KR20150085936A - Glass fiber-reinforce flame retardant polyamide compound - Google Patents
Glass fiber-reinforce flame retardant polyamide compound Download PDFInfo
- Publication number
- KR20150085936A KR20150085936A KR1020140005938A KR20140005938A KR20150085936A KR 20150085936 A KR20150085936 A KR 20150085936A KR 1020140005938 A KR1020140005938 A KR 1020140005938A KR 20140005938 A KR20140005938 A KR 20140005938A KR 20150085936 A KR20150085936 A KR 20150085936A
- Authority
- KR
- South Korea
- Prior art keywords
- polyamide
- copolyamide
- parts
- weight
- flame retardant
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
The present invention relates to glass fiber reinforced flame retardant polyamide compounds containing glass fibers, polyamide oligomers and flame retardants in appropriate proportions.
In order to overcome this problem, the flame retardant is included in the composition. In the case of polyamide, the choice of the flame retardant and the composition ratio of the flame retardant are determined by the compatibility problem between the flame retardant and the polymer resin in the case where the polymer resin is generally excellent in workability and relatively weak in heat. And the physical properties of the polyamide resin are influenced by the blending ratio of the flame retardant agent. That is, the physical properties of the polyamide resin are lowered as the blending ratio of the flame retardant agent is increased to improve the flame retardancy.
In addition, in the case of the polyamide containing the above-mentioned flame retardant, there is a limit to the physical properties of the resin itself for use in automobiles and mechanical parts, that is, a separate mechanical property improvement work is required to improve the mechanical strength. The inclusion of materials has problems in releasability and processability.
Therefore, there is a demand for a high-strength polyamide resin having flame retardancy, excellent mechanical strength, and satisfying three physical properties with high releasability and workability at the same time.
SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide compound having improved flame retardancy, processability, and mechanical properties by incorporating a polyamide oligomer, a triazine flame retardant, and glass fiber into a polyamide resin at an appropriate blending ratio.
According to one embodiment of the present invention, a glass fiber-reinforced flame-retardant polyamide compound comprises 1 to 20 parts by weight of a triazine flame retardant, 0.001 to 10 parts by weight of a polyamide oligomer, And 5 to 50 parts by weight of glass fiber.
Preferably, the polyamide resin or polyamide oligomer is selected from the group consisting of polyamide-6, polyamide-11, polyamide-12, polyamide-4,6, polyamide-4,8, polyamide- Amide-4,12, polyamide-6,6, polyamide-6,9, polyamide-6,10, polyamide-6,12, polyamide-10,10, polyamide- Polyamide-6, T / 6-copolyamide, polyamide-6, T / Polyamide-6,6 / 6, T / 6, I-copolyamide, polyamide-6, T / 2-MPMDT-copolyamide, polyamide-9, Polyamide-6/11-copolyamide, polyamide-6,6 / 11-copolyamide, polyamide-6,6 / 12-copolyamide, polyamide-6 / Polyamide-6,6 / 6,10-copolyamide, polyamide-4,6 / 6-copolyamide, polyamide-6 / 6,6 / 6,10-terpolyamideJean lure can be selected by one or more of the group.
Preferably, the triazine flame retardant may be melamine or cyanuric acid or a mixture thereof.
Preferably, the melamine is at least one selected from the group consisting of melamine, melamine phosphate, dimelamine pyrophosphate, ammercid, anomer, guanyl melamine, cyanomelamine and arylguanamine, The acids are composed of cyanuric acid, isocyanuric acid, methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, methyl isocyanurate, diethyl isocyanurate, tricyanurate and triisocyanurate. One or more of the groups may be selected.
Preferably, the glass fiber is a continuous filament forming a short fiber or nonwoven fabric having a length of 5 to 250 mm.
The flame retardancy of the polyamide resin can be remarkably increased by incorporating a triazine flame retardant into the polyamide resin in an appropriate ratio.
Further, since the glass fiber is included in the polyamide compound as the reinforcing material, the mechanical strength can be remarkably improved.
Further, the polyamide resin containing the flame retardant and the reinforcement can be improved in fluidity and releasability by using a polyamide oligomer having a high compatibility with the polyamide resin and a relatively low molecular weight oligomer by compounding the polyamide oligomer, It is possible to improve processability and process efficiency in actual product manufacture.
