is hard and brittle and PBS is soft.
- PLA has poor heat resistance.
- PBS has higher heat resistance than ABS.
- Patent Document 1 proposes to add about 0.5 to 20 wt% of synthetic strength to PLA in order to improve the heat resistance of PLA.
- Patent Document 2 proposes to add an additive (for example, a calpositimide compound) that suppresses the hydrolysis (biodegradation action) of biodegradable rosin.
- polystyrene (PS) resin which is not environmental resin, has a good balance between physical properties and cost. Containers, packaging, building materials, general goods, electrical appliances, electronic equipment, textiles, paints, adhesives, automobiles, It is widely used for products in various fields such as precision instruments. The amount of PS resin used is large, and polystyrene is one of the five general-purpose resins along with butyl chloride, polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET). Therefore, above In parallel with the development of environmental resins, it will continue to be necessary to use polystyrene resin.
- HIPS high-impact polystyrene
- Budagen rubber in which Budagen rubber is blended with PS
- HIPS is not the main PS, especially for consumer electronics, electronic products, building materials, and automobiles. It is used for.
- HIPS is a further improvement in the impact resistance of PS, and is used to construct parts or components that are used over a relatively long period of time, such as exterior bodies of various products.
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2002-173583
- Non-Patent Document 1 Serizawa et al., “Development of Kenaf Fiber Reinforced Polylactic Acid” (Proceedings of the 14th Annual Meeting of the Plastic Molding Society, 161, 162, 2003)
- the grease composition described in Patent Document 1 and Non-Patent Document 1 is a composition proposed for the purpose of improving heat resistance, and is applied to an exterior body of a home appliance. It does not mention providing essential flame retardancy.
- the resin composition described in the above document does not have flame retardancy. Therefore, the conventionally proposed PLA composition cannot be applied to an exterior body of an electrical product such as a television set having a high voltage portion inside.
- electrical appliances place importance on safety, and there is a tendency to adopt a flame retardant resin even in equipment that does not have high-voltage elements inside. Therefore, even if environmental resin has satisfactory properties in rigidity, impact strength, heat resistance, etc., its usefulness is extremely low as long as it does not have flame retardancy.
- HIPS resin which is a type of PS
- HIPS flame retardants are produced by blending halogen-based flame retardants and flame retardant aids, etc.
- HIPS has high flame retardancy due to these flame retardants and flame retardant aids.
- dioxin when the waste containing halogenated flame retardants is discarded and incinerated, and the use of specific halogenated flame retardants is being prohibited in Europe.
- a non-halogen flame retardant for example, a phosphorus flame retardant is known.
- Phosphorus flame retardants also exhibit a somewhat high flame retardant effect, but in order to obtain the same flame retardance as halogen flame retardants, it is necessary to mix them with a resin at a high blending ratio. For this reason, a resin composition containing a phosphorus-based flame retardant tends to have poor mechanical properties.
- the flame retardant mechanism varies from flame retardant to flame retardant.
- halogen flame retardants represented by bromine are decomposed by heat. Trap and suppress the combustion reaction.
- Phosphorus flame retardants are said to promote the formation of a carbonized layer (chia) by combustion, and this carbonized layer blocks oxygen and radiant heat and suppresses combustion.
- the metal hydroxide flame retardant is a mechanism that flame retardants by simply adding a large amount of non-combustible material, and a large amount is required.
- some compounds have a compounding ratio exceeding 50 wt%.
- the flame retardant is present in the greave composition in a larger amount than the greave component, and the physical properties of such a greave composition are not mixed with the flame retardant. It becomes completely different from the physical properties of greaves, making it difficult to say greaves. Therefore, when developing a flame retardant to be blended with rosin, it is required to develop a flame retardant exhibiting a flame retardant mechanism that exhibits a high flame retardant effect with a small amount of blend.
- the present invention has been made in view of the actual situation, and a non-halogen flame retardant is imparted to a general-purpose resin such as environmental resin or PS and HIPS, for example, for electrical appliances.
- a general-purpose resin such as environmental resin or PS and HIPS, for example, for electrical appliances.
- An object is to provide a resin composition useful as an exterior body.
- the present inventors have made the catalyst used when purifying, decomposing, synthesizing, or reforming hydrocarbons into a flame retardancy imparting component that imparts flame retardancy.
- the present invention includes one or more resin components and one or more flame retardancy imparting components, and at least one of the flame retardancy imparting components is a catalyst for purifying hydrocarbons, carbonization
- a catalyst that decomposes hydrogen A resin composition is provided that is at least one catalyst selected from a catalyst that synthesizes hydrocarbons and a catalyst that reforms hydrocarbons.
- wax is used to indicate a polymer in the rosin composition
- wax composition refers to a composition containing at least rosin.
- Plastic means a substance containing a polymer as an essential component.
- the resin composition of the present invention includes a resin component and a flame retardant component, and therefore can be called a plastic.
- flame retardancy refers to a property that does not continue combustion or cause no residue after the ignition source is removed.
- flame retardancy-imparting component that imparts flame retardancy refers to a flame retardant component that is a component that imparts flame retardancy to fat by adding it (this component is referred to as “flame retardant”).
- flame retardant when added alone, flame retardant cannot be made flame retardant.
- the flame retardant component when added together with the flame retardant component, the flame retardant component has a higher flame retardancy improving effect. It refers to flame retardant aids that play a role, and it is a generic term for ingredients that contribute to the improvement of flame retardancy of rosin.
- the flame retardant component used in the present invention is a catalyst used in the purification, decomposition, synthesis and Z or reforming of hydrocarbons, and does not contain any halogen or hardly produces dioxin. ⁇ It is a form of compound.
