WO2006003900A1 - 樹脂組成物、樹脂組成物の製造方法、樹脂組成物中間体及び成形品 - Google Patents
樹脂組成物、樹脂組成物の製造方法、樹脂組成物中間体及び成形品 Download PDFInfo
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- WO2006003900A1 WO2006003900A1 PCT/JP2005/011852 JP2005011852W WO2006003900A1 WO 2006003900 A1 WO2006003900 A1 WO 2006003900A1 JP 2005011852 W JP2005011852 W JP 2005011852W WO 2006003900 A1 WO2006003900 A1 WO 2006003900A1
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- WIPO (PCT)
- Prior art keywords
- fine particles
- resin composition
- inorganic oxide
- oxide fine
- polycarbonate
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- 0 CC(C)(c1ccc(*)cc1)c(cc1)ccc1O Chemical compound CC(C)(c1ccc(*)cc1)c(cc1)ccc1O 0.000 description 3
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
Definitions
- Resin composition resin composition production method, resin composition intermediate and molded article
- the present invention relates to a resin composition comprising polycarbonate resin as a constituent resin, a method for producing the resin composition, a resin composition intermediate, and a molded article including the resin composition.
- the window glass of an automobile occupies most of the outer shape, and is an important component for driving and appearance.
- the degree of freedom in the shape of window glass has increased and the area of use has also increased.
- the window glass is required to be lightweight and safe.
- recent headlamps have many new shapes, for example, the degree of freedom in shape and the demand for optical performance are increasing.
- Inorganic glass is used for applications such as window glass and headlamps.
- attempts have been made to use glass made of resin instead of inorganic glass.
- resin made of resin has a lower elastic modulus than inorganic glass, so it is difficult to apply it to, for example, a large window glass.
- the fiber filler has a diameter of about 10 m and a length of about 200 m, so that visible light is not transmitted but is reflected and the resinous glass becomes opaque. Therefore, a resin composition reinforced with a filler cannot be applied to automobile window glass as a resin glass.
- glass made of resin has a lower surface hardness than inorganic glass, and for example, is easily scratched by a wiper. From this point of view, it is difficult to apply glass resin to window glass parts.
- an attempt has been made to cure the surface of the resinous glass by applying a coupling treatment to the surface of the resinous composition constituting the resinous resin glass. Even in this case, it is impossible to achieve a surface hardness that can withstand long-term friction, and the problem of scratches should be solved.
- Calp Kogyo's "Composite material manufacturing method and resin molding material containing the composite material discloses a resin obtained by combining montmorillonite and a bull polymer compound. A method of making the composition is disclosed.
- Utica's “Reinforced polyamide resin composition and method for producing the same is a method in which fluorine mica and polyamide monomer are heated and polymerized to form a composite of fluorine mica and polyamide resin.
- a process for producing a reinforced polyamide resin composition is disclosed.
- Toyobo's “Thermoplastic polyester composition, its production method and its molded product discloses a method for producing a polyester resin composition in which clay and polyester resin are combined. Yes.
- the V slippage is formed by forming an inorganic filler such as clay or talc in layers, and intercalating a predetermined resin between the layers of the inorganic filler. Therefore, the obtained cocoon Although the strength characteristics of the fat composition are improved, it cannot be used for, for example, the application of window glass in terms of hygroscopicity, insufficient surface hardness and insufficient transparency.
- the "wax window and method for producing the same discloses that silica fine particles are blended during the synthesis of acrylic resin.
- the resin composition obtained here is not practical because acrylic resin is a base material, and thus heat resistance and impact resistance are insufficient.
- a method is disclosed in which polycarbonate resin is dissolved in a salty methylene solvent and silica fine particles are mixed therewith. In this method, when the silica concentration increases, mixing and dispersion become difficult. For example, transparency, strength, elastic modulus, and impact resistance are not sufficient, and it is difficult to put into practical use.
- Aromatic polycarbonate (hereinafter sometimes abbreviated as “PC”) suitable for use in automobiles that require impact resistance, such as window materials, has improved mechanical strength and dimensional stability.
- PC aromatic polycarbonate
- a method of mixing and dispersing inorganic oxide fine particles such as silica is known.
- the PC-based thermoplastic resin composition containing the fine acid oxide fine particles has problems in terms of transparency, although the mechanical strength and dimensional stability are improved. Even if the primary particle size of the inorganic oxide fine particles is reduced in order to improve transparency, secondary aggregation of the inorganic oxide fine particles occurs in the conventional technology, so the PC-based thermoplastic resin composition The transparency of is greatly reduced.
- Japanese Patent Application Laid-Open No. 2000-327930 describes that it is preferable to use metal oxide particles such as silica and titanium oxide having a particle size of ⁇ 001-0.1 ⁇ m.
- the main skeleton which is the main chain of the coalescence must have carbon atoms in the molecule and have functional groups capable of binding to the surface of the metal oxide particles in the molecule, such as aromatic polycarbonate having an alkoxysilyl group at the molecular end.
- An organic-inorganic hybrid material obtained by mixing the above organic polymer with PC resin is disclosed. This material has been shown to be suitable for high performance, high performance plastic materials with high mechanical properties and water resistance.
- This first organic polymer has good compatibility with the PC resin constituting the matrix, so it plays a role in adapting the metal oxide particles to the PC resin that is the matrix material. .
- the organic polymer forms an insoluble and infusible coarse gel.
- Some of these coarse gels have a size of 400 nm or more, which is the same as the visible light wavelength, and are dispersed in the PC resin matrix, so that even if the coarse gel is dispersed in the PC resin matrix, visible light is visible. Refractive index unevenness of the same size as the wavelength is generated, and the transparency of the PC resin is impaired. Further, this coarse gel generates infusible foreign matters during the thermoplastic molding process of PC resin, which causes poor fluidity of PC resin or poor molding surface gloss and impairs molding processability. Therefore, even if this technology has good transparency and film formability in a thin film state, there are problems with transparency and thermoplastic moldability in a Balta molded product.