- the terms “and Z or” are used assuming that a catalyst may be used in more than one process, eg, both cracking and reforming. These catalysts can act as flame retardant components by themselves, or can act as flame retardant components or flame retardant aids with other flame retardant components (ie, flame retardants).
- the catalyst used as a flame retardant imparting component is, for example, a catalytic cracking catalyst, an isomerization catalyst, a dehydrogenation catalyst, a metal complex, a hydrocracking catalyst, a desulfurization catalyst, a denitration catalyst, or a methanation catalyst.
- Sweetening catalyst hydrogenation catalyst, chlorination catalyst, oxidation catalyst, organic matter removal catalyst, polymerization catalyst, alkylation catalyst, dehalogenation catalyst, conversion catalyst, synthesis catalyst, reforming catalyst, organic compound removal catalyst, nitrogen oxidation
- One or more catalysts selected from a catalyst for removing substances, a deodorizing catalyst, a catalyst for decomposing ozone, a catalyst for recovering sulfur, a catalyst for producing an inert gas, a catalyst for producing sulfuric acid, a catalyst for producing nitric acid, a photocatalyst, and the like.
- These catalysts act to promote catalytic cracking of hydrocarbons and the like, and are conventionally used in chemical processes for obtaining a target compound, or gas It has been used in the past to adsorb and decompose specific compounds therein.
- the reaction conditions when using these catalysts are often high temperature and Z or high pressure.
- these catalysts are discharged out of the process as a waste catalyst after the reaction and do not remain in the desired reaction product.
- these catalysts are kneaded and dispersed in a resin in advance, so that in the process where the resin is actually combusted, an action peculiar to the catalyst is exerted during the combustion reaction. It was made as a result of finding out that it greatly contributes to flame retardancy.
- the flame retardant component is preferably a silica-magnesia catalyst (hereinafter sometimes referred to as MgOZSiO).
- MgOZSiO silica-magnesia catalyst
- the Nessia catalyst is a solid acid catalyst and can be used as a catalytic cracking catalyst for hydrocarbons. This catalyst is particularly preferably used because it imparts extremely good flame retardancy to biodegradable and plant-derived resin and PS resin.
- At least one rosin component is at least one rosin selected from biodegradable and plant-derived greaves.
- biodegradable rosin means a rosin that, after use, decomposes into low molecular weight compounds with the participation of microorganisms in nature, and finally decomposes into water and oxygen.
- Plant-derived coconut oil '' means rosin obtained by polymerizing monomers obtained from plant raw materials or by copolymerizing the monomers with other monomers (not necessarily plant-derived!). means. Plant-derived fats may or may not have biodegradability, and plant-derived fats having biodegradability may be classified as “biodegradable fats” as used herein. .
- biodegradable resin or plant-derived resin is used as the polymer component, these two types of resin are described in parallel. Please note that
- the rosin composition of the present invention preferably contains polylactic acid (PLA), a lactic acid copolymer or polybutylene succinate (PBS), or a mixture thereof as a rosin component. It is particularly preferable to contain As described above, it has been proposed that polylactic acid (PLA) is used as a plant-derived rosin that can be mass-produced for use in the housing of household appliances. Therefore, the usefulness can be further improved by imparting flame retardancy to the resin using a catalyst that is substantially non-halogen.
- PBS polybutylene succinate
- At least one rosin component is preferably polystyrene (PS).
- PS polystyrene
- a flame retardant component selected from the above-mentioned catalyst, which is substantially non-halogen allows polystyrene having good mechanical properties and flame retardancy to be in an environmentally friendly form. Can be provided.
- the present invention also provides a production method comprising kneading at least one resin component and at least one flame retardant component as a method for producing a flame retardant resin composition.
- the flame retardancy-imparting component selected from the above specific catalyst is indispensable for a conventional plastic production process or molding process. It is given to the rosin component. Therefore, according to this production method, a separate step of blending the flame retardancy-imparting component does not occur, and the flame retardant resin can be obtained without increasing the production cost.
- This production method can also be applied to misalignment in the case where the resin component is biodegradable resin or plant-derived resin and when the resin component is polystyrene. Gatsutsu In particular, this manufacturing method uses a generally used plastic manufacturing method when the coconut resin component is biodegradable coconut oil or plant-derived coconut oil. Is advantageous in that it can be obtained.
- a method for forming a flame retardant resin composition a composition obtained by kneading at least one resin component and at least one flame retardant component is injected.
- a molding method including molding by a compression molding method is provided. That is, the flame retardant resin composition of the present invention can be molded according to a conventional method without greatly changing the production equipment for conventionally used plastic molded products.
- the coconut resin composition of the present invention has a biodegradable plastic or plant-derived plastic, such as a thermoplastic resin, particularly when the coconut resin component is biodegradable coconut or plant-derived rosin.
- the raw material can be easily switched to the plastic.
- the resin composition of the present invention containing PS as a resin component can be molded using an apparatus conventionally used as a molding apparatus for PS as it is.
- non-halogen flame retardant that does not increase the production process to biodegradable rosin that is friendly to the global environment and PS that is widely used in plant-derived rosin and various products. It becomes possible to add flame retardancy using a catalyst which is an imparting component.
- the resin composition of the present invention can be an extremely environmentally friendly material because no harmful substances are generated or little even when incinerated after use.
- the resin composition of the present invention since the resin composition of the present invention has high flame retardancy and can be used as an exterior body for electronic products, the resin composition of the present invention has great industrial value and is useful. It is.
- FIG. 1 is a flow chart showing a method for producing a flame-retardant resin composition of the present invention.
- FIG. 2 is a flow diagram showing a method for producing the flame retardant resin composition of the present invention.
- the flame retardant resin composition of the present invention comprises one or more resin oils as a resin component.