- the present invention has been made in view of the above problems, and rigidity is excellent in mechanical strength such as impact resistance, surface hardness, thermal dimensional stability such as linear expansion coefficient, and transparency, and also in transparency.
- the object of the present invention is to provide a resin composition that has excellent melt fluidity and can be suitably used, for example, as an organic glass used in an automobile window glass.
- PC resin having inherently high mechanical strength and thermal dimensional stability is used as the base material of the intended resin composition, and various changes and improvements are added to this. Therefore, we attempted to realize mechanical strength, surface hardness, and thermal dimensional stability that can replace conventional inorganic glass.
- the surface of the inorganic oxide fine particles to be blended in the PC resin is applied to the surface.
- an inorganic oxide fine particle introduced with an epoxy group on the surface and then blended with a monomer used as a raw material for the PC resin by blending inorganic oxide fine particles with an epoxy group on the surface the surface of the inorganic oxide fine particle has an epoxy group. It was found to be covalently bonded to the PC molecule through the layer. Therefore, the inorganic oxide fine particles are stably bonded to the PC resin through a covalent bond.
- thermoplastic rosin composition thus obtained has excellent melt fluidity. This is because the covalent bond formed by the reaction between the epoxy group present on the surface of the inorganic oxide fine particles and the PC molecule is an aliphatic ether-type linking group, and therefore has excellent thermal mobility unique to the ether bond. In other words, it is thought to be derived from flexibility.
- the inorganic oxide fine particles are blended in the raw material monomer constituting the PC resin in advance, for example, instead of directly kneading the PC resin by kneading or the like, and then the ester exchange is performed. It was found that the inorganic oxide fine particles were uniformly dispersed in the Pc resin and dispersed at a high degree of transparency by being dispersed through the melt polymerization process by the method.
- the resin composition according to the first aspect of the present invention includes a thermoplastic resin comprising polycarbonate molecules in which inorganic oxide fine particles are bound by an aliphatic ether type linking group represented by the following general formula (1):
- the greaves composition :
- M is a trivalent or tetravalent metal element capable of binding to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 representing the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of the series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle
- * 1 one, * 2— and * 3— are the surface of the inorganic oxide fine particle.
- * 4— indicates the bond with the polycarbonate molecule. Represent each.
- the molded product according to the second invention is a thermoplastic resin yarn comprising a polycarbonate molecule in which inorganic oxide fine particles are bound by an aliphatic ether type linking group represented by the following general formula (1).
- M is a trivalent or tetravalent metal element capable of binding to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 that represents the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of the series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- at least one of * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle, and at least one of * 1, one, * 2— and * 3— is the surface of the inorganic oxide fine particle.
- * 4— represents the bond to the polycarbonate molecule.
- the method for producing a resin composition according to the third invention comprises an aliphatic ether represented by the following general formula (1) on an inorganic oxide fine particle having an average primary particle diameter of 380 nm or less. Forming a surface layer having an epoxy group by using a connecting group of the mold;
- a method for producing a rosin composition comprising:
- M is a trivalent or tetravalent metal element capable of binding to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 representing the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of the series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle
- * 1 one, * 2— and * 3— are the surface of the inorganic oxide fine particle.
- * 4— represents the bond to the polycarbonate molecule.
- the resin composition intermediate according to the fourth invention has a primary particle diameter of 380 nm or less, and also has an inorganic oxide fine particle force in which a monomer is covalently bonded to an epoxy group of the surface layer.
- FIG. 1 is a diagram showing a production process of a resin composition of the present invention.
- FIG. 2 is a reaction formula when silica fine particles are surface-treated with (3-glycidoxypropyl) trimethoxysilane to introduce epoxy groups on the surface of the silica fine particles.
- FIG. 3 is a reaction formula relating to the production of the resin composition intermediate of the present invention.
- FIG. 4 is a reaction formula relating to the production of the resin composition of the present invention.
- Fig. 1 shows the production process of the coconut resin composition
- Fig. 1 shows the production process of the coconut resin composition
- Fig. 1 shows the production process of the coconut resin composition
- Fig. 1 shows the production process of the coconut resin composition
- the resin composition according to the embodiment of the present invention is a thermoplastic resin comprising a polycarbonate molecule in which inorganic oxide fine particles are bound by an aliphatic ether type linking group represented by the following general formula (1).
- M is a trivalent or tetravalent metal element capable of binding to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 representing the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of this series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- at least one of * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle, and at least one of * 1, one, * 2— and * 3— is the surface of the inorganic oxide fine particle.
- * 4— represents the bond to the polycarbonate molecule.
- the resin composition introduces an aliphatic ether type linking group represented by the general formula (1) on the surface of the silica force.
- Epoxy group-treated silica 31 with an epoxy group introduced is blended with bisphenol A41 as shown in Fig. 1 to add bisphenol A41 to the linking group.
- diphenol carbonate 61 and bisphenol A62 are further added to the silica ZBPA compound 51 produced by the addition reaction, and silica ZPC compound 71 is produced by transesterification.
- silica fine particles 11 and (3-glycidoxypropyl) trimethoxysilane are formed to produce 3-glycidoxypropyldimethylsilanol 21.
- the produced 3-glycidoxypropyldimethylsilanol 21 and silica fine particles 11 are reacted to introduce a linking group onto the surface of the silica fine particles 11 to obtain an epoxy group-treated silica 31.
- the epoxy group-treated silica 31 is blended and melted in bisphenol A41, and the resulting melt is heated at a temperature of 160 to 250 ° C., for example, so that the surface of the epoxy group-treated silica 31 is bisphenol.
- a resin composition intermediate in which A41 is covalently bonded via a linking group, i.e., silica ZBP A Compound 51 is obtained.
- diphenol carbonate 61 and bisphenol A62 are added to the melt in the required amount to form a polymerization reaction solution.
- the polymerization reaction solution is reduced to a pressure of lOOmmHg or less, preferably lOmmHg or less, for example, 200 ° C.
- silica fine particles 11 which are inorganic oxide fine particles are uniformly dispersed in a polycarbonate-polycarbonate resin, rigidity, impact strength and other mechanical strength, surface height, thermal dimensional stability and A resin composition 72 having excellent transparency and usable as practical organic glass such as window glass is obtained.
- the inorganic oxide fine particles used in the present invention are dispersed in a polycarbonate resin matrix in a state of being bonded to polycarbonate molecules by an aliphatic ether type linking group represented by the following general formula (1). is there.
- M is a trivalent or tetravalent metal element capable of binding to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 representing the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of this series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- at least one of * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle, and at least one of * 1, one, * 2— and * 3— is the surface of the inorganic oxide fine particle.
- * 4 Each represents a bond with a polycarbonate molecule.
- Examples of the trivalent or tetravalent metal element (M) that can be bonded to the surface of the inorganic oxide fine particles include, for example, tetravalent metal atoms such as silicon, titanium, zirconium, germanium and tin, aluminum Of the trivalent metal atoms such as sulfur and boron, silicon, titanium, and aluminum are more preferred.
- * 1-, * 2 and * 3 are bonds capable of binding to the surface of the inorganic oxide fine particles, respectively.
- * 1 One, * 2 and * 3 are inorganic oxide fine particles. As long as it is bonded to the surface, it may be bonded.
- the substituent bonded to * 1, 1, * 2 and * 3 includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and n-propyl.
- aryl group having 6 to 10 carbon atoms for example, phenyl group, 4-methylphenol group, 4-ethylphenyl group, 4-isopropylphenol group, 4t— Examples thereof include aryloxy groups having 6 to 10 carbon atoms such as butylphenol group, such as phenoxy group, 4 methylphenoxy group, 4 ethylphenoxy group, 4 isopropylphenoxy group, 4 t-butylphenoxy group, etc.
- a methyl group or a methoxy group in which an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is preferable in terms of the bondability of the linking group of the above formula (1) to the inorganic oxide fine particles.
- a methyl group is preferable in terms of the bondability of the linking group of the above formula (1) to the inorganic oxide fine particles.
- Most preferred is a methyl group.
- the polycarbonate molecules bonded to the surface of the inorganic oxide fine particles in this way are entangled in the polymer chain with the polycarbonate molecules constituting the matrix, or, for example, hydrogen bonds between the carbonate and the carbonate.
- the inorganic oxide fine particles are aggregated with each other and stably dispersed.
- the method for forming the aliphatic ether type linking group represented by the general formula (1) is not limited.
- the surface of the inorganic oxide fine particle has an epoxy group covalently bonded to the polycarbonate resin. This is preferably carried out by a method for forming the surface layer in advance.
- the surface layer is formed of, for example, an alkoxysilane compound having an epoxy group or a glycidyl group, an organic silicon compound such as a chlorosilane compound, an alkoxy titanium having an epoxy group or a glycidyl group, for example, an organic titanium compound such as black titanium.
- Organic compounds such as compounds, alkoxyzirconium having an epoxy group or glycidyl group, for example, zirconium oxide It is formed by surface treatment using a zirconium compound.
- organic key compounds such as compounds, alkoxyzirconium having an epoxy group or glycidyl group, for example, zirconium oxide It is formed by surface treatment using a zirconium compound.
- Examples of the organic titanium compound include 2- (3,4-epoxycyclohexyl) ethyltrimethoxytitan, 5,6-epoxyhexyltriethoxytitanium, (3-glycidoxypropyl) trimethoxytitanium, (3-glycidoxypropyl) methyldimethoxytitanium, (3-glycidoxypropyl) methyljetoxytitanium, (3-glycidoxypropyl) dimethylethoxytitanium, and the like can be listed.
- Examples of the organic zirconium compound include 2- (3,4-epoxycyclohexyl) ethyltrimethylzirconium, 5,6-epoxyhexylenotriethoxydinoleconium, (3-glycidoxypropyl) trimethoxyzirconium, Examples thereof include 3- (3-glycidoxypropyl) methinoresin methoxydinoleco dimethyl, (3-glycidoxypropinole) methinolegetoxy dinoleconium, (3-glycidoxypropyl) dimethylethoxyzirconium and the like. .
- organic key compound organic titanium compound, and organic zirconium compound
- surface treatment using the organic key compound is preferred.
- Silica fine particles are surface-treated with (3 glycidoxypropyl) dimethylethoxysilane to form a surface layer having an epoxy group in the silica fine particles, that is, when an epoxy group is added to the surface of the silica fine particles.
- the reaction formula is shown in FIG. In this example, silica fine particles 11 and (3 glycidoxypropyl) trimethoxysilane 12 are melted in water 13 and (3 glycidoxypropyl) trimethoxysilane 12 and water 13 are reacted to form 3 glycidoxypropyldimethylsilanol. 21 produces.
- the surface modification rate of the inorganic oxide fine particles by the epoxy group is preferably 5 to 50%. That's right. If the surface modification rate is less than 5%, the ratio of the covalent bond between the inorganic oxide fine particles and the polycarbonate resin is reduced, and the finally obtained resin composition becomes brittle. The bending strength characteristics may be insufficient. On the other hand, if the surface modification rate exceeds 50%, the finally obtained resin composition tends to cause gelling and may be difficult to process.