- it includes one or more flame retardancy-imparting components that are selected for specific catalytic power.
- the rosin component will be described.
- One of the preferred forms of the composition of the present invention includes at least one resin component selected from biodegradable resin and plant-derived resin.
- Known biodegradable and plant-derived fats can be arbitrarily used.
- biodegradable fats and oils are produced from petrochemical raw materials such as poly-force prolatatone (PCL), polybutylene succinate (PBS) and modified polyethylene terephthalate (for example, copolymer) (modified PET), and microorganisms.
- PCL, PBS and modified PET may be obtained by polymerizing monomers obtained from plant raw materials.
- Typical examples of plant-derived sorghum are polylactic acid (PLA) and lactic acid copolymers.
- PLA and a lactic acid copolymer are coconuts obtained by polymerizing lactic acid obtained by fermenting starch or sugar obtained from corn or sweet potato.
- PLA is a hydrolyzable biodegradable rosin and may be used by adding a compound that reduces hydrolyzability in applications where biodegradability is not preferred. In that case, the biodegradability is low or not biodegradable.
- plant-derived coconut oil regardless of whether it is biodegradable, does not use petroleum resources, has a small amount of combustion heat, and the plant as a raw material absorbs carbon dioxide. From the viewpoint of growth, the viewpoint of environmental protection is also preferably used in the present invention.
- the fat component selected from biodegradable fat and plant-derived fat PBS or PLA is preferably used, and in particular, PLA or a mixture of PLA and another resin is preferred. used. Since PLA has excellent transparency and rigidity, a molded product made of the PLA can be used for various applications. On the other hand, PLA has the disadvantages of low heat resistance and impact resistance and slightly low injection moldability. For this reason, PLA is preferably used in combination with other resins and Z or modifiers, particularly when injection molding. For example, PBS is suitable for mixing with PLA because of its excellent heat resistance and biodegradability itself. Specifically, PLA and PBS are preferably mixed at a ratio of 95: 5 to 55:45 (weight ratio).
- PLA may be modified using a commercially available polylactic acid modifier.
- the scab component selected from biodegradable sallow and plant-derived sachet is optionally biodegradable sallow and other non-plant-derived sallow (for example, biodegradable It may be used in combination with a resin made from petrochemical materials. In such a case, it is desirable that the other rosin is contained in a proportion of up to 45 wt% of the total rosin component.
- polystyrene As a resin component.
- PS polystyrene
- Polystyrene has a greater impact on the environment than biodegradable fat, as long as it is not biodegradable fat but also plant-derived fat.
- polystyrene is widely used in various products, and if it can be flame retardant with a substantially non-halogen flame retardant, it can eliminate or reduce harmful substances generated during combustion. In that sense, it can constitute an environmentally friendly rosin composition.
- PS has sufficiently good physical properties even when used alone (that is, without being mixed with other oil components), and can be used in various products. You may mix with other resin.
- a rubber-based resin as a resin component to obtain HIPS.
- the rubber-based resin for example, butadiene, silicone-based rubber, acrylic rubber, or the like is selected, and one or more resins selected, and preferably butadiene-based rubber is added. It is preferable to mix rubber-based resin such as butadiene rubber at a ratio of 5 to 45 wt% with respect to the total amount of PS and rubber-based resin. Will greatly improve.
- the resin component constituting the resin composition of the present invention may be a resin other than the resin components exemplified above!
- the resin component constituting the resin composition of the present invention may be a resin other than the resin components exemplified above!
- Thermoplastic resin such as polyethylene, polypropylene, polystyrene, ethylene acetate butyl copolymer, polysalt butyl, AS, ABS, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT),
- BR butadiene rubber
- IR isoprene rubber
- SBR styrene Z butadiene copolymer
- Thermoplastic elastomers such as styrene Z ethylene butylene copolymer (HSBR) and styrene Z isoprene copolymer (SIR),
- Thermoplastic engineering resins such as polyamide (PA), polycarbonate (PC) and polyphenylene ether (PPE),
- Super engineering rings such as polyarylate (PAR) and polyetheretherketone (PEEK), and
- Thermosetting resins such as epoxy resin (EP), bull ester resin (VE), polyimide (PI) and polyurethane (PU)
- One or a plurality of rosins whose forces are also selected may be included as a rosin component in the rosin composition of the present invention.
- the flame retardancy imparting component imparting flame retardancy As the flame retardant imparting component, as described above, a catalyst used in hydrocarbon purification, cracking, synthesis and Z or reforming process is used. Specifically, for example, a catalytic cracking catalyst, An isomerization catalyst, a dehydrogenation catalyst, a hydrocracking catalyst, an organic compound removal catalyst, and the like can be used as a flame retardant imparting component. It is preferable that these catalysts contain no halogen in the molecule from the viewpoint of environmental protection.
- non-halogen-based or “not containing a halogen” with respect to a flame retardant component such as a flame retardant component or a flame retardant includes a catalyst containing a halogen atom exemplified below. Used to encompass.
- catalytic cracking catalyst that can be used as a flame retardancy-imparting component
- silica-alumina catalyst SiO ZA1 O
- silica-magnesia catalyst MgOZSiO
- activated clay SiO ZA1 O
- silica-magnesia catalyst MgOZSiO
- Such as zeolite and silica alumina magnesia catalyst (SiO ZA1 O ZMgO)
- Z used for a catalyst indicates that two or more components are combined, and, for example, two or more compounds such as a complex oxide Forming the next compound or compound compound! / Single, mixing two or more components together, or one or more of the two or more components as a carrier and the other components as a carrier It means that it is supported.
- each “Z” in each of the catalysts has a meaning commonly used in the field of purification or catalytic cracking of hydrocarbons (for example, petrochemical industry). And its meaning will be apparent to those skilled in the art.