- the surface modification rate can be controlled by changing the treatment time with the surface treatment agent.
- the surface modification rate can be determined by quantifying the unreacted hydroxyl group on the surface of the inorganic oxide fine particles by the infrared absorption spectrum.
- the average primary particle size of the inorganic oxide fine particles needs to be 380 nm or less, which is the minimum wavelength in the visible light region that ensures the transparency of the intended resin composition, and preferably 5 nm to 200 nm, more preferably 5 nm to: LOOnm.
- the kind of inorganic oxide fine particles is not particularly limited, but preferably silica, alumina, titer, zirconia or complex oxides thereof can be used.
- silica or alumina in view of easy availability, cost, and ease of surface treatment, it is preferable to use silica or alumina, and it is particularly preferable to use silica.
- Silicon oxides typified by silica are preferably used as the material of the inorganic oxide fine particles in the present invention.
- Oxidized silicons have silicon atoms and oxygen atoms as the main chemical structure.
- the most preferred chemical composition of silicon oxides is the silica composition (SiO 2). Shi
- Nonmetallic elements such as boron, carbon, nitrogen, fluorine, phosphorus, sulfur, chlorine, etc.
- alkali metal elements such as sodium and potassium
- alkali metal elements such as magnesium and calcium
- metal elements such as aluminum, titanium, zirconium, yttrium, lanthanum, cerium, europium, terbium, and zinc.
- a metal element When a metal element is contained, its content is usually as small as possible from the viewpoint of chemical stability or colorlessness, and is usually 0 to 30% by weight as the weight of the element in the composition of silicon oxides.
- the upper limit is preferably 20% by weight, more preferably 10% by weight.
- the chemical composition of silicon oxides is determined by composition analysis of the residue obtained by burning a thermoplastic resin composition containing silicon oxides in air at 650 ° C. for 2 hours.
- Water glass can be used at low cost as a raw material for silicon oxides.
- Use water glass In some cases, for example, an alkali metal such as sodium remains, which may impair the chemical stability of the thermoplastic resin composition. Therefore, it is preferable that the silicon oxides have a silica composition with as high a purity as possible.
- a hydrolytic condensation reaction using alkoxysilanes and Z or oligomers thereof as raw materials a so-called sol-gel method. It is preferable to produce silicon oxides.
- alkoxysilanes examples include tetramethoxysilane, tetraethoxysilane tetraalkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3 —Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-ataryloxypropyltrimethoxysilane, 3— Examples include trialkoxysilanes such as talyloyloxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, such as dimethyldimethoxysilane, dialkoxysilanes of dimethyljetoxysi
- the silica is preferably composed of colloidal silica from the viewpoint that the size and shape can be easily controlled.
- the inorganic oxide fine particles preferably have a spherical, dumbbell or chain shape.
- the blending effect of the inorganic oxide fine particles as filler in the resin composition is increased, and apart from the effect of the covalent bond between the inorganic oxide fine particles and the polycarbonate resin, the inorganic oxide fine particles are separated.
- the mechanical strength of the resin composition can be increased by blending the fine particles.
- Polycarbonate resin is a polymer produced by the reaction of one or more diols with carbonates such as bisalkyl carbonate, bisaryl carbonate, phosgene and the like.
- the polycarbonate resin may be used alone or in combination of plural kinds.
- aromatics because of excellent heat resistance, that is, mechanical strength with a high glass transition temperature, and particularly high impact resistance.
- polycarbonate resin it is preferable to use polycarbonate resin.
- Bisphenols are preferably used as the aromatic polycarbonate. In this case, trivalent or higher polyhydric phenols may be contained as a copolymer component. Further, if necessary, aliphatic diols may be copolymerized.
- the aromatic polycarbonate resin in the present invention uses, for example, (a) an alkali metal salt of bisphenolanol and a carbonate ester derivative active in nucleophilic attack such as phosgene as a raw material, and dissolves the produced polymer.
- Interfacial polymerization method in which polycondensation reaction is performed at the interface between an organic solvent and alkaline water, (b) Bisphenols and carbonate derivatives that are active in nucleophilic attack such as phosgene as raw materials, and organic materials such as pyridine Pyridine method in which a polycondensation reaction is carried out in a base, (c) Bisphenols and carbonate esters such as bisalkyl carbonate and bisaryl carbonate, preferably diphenol carbonate, are used as raw materials, It may be produced by a conventionally known method such as a melt polymerization method in which condensation is performed!
- the inorganic oxide fine particles and / or the raw materials thereof can be used at any stage of the method for producing these aromatic polycarbonate resins, such as a raw material liquid preparation stage, a polymerization stage, and an extruder. It may be added at the pelletizing stage or the like.
- the degree of polymerization of the polycarbonate resin used in the composition of the present invention is measured by GPC (gel permeation chromatography) using 40 ° C black mouth form as a developing solvent.
- the polystyrene equivalent weight average molecular weight is preferably 800 to 70000. If the molecular weight is less than 800, the finally obtained resin composition becomes brittle and various properties such as izotto impact and bending strength may be insufficient. On the other hand, if the molecular weight exceeds 7000, the melt viscosity becomes too high and processing becomes difficult.
- the molecular weight can be controlled by changing the polymerization time in the polymerization reaction in the production method described in detail below. The molecular weight of such a polycarbonate resin is measured by separating the insoluble components when the given resin composition is dissolved in black mouth form with a membrane filter etc. To be performed.
- the resin composition of the present invention is obtained by dispersing inorganic oxide fine particles in a polycarbonate resin matrix bound by an aliphatic ether type linking group represented by the following general formula (1): It is.
- M is a trivalent or tetravalent metal element that can be bonded to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 that represents the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of this series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- at least one of * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle, and at least one of * 1, one, * 2— and * 3— is the surface of the inorganic oxide fine particle.