- Specific examples of the isomerization catalyst that can be used as the flame retardancy-imparting component include Pt / Al 2 O 3.
- dehydrogenation catalyst that can be used as the flame retardancy-imparting component include CeO, La
- 2 2 3 2 can be used as a flame retardant component.
- NiZCuCrZKG Al O, CuCr / Mn / Ba, CuCe / Mn, NiZKG (diatomaceous earth), NiZCuCrZKG and
- the desulfurization catalyst that can be used as the flame retardancy-imparting component include activated carbon, ZnO, CuO, Ni, and CrO.
- alkylation catalyst that can be used as a flame retardant component
- a flame retardant component include, for example, Fe 2 O 3.
- Specific examples of the synthetic catalyst that can be used as the flame retardant component include Fe, FeO, FeO, CaO, K0, and Na2O.
- An organic compound removal catalyst that can be used as a flame retardant component is, for example, Pt / Al 2 O 3
- the activity of the catalyst may be increased as needed (ie, activated to increase the strength) and then mixed with the resin component. Activation is performed, for example, by heating the catalyst.
- two or more flame retardant components may be used in combination.
- the combination of two or more flame retardancy-imparting components may be a combination of two or more catalysts selected from the above catalysts, or may be a combination of a catalyst and a known general flame retardant. .
- the ratio of each flame retardant component can be set according to the desired flame retardant!
- the catalyst and a known flame retardant when used in combination, an effect of reducing the amount of the known flame retardant used can be obtained.
- the above catalyst for example, silica magnesia catalyst
- a phosphorus-based flame retardant if used in combination, if the catalyst is added so as to occupy 5 wt% of the resin composition, phosphorus Even if the proportion of the flame retardant is reduced to about 10%, it is possible to obtain the same flame retardancy as that of the resin composition in which only the phosphorus flame retardant accounts for about 40 wt%.
- a catalyst as a flame retardancy-imparting component, it is possible to obtain a resin composition having high flame retardancy even if the blending ratio of known flame retardants is reduced, Complete non-halogenated resin composition Even if things cannot be realized, the burden on the environment can be reduced more than before.
- Known flame retardants are, for example, phosphorus flame retardants, halogen flame retardants, and metal hydroxide flame retardants.
- Hydroxyl metal flame retardant for example, hydroxide magnesium (Mg (OH))
- a metal hydroxide flame retardant is preferably used when it is desired to increase the strength and rigidity of the molded body, for example, in a television receiver back cover.
- flame retardancy-imparting components those that exhibit a high flame retardant effect in a small amount when added to biodegradable fat and plant-derived fat, especially plant-derived fat and PS Examples include silica-alumina catalysts, silica-magnesia catalysts, and catalysts such as La 2 O and CeO.
- Silica magnesia catalyst (MgO / SiO 2) is one of the solid acid catalysts.
- a silica magnesia catalyst having a MgO ratio of 10 wt% to 50 wt%.
- the ratio force of MgO is less than SlOwt%, the catalytic action is not sufficiently exhibited (that is, the action of decomposing the resin is weak), and the effect of flame-retardant soot tends to be low.
- the proportion of MgO exceeds 50 wt%, the catalytic action becomes too strong, and the resin is decomposed into large molecular weight molecules to increase the amount of combustion heat, and as a result, the flame retardant effect may be reduced. .
- the mixing ratio of the flame retardancy-imparting component depends on the type of flame retardancy imparting component, the type of resin component, the degree of flame retardancy required for the resin composition, and the amount of flame retardancy imparting component added. It is determined according to the amount of change in the physical properties of the composition. Specifically, for example, in the rosin composition, The flame retardancy-imparting component selected from the catalyst preferably occupies about 0.5 wt% to 40 wt%.
- the proportion of the flame retardant imparting component is less than 0.5 wt%, it is difficult to obtain a significant flame retardant improvement effect. If it exceeds 40 wt%, undesirable effects resulting from the mixing of the flame retardant imparting component (for example, , Poor moldability due to a decrease in fluidity, etc.).
- the mixing ratio of the above-described flame retardancy-imparting component is an exemplification, and the optimum range of the mixing ratio of the flame retardancy-imparting component varies depending on the type of the resin component and the type of flame retardancy-imparting component.
- polylactic acid, a lactic acid copolymer, or a mixture of at least one of these resins and another resin is used as a resin component, and a catalyst (particularly silica-magnesia catalyst) is used as a flame retardant component.
- a catalyst particularly silica-magnesia catalyst
- the catalyst is l to 45 wt% of the resin composition. It is preferable to mix the catalyst so as to account for%.
- the flame retardancy-imparting component selected from the above catalyst is preferably dispersed in the resin while being supported on the inorganic porous body. Specifically, the flame retardancy-imparting component is supported on the inorganic porous material, and this is kneaded with the resin component to pulverize the inorganic porous material into fine particles and disperse it in the resin. It is preferable that the property-imparting component is dispersed in the resin.
- a resin composition in which the flame retardancy-imparting component is more uniformly dispersed can be obtained, so that the amount of flame retardant imparting component added can be reduced.
- an inorganic porous material when used, it is added at the start of kneading as a large granular material so that aggregation does not occur, and is pulverized into fine particles and uniformly dispersed during kneading. Compared with the case where only the flame retarding component is added, the dispersibility of the flame retarding component is improved. Further, since the inorganic porous body itself has a property of imparting flame retardancy to the resin, it enhances the flame retardancy of the resin composition synergistically with the supported flame retardancy imparting component.
- the inorganic porous body is, for example, a porous body that also has an oxygen and Z or acid aluminum strength and has pores having a pore diameter of 10 to 50 nm at a ratio of 45 to 55 vol%.