- * 4— represents the bond to the polycarbonate molecule.
- the integer n in the general formula (1) is preferably 6 and more preferably 4, most preferably, so as not to extremely reduce the heat distortion temperature of the resin composition of the present invention.
- the value of the integer n is 3.
- the number of carbon atoms in the series chain formed by connecting the carbon atoms contained in R 1 to each other is preferably 6 for the same reason, more preferably 4, and the most preferable value of the integer n Is 3. If these two values are smaller than the above ranges, thermal decomposition may be deteriorated and mechanical strength or melt fluidity may be reduced.
- the means for forming the aliphatic ether type linking group represented by the general formula (1) is not limited, but it is preferable to utilize the reactivity of the epoxy group. That is, a surface layer having an epoxy group is provided on the surface of the inorganic oxide fine particles, and this epoxy group is reacted with polycarbonate resin or its raw material. More specifically, this is considered to be a reaction in which the terminal hydroxyl group of the polycarbonate resin or the hydroxyl group power epoxy group of the diol as a raw material thereof undergoes nucleophilic attack to open the ring.
- the linking group of the general formula (1) formed by this reaction is represented by the following formula (2) or (3). [Chemical 7]-(CH 2 ) n -0-CH 2 -CH-0-R pc (2)
- a characteristic of the resin composition of the present invention is that it is inorganic oxide fine particles in which the chloroform form-insoluble component power polycarbonate molecules of the resin composition described above are bonded via a linking group. .
- This can be confirmed by the following analysis. In other words, in order to completely remove the organic components such as free polycarbonate remaining in the black mouth form insoluble component, the removal of the supernatant liquid by, for example, black mouth form washing using a Soxhlet extractor or centrifugation is repeated.
- polycarbonate molecules bonded to the surface of inorganic oxide fine particles through a linking group (hereinafter referred to as “surface-fixed polycarbonate molecules”).
- the heat loss derived from (sometimes noted) is observed.
- the above-mentioned heat loss components are bonded via the linking groups. It turns out to be a molecule.
- the amount of the surface-fixed polycarbonate molecule is usually 1 to 70% by weight of the solid form insoluble component after purification, that is, the solid residue.
- the lower limit is preferably 5% by weight, more preferably 10% by weight in terms of the dispersibility of the core, while the upper limit is preferably 60% by weight because the melt viscosity of the resin composition is not significantly increased. %, More preferably 50% by weight.
- the amount of such surface-fixed polycarbonate molecules can be controlled, for example, by the amount of the surface layer having an epoxy group bonded in advance to the surface of the inorganic oxide fine particles.
- the inorganic oxide fine particles have excessive epoxy groups, they generate excessively surface-fixed polycarbonate molecules, and some of them may crosslink the inorganic oxide fine particles and inorganic oxide fine particles. is there. In that case, there exists a possibility that a coarse gel component may produce
- the resin composition of the present invention has a linear expansion coefficient of 30 to 60 ppm ZK when heated from 30 ° C to 80 ° C due to the effect of containing a predetermined amount of inorganic oxide fine particles. . Since it is preferable that the value of the present invention is as small as possible, the upper limit is preferably 50 ppm Z: and the lower limit is preferably 35 ppmZ: more preferably 40 ppmZK in terms of transparency.
- the linear expansion coefficient of ordinary aromatic polycarbonate resin is about 70ppmZK.
- the linear expansion coefficient was measured by thermomechanical analysis (TMA) with a given aromatic polycarbonate resin composition molded into a cylindrical shape with a bottom diameter of 5 mm and a height of 10 mm, and a heating rate of 5 ° CZ. ) Or by dilatometer measurement.
- TMA thermomechanical analysis
- the content of the inorganic oxide fine particles in the resin composition is preferably set to be in the range of 5 wt% to 70 wt%. If the content is less than 5% by weight, it is difficult to improve various properties such as mechanical strength. If the content exceeds 70% by weight, if the increase in specific gravity cannot be ignored, it is disadvantageous not only in terms of force but also in terms of cost, and a decrease in impact strength cannot be ignored.
- the content is preferably at least 10% by weight, more preferably at least 15% by weight, while the upper limit is preferably 60% by weight or less, more preferably 50% by weight or less.
- the content of the inorganic oxide fine particles in the composition of the present invention is measured by thermal loss by thermogravimetric analysis in air, and the measurement is performed on a commercially available thermogravimetric analyzer (TG-DTA). Increase the temperature from room temperature to 600 ° C in 60 minutes, and continue! Hold at 600 ° C for 60 minutes.
- TG-DTA thermogravimetric analyzer
- the resin composition of the present invention comprises an epoxy group using an aliphatic ether type linking group represented by the following general formula (1) on an inorganic oxide fine particle having an average primary particle diameter of 380 nm or less.
- Forming a surface layer comprising: a step of mixing inorganic oxide fine particles formed with a surface layer having an epoxy group with a polycarbonate molecule raw material to obtain a mixture; and the mixture at 150 to 350 ° C. Heating in a temperature range;
- M is a trivalent or tetravalent metal element capable of binding to the surface of the inorganic oxide fine particles
- m is 0 or 1
- n is an integer of 2 to 8 representing the number of chains of a methylene group
- R 1 contains a series chain in which 2 to 8 carbon atoms are connected to each other, and an aliphatic group in which both ends of the series chain are bonded to two adjacent oxygen atoms is represented as * 1 one, * 2—
- at least one of * 3— is a binding species capable of binding to the surface of the inorganic oxide fine particle, and at least one of * 1, one, * 2— and * 3— is the surface of the inorganic oxide fine particle.
- * 4— represents the bond to the polycarbonate molecule.