- Such an inorganic porous body is preferably a granular body having a particle diameter of 100 to 1000 nm when the flame retardant imparting component is supported. If the particle size is too small, agglomeration occurs and the particles May become huge. On the other hand, if the particle size is too large, the particle size of the inorganic porous material after being pulverized in the kneading step becomes large and may not be uniformly dispersed.
- the porous resin composition finally obtained that is, after kneading the inorganic porous body, the inorganic porous body is
- the flame retardant component may be supported in an amount of 3 to 50 parts by weight with respect to 100 parts by weight of the inorganic porous material.
- the inorganic porous material carrying the flame retardancy-imparting component may be added and kneaded so as to occupy 1 to 40 wt% of the entire resin composition.
- the amount of the flame retardant imparting component and the amount of the inorganic porous material added here are examples, and may be outside these ranges depending on the type of the flame retardant imparting component.
- the flame retardancy-imparting component is, for example, a method in which the inorganic porous body is immersed in a liquid in which the supported flame retardancy imparting component is dissolved or dispersed in a solvent, and then the solvent is evaporated by heating. Thus, it can be supported on the inorganic porous body.
- the inorganic porous body itself can be produced according to a known method.
- the pore-forming agent for example, a water-soluble inorganic salt
- the inorganic porous material may be porous glass or zeolite.
- the inorganic porous material When the inorganic porous material has, for example, zeolite strength, the inorganic porous material itself functions as a hydrocarbon catalytic cracking catalyst, and the inorganic porous material can be regarded as a flame retardant component. There is. Even when the inorganic porous material is regarded as a flame retardancy-imparting component, the preferable upper limit of the amount added is 40 wt% as described above, which is the preferred upper limit of the flame retardancy imparting component described above. Is the same
- the inorganic porous material is a porous material made of acid silicate (silica) having pores with a pore diameter of 10 to 50 nm at a ratio of 45 to 55 vol% and a particle size of 100 Those of ⁇ 500 nm are preferably used.
- the silica porous material is supported at a ratio of 5 to 45 parts by weight, and more preferably 10 to 35 parts by weight.
- Supports CeO and Z or La O The silica porous body is preferably added so as to occupy 5 to 40 wt% of the entire composition, and more preferably added so as to occupy 5 to 15 wt%.
- the inorganic porous material is dispersed in the resin as fine particles having a particle size of 25 to 150 nm, and CeO and Z or La O is a rosin composition,
- the use of the inorganic porous material can reduce the addition ratio of the flame retardancy-imparting component.
- the resin composition of the present invention may contain other flame retardant aids in addition to the flame retardant component selected from the above catalysts.
- the flame retardant aid does not become a flame retardant component by itself, but when added together with the flame retardant component, it serves to enhance the flame retardancy improving effect of the flame retardant component. Therefore, when one or more catalysts selected from the above catalysts are used as flame retardant components, the amount of catalyst added can be further reduced by using a flame retardant aid.
- the flame retardant aid include organic peroxides such as ketone peroxide, peroxyketal, hard mouth peroxide, dialkyl peroxide, peroxyester, and peroxydicarbonate, and dimethyl-diphenol.
- One or more compounds selected from rubbutane and derivatives thereof can be used.
- organic peroxides are used as flame retardant aids, it is estimated that organic peroxides release oxygen in the resin composition, thereby improving the flame retardancy of the resin composition.
- dimethyl-diphenylbutane is used as a flame retardant aid, it is estimated that dimethyl-diphenylbutane exhibits a radical trapping effect, thereby improving the flame retardancy of the resin composition.
- these estimations do not affect the category of the present invention.
- the mixing ratio is not particularly limited, and is arbitrarily selected so as to obtain desired flame retardant characteristics.
- the flame retardant aid may be added, for example, in an amount of 5 to 45 parts by weight with respect to 100 parts by weight of the flame retardant component, depending on the type and amount of the flame retardant component. Further, the total amount of the flame retardant aid and the flame retardant component (that is, the amount of the flame retardant imparting component) is preferably an amount corresponding to 5 to 40 wt% of the entire resin composition. The reason is as described above.
- the greave composition of the present invention includes other components in addition to the above components (that is, the greave component and the flame retardancy-imparting component (including the inorganic porous material when supported on the inorganic porous material) May contain .
- a coloring agent or the like may be included to make the rosin composition have a desired color.
- butadiene rubber may be included in order to improve the impact resistance, in order to make the physical properties of the resin composition desired.
- acrylic rubber and / or silicone rubber may be included in addition to this. These rubbers can also be used where it is desired to improve the impact resistance of biodegradable and Z or plant derived fats.
- the resin composition of the present invention is produced by kneading a resin component and a flame retardant component.
- the kneading may be performed before obtaining pellets, for example, in the case of producing a pellet-shaped resin composition.
- pellet-shaped rosin or rosin composition
- the flame retardancy-imparting component can be mixed with a dissolved resin that does not contain the flame retardancy-imparting component.
- the resin when manufacturing the exterior body of electronic products by plastic molding, the resin is dissolved and injection molded into a mold having a predetermined shape, or the upper and lower molds are dissolved by dissolving the resin.
- a compression molding method is used in which pressure is applied using.
- a step of kneading the melted resin using a kneader or the like is performed. Therefore, at the time of the kneading, the flame retardancy-imparting component may be mixed with the resin component to obtain a molded product comprising the flame retardant resin composition composition. If the flame retardancy-imparting component is added in such a manner, a separate step for adding the flame retardancy-imparting component is not required, and thus the resin composition of the present invention can be efficiently obtained.
- the resin composition of the present invention is an environment-friendly resin or flame retardant imparted with flame retardancy using a substantially halogen-free catalyst as a flame retardant imparting component.
- a molded body it is preferably used for a housing or a part of various electronic products.
- the resin composition of the present invention is a computer, mobile phone, audio product (for example, radio, cassette deck, CD player, MD player), microphone, keyboard, and portable audio player housing and parts. Used as a member.
- the resin composition of the present invention may be used for automobile interior materials, motorcycle exterior materials, and various household goods.
- Pellets were prepared by kneading 70 wt% of polylactic acid (PLA) synthesized from corn and 30 wt% of polybutylene succinate (PBS) using a twin-screw kneader (Step 1).
- PBS polybutylene succinate
- the pellets thus obtained are mixed with a powder of silica magnesia catalyst (MgO: 24.5 wt%) as a flame retardant component, and are necessary to obtain a flame retardant resin composition that meets UL standard VO.
- the mixing ratio of the silica-magnesium catalyst was determined.
- Step 2 The blending sequence of the composition in this test is shown in the flow chart shown in FIG.
- the pellets obtained in Step 1 and the silica-magnesia catalyst activated by heat treatment in advance as a flame retardant component were kneaded at 185 ° C in a biaxial kneader (Step 2), and 125 m It was press-molded into m x 13 mm x 3.2 mm test pieces (molding temperature 180 ° C, pressure 120 kgZ cm 2 ) (Step 3).
- a plurality of test pieces were prepared by changing the mixing ratio of the pellet and the silica magnesia catalyst, and the flame retardancy was evaluated for each of the test pieces.
- the silica-magnesia catalyst was used in the form of a powder having a particle size of about 2-80 m.
- the catalyst was not crushed by the kneading and was dispersed in the resin while maintaining the initial powder size.
- the blending ratio of PLA-PBS pellets and silica-magnesium catalyst was required to be 90:10 (weight ratio).
- Table 3 shows the results of the UL-94 vertical combustion test conducted on test specimens containing 10 wt% of silica-magnesia catalyst.
- Table 3 shows the results of UL-94 vertical combustion test conducted on the test piece containing 10% by weight of silica-magnesia catalyst.
- polylactic acid (PLA) and polybutylene succinate (PBS) were kneaded to prepare pellets (Step 1).
- composition sequence (order) of the composition in this test is also shown in the flow diagram shown in FIG.
- La O catalyst which is a flame retardant component, is converted into a porous SiO.
- La O catalyst is supported at a ratio of 40 parts by weight per 100 parts by weight of the porous material.
- the mixture was kneaded at 185 ° C. with a twin-screw kneader (step 2) and press-molded into a 125 mm ⁇ 13 mm ⁇ 3.2 mm test piece (molding temperature 180 ° C., pressure 120 kgZcm 2 ) (step 3).
- the porous SiO used in this test has a porosity of about 45-50 vol%, about 100 nm-1000 nm.
- This SiO porous body is subjected to shearing force when kneaded with resin.
- the content of 2 3 medium was calculated to be 4 wt%.
- test piece was subjected to UL-94 vertical combustion test in the same manner as in Test 1. The results are shown in Table 3. From the results in Table 3, this sample was evaluated as UL standard V0.
- composition sequence (order) of the composition in this test is also shown in FIG. Shown in the flow diagram.
- the pellets obtained in Step 1 and the La O catalyst as a flame retardant component were kneaded at 185 ° C in a twin-screw kneader (Step 2), and 125mm x 13mm
- X 3.2 mm was press-molded (molding temperature 180 ° C, pressure 120 kgZcm 2 ) (Step 3).
- several test pieces were prepared by changing the mixing ratio of pellets and La O catalyst.
- the mixing ratio of the medium was required to be 86:14 (weight ratio). 14 wt% La O catalyst
- Table 3 shows the results of the UL-94 vertical combustion test conducted for the test pieces included in Table 3.
- silica magnesia catalyst necessary to obtain a flame retardant resin composition that meets UL standard V0 by kneading PS resin pellets and silica magnesia catalyst (MgO: 24.5 wt%) powder. Asked.
- the blending ratio of the pellet and the silica magnesia catalyst has to be 88:12 (weight ratio).
- Table 3 shows the results of the UL-94 vertical combustion test conducted on a test piece containing 12 wt% of silica magnesia catalyst.
- composition sequence of the composition in this test is shown in the flow chart shown in FIG.
- PS resin pellets and CeO catalyst powder as a flame-retardant component were kneaded at 180 ° C using a twin-screw kneader (step 1) and pressed onto a 125 mm x 13 mm x 3.2 mm test piece. Molded (molding temperature 180 ° C, pressure 120kgZcm 2 ) (Step 2).
- a plurality of test pieces were prepared by changing the mixing ratio of the pellet and the Ce 2 O catalyst, and the flame retardancy was evaluated for each.
- the CeO catalyst was used in the form of a powder having a particle size of about 8-70 m. In this case, the powder was not crushed by kneading, and was dispersed in the resin with the initial powder size.
- the blending ratio of the pellet and the CeO catalyst has to be 88:12 (weight ratio).
- Table 3 shows the results of UL 94 vertical combustion test conducted on specimens containing CeO catalyst at a rate of 12 wt%.
- composition sequence (order) of the composition in this test is shown in the flow chart shown in FIG.
- the flame retardant component CeO catalyst was supported on a porous SiO. CeO touch
- the medium was supported at a ratio of 42 parts by weight with respect to 100 parts by weight of the porous body.
- PS Oxidized pellets 9 Owt% and SiO porous material 10wt% carrying CeO catalyst were mixed at 180 ° C in a twin-screw kneader.
- test piece was subjected to UL-94 vertical combustion test in the same manner as in Test 1. The results are shown in Table 3. From the results in Table 3, this sample was evaluated as UL standard V0. [0088] (Test 8)
- polylactic acid (PLA) and polybutylene succinate (PBS) were kneaded to prepare pellets (Step 1).