- inorganic oxide fine particles on which a surface layer having an epoxy group is formed as described above are mixed with a monomer that is a raw material of polycarbonate molecules to obtain a mixture, and the mixture is heated. Thus, it is preferably produced by polymerization.
- the polymerization in this case is S Melt polymerization by the tellurium exchange method.
- the desired resin composition in which the inorganic oxide fine particles are covalently bonded to the polycarbonate molecules through the surface layer and dispersed in the polycarbonate resin can be obtained.
- the inorganic oxide fine particles may be added during the polymerization reaction or in the melt-kneading stage during the pelletization.
- a transesterification method is used in the synthesis of polycarbonate resin.
- a predetermined dicarbonate compound and a diol compound are used as monomers.
- the dicarbonate compound is selected from dialkyl carbonates, dicycloalkyl carbonates, and diaryl carbonates. Of these, diaryl carbonates are preferred.
- V is diphenyl carbonate.
- the diol compound used in the present invention is a bisphenol-based fragrance because of the physical properties of the composition and the availability of the composition.
- bisphenol-based aromatic diol examples include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (commonly known as bis) Phenol Z), 2,2-bis (4-hydroxy-3,5-dichlorophenol) puffer, 2,2-bis (4-hydroxy-3-cyclopentaphenol) propane, 2,2-bis ( Examples include 4-hydroxy-3-methylphenol) propane, bis (4-hydroxyphenyl) diphenylmethane, and 4,4,2-dihydroxybiphenyl. These can be used in combination of two or more. Particularly preferred is bisphenol A.
- a monomer is covalently bonded to the surface of the inorganic oxide fine particles to form a resin composition intermediate.
- the condensation polymerization reaction proceeds with the inorganic oxide fine particles as nuclei, the uniform dispersibility of the inorganic oxide fine particles in the finally obtained resin composition is improved, and the inorganic oxide fine particles described above are also obtained.
- a stronger covalent bond is formed between the polycarbonate resin and the polycarbonate resin through the surface layer. Therefore, various properties such as the mechanical strength Can be further improved.
- any of the above-mentioned dicarbonate compounds and diol compounds may be used.
- a diol compound is preferable. Since bisphenol A is preferred as the diol compound, it is preferable to form a resin composition intermediate by covalently bonding bisphenol A to the surface of the inorganic oxide fine particles.
- FIG. 1 epoxy group-treated silica 31 having a surface layer having an epoxy group shown in FIG. 3 is blended in bisphenol A41 and melted, and the resulting melt is heated at a temperature of 160 to 250 ° C., for example.
- a resin composition intermediate in which bisphenol A is covalently bonded to the surface of the epoxy group-treated silica 31 through a linking group by an addition reaction that is, a silica ZBPA compound 51 is obtained.
- diphenol carbonate 61 and bisphenol A62 are added as necessary as dicarbonate compounds to form a polymerization reaction solution.
- the polymerization reaction solution is less than lOOmmHg, preferably less than lOmmHg.
- a polycondensation reaction is carried out by a transesterification method to produce a polycarbonate to obtain a resin composition 72.
- an alkali metal catalyst may be added to the polymerization reaction solution in order to promote the condensation polymerization reaction.
- the catalyst may be selected as appropriate, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide hydroxide, rubidium hydroxide, hydroxide hydroxide, etc., such as magnesium hydroxide, Alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, barium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, carbonic acid Examples include alkaline earth metal carbonates such as magnesium, calcium carbonate, strontium carbonate, and barium carbonate.
- lithium hydroxide sodium hydroxide, potassium hydroxide, rubidium hydroxide, and lithium hydroxide.
- Alkali metal hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidi carbonate Beam, of an alkali metal such as cesium carbonate Carbonates are preferred.
- the resin composition obtained through the above-described process maintains the hot moldability equivalent to that of a single resin, and has undergone a molding process such as melt extrusion, injection molding, blow molding, etc. It can be processed into molded products of various sizes.
- the resin composition achieves improved rigidity without sacrificing transparency and impact strength, and also has the characteristics of being able to suppress warpage at high temperatures with a low coefficient of thermal expansion, It is suitable for members that require these functions.
- This resin composition is used for, for example, a transparent cover of an instrument panel as an automobile interior material, a window glass, a headlamp, a sunroof and a combination lamp cover for an automobile exterior material, and further used in household appliances and houses. It can be said that it is a material suitable for the furniture 'components'.
- thermomechanical measurement device (TMO120C manufactured by Seiko Ichi Kogyo)
- Aerosil silica (AERO SI L: made by Nippon Aerosil Co., Ltd., average primary particle diameter of about 20 nm) is used as the silica fine particle, and the silica fine particle is surface-treated with (3-glycidoxypropyl) dimethylethoxysilane to form a silica fine particle surface An epoxy group addition reaction was carried out. The surface modification rate of silica fine particles was 25%.
- Spherical colloidal silica (Snowtex ST: manufactured by Nissan Chemical Co., Ltd., average primary particle size of about 20 nm) is used as the silica fine particles, and the silica fine particles are surface-treated with (3-glycidoxypropyl) dimethylethoxysilane to form silica fine particles on the surface.
- An epoxy group addition reaction was carried out.
- the surface modification rate of the silica fine particles was 50%.
- a polymerization reaction by an ester exchange method was carried out in the same manner as in Example 1 to produce a resin composition.
- the blending amount of silica fine particles with respect to the resin composition was 20% by weight.
- the surface treatment of the silica fine particles was performed in the same manner as in Example 2, and further the polymerization reaction by the ester exchange method To obtain a rosin composition.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance to the molded product, the dispersion state with a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient,
- various tests such as Izod test were conducted. The results are shown in Table 2.
- the silica fine particles were subjected to a surface treatment, and a polymerization reaction was carried out by a transesterification method to obtain a resin composition.