- the composition sequence (order) of the compositions in this test is also shown in the flow diagram shown in FIG. In this test, 90% by weight of the pellets obtained in Step 1, 5% by weight of the silica-magnesia catalyst, the same flame retardant component used in Test 1, and t-butyltrimethylsyl peroxide as a flame retardant aid (Nippon Oils and Fats).
- test piece was subjected to UL-94 vertical combustion test in the same manner as in Test 1. The results are shown in Table 3. From the results in Table 3, this sample was evaluated as UL standard VO.
- the kenaf stalk was crushed with a non-marmer or the like, and water was added thereto, and the mixture was cut by stirring with a mixer until the fiber length S reached about 100 m.
- the mixture of kenaf and water was spread on a vat, placed in a drying oven (60 ° C), and dried for 48 hours. After drying, Batka also scraped the kenaf to obtain a kenaf fiber to be mixed with polylactic acid.
- Polylactic acid (PLA) pellets and kenaf fibers were put in a biaxial kneader at a ratio of 70:30 (weight ratio) and kneaded to prepare pellets.
- the mixture was kneaded at 500 rpm and 195 ° C. to produce pellets.
- the obtained pellets were put into an injection molding machine, and injection molding was performed using a mold for a television receiver back cover.
- the molding temperature was set to 180 ° C
- the mold temperature was set to 80 ° C to avoid elution of flame retardant components due to rapid cooling.
- After molding cool the mold, take out the molded product at room temperature, I got a television receiver back cover.
- HIPS resin containing 8 wt% of butadiene rubber with respect to 92 wt% of polystyrene (PS) and 12 wt% of silica magnesia catalyst (MgO: 24.5 wt%) were put into a twin-screw kneader, 500 rpm, Kneading was performed at 180 ° C. to produce pellets.
- the obtained pellets were put into an injection molding machine, and injection molding was performed using a mold for a television receiver back cover. At this time, the molding temperature was 180 ° C., and the mold temperature was room temperature. After molding, the mold was cooled, and the molded product was taken out at room temperature to obtain a knock cover for a television receiver.
- polylactic acid (PLA) and polybutylene succinate (PBS) were kneaded to prepare pellets (Step 1).
- MgO powder and SiO powder were mixed at a ratio of 1: 3 (weight ratio) as flame retardant components to the pellets obtained in this way.
- the mixed powder was mixed.
- composition sequence (order) of the composition used in this test is also shown in FIG. This is shown in the flow diagram.
- the pellets obtained in Step 1 MgO activated by heat treatment in advance and SiO similarly heat treated at 185 ° C in a biaxial kneader.
- step 2 The mixture was kneaded (step 2) and press-molded into a 125 mm ⁇ 13 mm ⁇ 3.2 mm test piece (molding temperature 180 ° C., pressure 120 kg / cm 2 ) (step 3).
- step 3 a plurality of test pieces were produced by changing the mixing ratio of the pellet and the mixed powder, and each was evaluated for flame retardancy.
- MgO and SiO were used in the form of powders each having a particle size of about 2-80 / ⁇ ⁇ .
- the ratio was 90: 2.5: 7.5 (weight ratio).
- Test pieces were prepared at this blending ratio and subjected to UL-94 vertical combustion test. The results are shown in Table 3 as the results of this test.
- Polylactic acid (PLA) synthesized from corn was mixed with MgO powder and SiO powder as flame retardant components.
- Step 2 It was press-molded into a test piece of X 13 mm X 3.2 mm (molding temperature 180 ° C, pressure 120 kgZcm 2 ) (Step 2). In this test, the mixing ratio of pellets, MgO powder and SiO powder was changed.
- test pieces were prepared, and each was evaluated for flame retardancy.
- the same MgO powder and Si 2 O powder used in Test 12 were used. This powder is obtained by kneading.
- composition sequence of the composition used is shown in the flow diagram shown in FIG.
- PS resin pellets, pre-heated and activated MgO, and similarly heat-treated SiO were kneaded at 185 ° C in a twin-screw kneader (step 1), 125 mm X 13 mm X 3. 2mm
- the specimen was press-molded (molding temperature 180 ° C, pressure 120 kgZcm 2 ) (Step 2).
- multiple test pieces were prepared by changing the mixing ratio of pellets and MgO and SiO.
- Table 3 shows the evaluation results of the flame retardancy of the test pieces having this mixing ratio as the results of Test 14.
- MgO powder and SiO powder as a flame retardant component were kneaded into HIPS resin pellets.
- composition sequence of the composition used in this test is shown in the flow diagram shown in FIG.
- HIPS resin pellets, pre-heated and activated MgO, and similarly heat-treated SiO were kneaded at 185 ° C in a twin-screw kneader (Step 1), 125mm x 13m
- Step 2 It was press-molded into a test piece of m x 3.2 mm (molding temperature 180 ° C, pressure 120 kgZcm 2 ) (Step 2). In this test, multiple tests were performed by changing the mixing ratio of pellets, MgO, and SiO.
- Table 3 shows the evaluation results.
- composition sequence of the composition used in this test is shown in the flow diagram shown in FIG.
- polylactic acid (PLA) pellets and silica-magnesia catalyst activated by heat treatment as a flame retardant component were kneaded at 185 ° C in a twin-screw kneader (step 1), and 125 mm X It was press-molded into a 13 mm x 3.2 mm test piece (molding temperature 180 ° C, pressure 120 kgZcm 2 ) (Step 2).
- a plurality of test pieces were prepared by changing the mixing ratio of the pellet and the silica magnesia catalyst, and the flame retardancy was evaluated for each of the test pieces.