- the surface modification rate of silica fine particles is 25%
- the reaction time of the polymerization reaction was adjusted so that the molecular weight of the polycarbonate resin constituting the resin composition was 10,000.
- the silica fine particles were subjected to a surface treatment, and a polymerization reaction was carried out by a transesterification method to obtain a resin composition.
- the reaction time of the polymerization reaction was adjusted so that the surface modification rate of the silica fine particles was 25% and the molecular weight of the polycarbonate resin constituting the resin composition was 5000.
- the silica fine particles were subjected to a surface treatment, and a polymerization reaction was carried out by a transesterification method to obtain a resin composition.
- the reaction time of the polymerization reaction was adjusted so that the surface modification rate of the silica fine particles was 25% and the molecular weight of the polycarbonate resin constituting the resin composition was 20000.
- the silica fine particles were surface-treated in the same manner as in Example 2 except that the average primary particle diameter of the silica fine particles was 50 nm, and the surface modification rate of the silica fine particles was 25%, and the polymerization reaction was further performed by an ester exchange method. It was carried out to obtain a rosin composition.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance to the molded product, the dispersion state with a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient, Various tests such as Izod test were conducted. The results are shown in Table 2. [Example 8]
- the silica fine particles were subjected to a surface treatment in the same manner as in Example 2 except that the surface modification rate of the silica fine particles was changed to 5%, and further a polymerization reaction was carried out by a transesterification method to obtain a resin composition.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance of the molded product, the dispersion state with a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient. And various tests of Izod test were conducted. The results are shown in Table 2.
- silica fine particles chain colloidal silica (Snowtex ST-UP: manufactured by Nissan Chemical Co., Ltd.) V is used, and the silica fine particles are surface treated with (3-glycidoxypropyl) dimethylethoxysilane. An addition reaction was performed. The surface modification rate of silica fine particles was 25%. Next, a polymerization reaction by a transesterification method was carried out in the same manner as in Example 1 to produce a resin composition. The blending amount of silica fine particles with respect to the resin composition was 20% by weight.
- dumbbell-shaped colloidal silica (Snowtex PS: manufactured by Nissan Chemical Co., Ltd.) as silica fine particles
- the silica fine particles are surface-treated with (3-glycidoxypropyl) dimethylethoxysilane, and epoxy group addition reaction is performed on the surface of silica fine particles. went.
- the surface modification rate of silica fine particles was 25%.
- a polymerization reaction by a transesterification method was carried out in the same manner as in Example 1 to produce a resin composition.
- the blending amount of silica fine particles with respect to the resin composition was 20% by weight.
- Spherical colloidal silica (Snowtex ST: Nissan Chemical, average primary as silica fine particles A particle size of about 20 nm) was used, and a resin reaction was carried out by the same transesterification method as in Example 1 without surface treatment to obtain a resin composition.
- the blending amount of silica fine particles with respect to the resin composition was 20% by weight.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance, the dispersion state with a transmission electron microscope, the bending strength, the bending elastic modulus, and the linear expansion of the molded product were formed.
- Various tests of coefficient and Izod test were conducted. The results are shown in Table 3.
- a linear colloidal silica (Snowtex ST-UP: manufactured by Nissan Chemical Industries) is used as the silica fine particles, and the polymerization reaction is carried out by the same transesterification method as in Example 1 without surface treatment, to obtain a resin composition. It was. The blending amount of silica fine particles with respect to the resin composition was 20% by weight. Next, a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance of the molded product, the dispersion state with a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient, And various tests of Izod test were carried out. The results are shown in Table 3.
- dumbbell-shaped colloidal silica (Snowtex PS: manufactured by Nissan Chemical Co., Ltd.) as the silica fine particles
- a polymerization reaction was carried out by the same transesterification method as in Example 1 without any surface treatment, to obtain a resin composition.
- the blending amount of silica fine particles with respect to the resin composition was 20% by weight.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance of the molded product, the dispersion state with a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient, And various tests of Izod test were carried out. The results are shown in Table 3.
- Spherical colloidal silica (Snowtex ST: Nissan Chemical, average primary particle size of about 20nm) is used as silica fine particles, and 30g of silica fine particles is made of polycarbonate carbonate (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics) without surface treatment.
- a resin composition was obtained by melt-mixing with 120 g and small size.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance, the dispersion state with a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient, and the Izod for the molded product were formed. Various tests were conducted. The results are shown in Table 3.
- dumbbell colloidal silica (Snowtex PS: manufactured by Nissan Chemical Co., Ltd.) as the silica fine particles
- 30g of the silica fine particles can be converted into 120g of polycarbonate resin (Iupilon S2000 Mitsubishi Mitsubishi Plastics) without surface treatment.
- the resin composition was obtained by melt mixing.
- a sheet-like molded product was formed from the greave composition in the same manner as in Example 1, and the total light transmittance for the molded product, the state of dispersion in a transmission electron microscope, the bending strength, the flexural modulus, the linear expansion coefficient, and Various tests of Izod test were conducted. The results are shown in Table 3.
- the resin composition of the present invention according to the examples is more transparent than the polycarbonate resin (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics) shown as a reference value. It can be seen that the bending strength and flexural modulus are improved and the linear expansion coefficient is lowered while maintaining the properties.
- the resin composition according to the comparative example has insufficient increase in bending strength and flexural modulus and insufficient decrease in the linear expansion coefficient compared with the resin composition according to the example. I understand that. In particular, as shown in Comparative Examples 4 to 6, when silica fine particles are blended with polycarbonate resin by a single method, the decrease in linear expansion coefficient is further insufficient because the bending strength is further reduced. Can be divided.
- melt extrusion was performed at 280 ° C using a microkneader manufactured by Imoto Seisakusho Co., Ltd., and a cloudy strand was obtained.
- the surface was not smooth and was rough. This proved that a large amount of the coarse gel component was contained.
- the polycarbonate resin composition of the present invention includes, as necessary, an acid proofing agent containing, for example, hindered phenol, hydroquinone, thioether, phosphites, and their substitution products and combinations thereof.
- Heat stabilizers such as UV absorbers such as resorcinol, salicylate, benzotriazolene, benzophenone, lubricants such as silicone resin, montanic acid and salts thereof, stearic acid and salts thereof, release agents such as stearyl alcohol and stearylamide Agents, for example, dyes such as -trocin, colorants including facials such as cadmium sulfate and phthalocyanine, additive additives such as silicone oil, and crystal nucleating agents such as talc and kaolin alone Or it can add combining suitably.
- the resin composition of the present invention achieves improved rigidity without sacrificing transparency and impact strength, and also has the characteristics of being able to suppress warpage at high temperatures with low thermal expansion coefficient. Therefore, it is suitable for members that require these functions.For example, it is suitable for automobile interior materials such as transparent covers on instrument panels, and for automotive exterior materials such as windows, headlamps, sunroofs, and combination lamp covers. Can be used for transparent material 'equipment' furniture used in home appliances and houses.
Description
Claims
Priority Applications (2)
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EP05755774.6A EP1767562B8 (en) | 2004-07-02 | 2005-06-28 | Resin composition, process for producing resin composition, intermediate for resin composition, and molded article |
US11/631,313 US20080015329A1 (en) | 2004-07-02 | 2005-06-28 | Resin Composition, Method for Producing the Same, and Intermediate and Molded Article of the Same |
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JP2004196973A JP2006016538A (ja) | 2004-07-02 | 2004-07-02 | 樹脂組成物、樹脂組成物の製造方法及び樹脂組成物中間体 |
JP2004-196973 | 2004-07-02 |
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PCT/JP2005/011852 WO2006003900A1 (ja) | 2004-07-02 | 2005-06-28 | 樹脂組成物、樹脂組成物の製造方法、樹脂組成物中間体及び成形品 |
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US (1) | US20080015329A1 (ja) |
EP (1) | EP1767562B8 (ja) |
JP (1) | JP2006016538A (ja) |
WO (1) | WO2006003900A1 (ja) |
Cited By (1)
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US8834364B2 (en) | 2006-11-01 | 2014-09-16 | Resmed Sensor Technologies Limited | System and method for monitoring cardiorespiratory parameters |
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FR2925059B1 (fr) * | 2007-12-13 | 2012-08-17 | Armines | Procede de preparation d'un materiau polymere transparent comprenant un polycarbonate thermoplastique et des nanoparticules minerales modifiees en surface. |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0661311A2 (en) * | 1993-11-09 | 1995-07-05 | Nippon Shokubai Co., Ltd. | Compound fine particles and compositions for forming film |
EP0918061A2 (en) * | 1997-11-21 | 1999-05-26 | Orient Chemical Industries, Ltd. | Organic-inorganic hybrid polymer material and process for preparing the same |
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US4482656A (en) * | 1983-09-29 | 1984-11-13 | Battelle Development Corporation | Method for manufacturing a composition for coating substrates with an abrasion-resistant transparent and translucent film |
US6599631B2 (en) * | 2001-01-26 | 2003-07-29 | Nanogram Corporation | Polymer-inorganic particle composites |
JP4214203B2 (ja) * | 1999-05-18 | 2009-01-28 | オリヱント化学工業株式会社 | 有機−無機複合材料およびその製造方法 |
JP4186002B2 (ja) * | 2001-10-31 | 2008-11-26 | 学校法人日本大学 | 樹脂組成物およびそれを用いた熱可塑性樹脂積層体とそれらの製造方法 |
JP2003201114A (ja) * | 2001-10-31 | 2003-07-15 | Univ Nihon | 改質シリカ組成物、透明樹脂組成物、およびこれらを用いた熱可塑性樹脂積層体、自動車用部品、それらの製造方法 |
JP4135881B2 (ja) * | 2002-03-29 | 2008-08-20 | 日産自動車株式会社 | 樹脂組成物およびこれを用いた成形体と部品 |
-
2004
- 2004-07-02 JP JP2004196973A patent/JP2006016538A/ja not_active Withdrawn
-
2005
- 2005-06-28 EP EP05755774.6A patent/EP1767562B8/en not_active Expired - Fee Related
- 2005-06-28 US US11/631,313 patent/US20080015329A1/en not_active Abandoned
- 2005-06-28 WO PCT/JP2005/011852 patent/WO2006003900A1/ja active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0661311A2 (en) * | 1993-11-09 | 1995-07-05 | Nippon Shokubai Co., Ltd. | Compound fine particles and compositions for forming film |
EP0918061A2 (en) * | 1997-11-21 | 1999-05-26 | Orient Chemical Industries, Ltd. | Organic-inorganic hybrid polymer material and process for preparing the same |
Non-Patent Citations (1)
Title |
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See also references of EP1767562A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US8834364B2 (en) | 2006-11-01 | 2014-09-16 | Resmed Sensor Technologies Limited | System and method for monitoring cardiorespiratory parameters |
US10893811B2 (en) | 2006-11-01 | 2021-01-19 | Resmed Sensor Technologies Limited | System and method for monitoring cardiorespiratory parameters |
Also Published As
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US20080015329A1 (en) | 2008-01-17 |
EP1767562A1 (en) | 2007-03-28 |
EP1767562B8 (en) | 2013-05-22 |
EP1767562B1 (en) | 2013-03-13 |
EP1767562A4 (en) | 2009-12-09 |
JP2006016538A (ja) | 2006-01-19 |
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