- the blending sequence of the composition used in this test is shown in the flowchart shown in FIG.
- polylactic acid (PLA) pellets and pre-heated as a flame retardant component were activated.
- Silica-magnesia catalyst was kneaded with a twin-screw kneader at 185 ° C (step 1) and press-molded into 125mm x 13mm x 3.2mm test pieces (molding temperature 180 ° C, pressure 120kgZc m 2 ) (Step 2).
- a plurality of test pieces were prepared by changing the mixing ratio of the pellet and the silica magnesia catalyst, and the flame retardancy was evaluated for each of the test pieces.
- the same silica-magnesia catalyst as used in Test 1 was used. This catalyst was not crushed by kneading and was dispersed in the resin while maintaining the initial powder size. As a result of evaluation, the blending ratio of the PLA non-flammable pellet and the silica-magnesia catalyst which was most difficult to burn was 90: 1 (weight ratio). Test specimens were prepared at this mixing ratio, and the UL-94 vertical combustion test was conducted. The results are shown in Table 3 as the results of Test 17. As a result, the test piece has VO flame retardancy, but the burning time is almost the same as that of the test piece made in Test 2 where the catalyst mixing ratio is the same. This is considered to indicate that the effect of the flame retardant does not change even if MgO is contained in the silica magnesia catalyst in a large amount exceeding a certain ratio.
- PS and polyphenylene ether (PPE) are mixed by 50 wt% each! PSZPPE pellet mixed with silica magnesia catalyst (MgO: 24.5 wt%) powder meets UL standard V0 The mixing ratio of the silica magnesia catalyst necessary for obtaining the flame retardant resin composition was determined.
- silica-magnesia catalyst which is a catalytic cracking catalyst, was exemplified as the flame retardant component.
- the resin composition of the present invention has a low environmental impact in terms of obtaining raw materials or disposal after use. It is obtained by adding flame retardancy to coconut biodegradable rosin and Z or plant-derived rosin, and is characterized by high industrial practicality.
- the present invention has been conventionally performed using a halogen-based flame retardant in many cases, and by realizing the flame retardancy of PS resin using a non-halogen flame retardant imparting component, It is characterized by the fact that it is possible to obtain PS oils with low environmental impact and high industrial value.
- the flame retardant component used in the present invention is a catalyst used in the chemical industry, for example, the waste catalyst used in the catalytic cracking of hydrocarbons is recovered to produce the resin composition of the present invention. Therefore, the present invention has a high industrial value from the viewpoint of waste recycling. Therefore, the resin composition of the present invention is suitable for constituting various articles, and is particularly useful as a material constituting exterior bodies such as electrical appliances.
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Abstract
Description
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EP05805898A EP1816169B1 (en) | 2004-11-19 | 2005-11-11 | Flame-retardant resin composition, process for producing the same, method of molding the same |
JP2006544979A JP5054978B2 (ja) | 2004-11-19 | 2005-11-11 | 難燃性樹脂組成物、その製造方法およびその成形方法 |
CN2005800390552A CN101056948B (zh) | 2004-11-19 | 2005-11-11 | 难燃性树脂组合物及其制造方法以及其成形方法 |
KR1020077011292A KR101317503B1 (ko) | 2004-11-19 | 2005-11-11 | 난연성 수지 조성물, 그 제조 방법 및 그 성형 방법 |
US11/791,174 US20080194739A1 (en) | 2004-11-19 | 2005-11-11 | Flame-Retardant Resin Composition, Process for Producing the Same, Method of Molding the Same |
US13/005,193 US8735486B2 (en) | 2004-11-19 | 2011-01-12 | Flame-retardant resin composition, process for producing the same, method of molding the same |
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US13/005,193 Division US8735486B2 (en) | 2004-11-19 | 2011-01-12 | Flame-retardant resin composition, process for producing the same, method of molding the same |
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- 2005-11-11 KR KR1020077011292A patent/KR101317503B1/ko active IP Right Grant
- 2005-11-11 CN CN2005800390552A patent/CN101056948B/zh not_active Expired - Fee Related
- 2005-11-11 JP JP2006544979A patent/JP5054978B2/ja not_active Expired - Fee Related
- 2005-11-11 EP EP10188452A patent/EP2333016A1/en not_active Withdrawn
- 2005-11-11 CN CN2011100420790A patent/CN102161832B/zh not_active Expired - Fee Related
- 2005-11-11 EP EP05805898A patent/EP1816169B1/en not_active Expired - Fee Related
- 2005-11-11 US US11/791,174 patent/US20080194739A1/en not_active Abandoned
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JP2011006597A (ja) * | 2009-06-26 | 2011-01-13 | Nec Corp | ポリ乳酸系樹脂組成物およびその成形体 |
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Also Published As
Publication number | Publication date |
---|---|
KR20070095875A (ko) | 2007-10-01 |
JP5054978B2 (ja) | 2012-10-24 |
JP2012162724A (ja) | 2012-08-30 |
CN101056948B (zh) | 2011-04-13 |
KR101317503B1 (ko) | 2013-10-15 |
JP5345720B2 (ja) | 2013-11-20 |
EP2333016A1 (en) | 2011-06-15 |
CN101056948A (zh) | 2007-10-17 |
CN102161832A (zh) | 2011-08-24 |
CN102161832B (zh) | 2013-06-26 |
US20080194739A1 (en) | 2008-08-14 |
EP1816169A4 (en) | 2009-09-16 |
EP1816169A1 (en) | 2007-08-08 |
JPWO2006054493A1 (ja) | 2008-05-29 |
US8735486B2 (en) | 2014-05-27 |
EP1816169B1 (en) | 2012-01-11 |
US20110101566A1 (en) | 2011-05-05 |
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