According to the present invention, it is possible to simultaneously improve the three required physical properties of flame retardance, releasability and mechanical strength by providing an optimum blending ratio of the polyamide oligomer, the flame retardant and the glass fiber, and accordingly the excellent thermal properties, And various applications such as automobiles, electric appliances, and mechanical parts requiring complex structures and shapes at the same time.
Hereinafter, preferred embodiments of the present invention will be described in detail.
The present invention relates to a glass fiber reinforced flame retardant polyamide compound which comprises 1 to 20 parts by weight of a triazine flame retardant, 0.01 to 10 parts by weight of a polyamide oligomer and 5 to 50 parts by weight of glass fibers, based on 100 parts by weight of a polyamide resin .
The polyamide used in the present invention is a polycondensation product of cyclic lactam ring-opening polymer, aminocarboxylic acid condensate polymer, dibasic acid and diamine, and is a melt-processable, crystalline, semi-crystalline and amorphous polyamide- All polyamides known to those skilled in the art.
The polymerization degree of the polyamide of the present invention is not particularly limited, but is a high molecular weight polyamide having a weight average molecular weight of 10,000 g / mol or more, preferably 15,000 g / mol or more, more preferably 20,000 g / mol or more, The method is not particularly limited, and melt polymerization, interfacial polymerization, solution medium pressure, solid medium pressure and a combination of these methods can be used, and melt polymerization is preferably used.
The polyamide oligomer used in the present invention has a weight average molecular weight of not more than 5,000, more preferably not more than 4,000 g / mol, and still more preferably not more than 3,000 g / mol. The molecular weight of the polyamide oligomer should not be too low, for example, to avoid the risk of lowering the glass transition temperature, and preferably the weight average molecular weight is greater than about 1,000 g / mole.
Specific examples of suitable polyamide resins and polyamide oligomers according to the present invention include aliphatic polyamides such as polyamide-6, polyamide-11, polyamide-12, polyamide-4,6, polyamide- 8, polyamide-4,10, polyamide-4,12, polyamide-6,6, polyamide-6,9, polyamide-6,10, polyamide-6,12, polyamide- Polyamide-6/12-copolyamide, polyamide-6/11-copolyamide, polyamide-6,6 / Polyamide-6,6 / 12-copolyamide, polyamide-6 / 6,10-copolyamide, polyamide-6,6 / 6,10-copolyamide, polyamide- 4,6 / 6-copolyamide, polyamide-6 / 6,6 / 6,10-terpolyamide and 1,4-cyclohexanedicarboxylic acid and 2,2,4- and 2,4,4- Copolyamides obtained from trimethylhexamethylenediamine, aromatic polyamides, such as, for example, Polyamide-6, I / polyamide-6, I / 6,6-copolyamide, polyamide-6, T, polyamide- Polyamide-6, T / 2 copolyamide, polyamide-6,6 / 6, T / 6, I-copolyamide, polyamide- -MPMDT-copolyamide (2-MPMDT = 2-methylpentamethylenediamine), polyamide-9, T, terephthalic acid, 2,2,4- and 2,4,4-trimethylhexamethylene diamine Isophthalic acid, lauryllactam and copolyamides, isophthalic acid, azelaic acid and / or sebacic acid and 4, 4-diaminodiphenylmethane obtained from 3,5-dimethyl-4,4-diamino-dicyclohexylmethane. , Copolyamides obtained from 4-diaminodicyclohexylmethane, copolyamides obtained from caprolactam, isophthalic acid and / or terephthalic acid and 4,4-diaminodicyclohexylmethane, caprolactam, SOFTAL And / or copolyamides obtained from copolyamides, isophthalic acid and / or terephthalic acid and / or other aromatic or aliphatic dicarboxylic acids obtained from terephthalic acid and isophoronediamine, optionally alkyl-substituted hexamethylenediamine and alkyl -Substituted 4,4-diaminodicyclohexylamine, and also the copolyamides and mixtures of the abovementioned polyamides. Preferably the polyamide is selected from the group consisting of polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-4,6, polyamide-11, polyamide-12, polyamide- Amide-6, I, polyamide-6, T, polyamide-6, T / 6,6-copolyamide, polyamide-6, T / 6- copolyamide, polyamide- Polyamide-6, T / 6, I-copolyamide, polyamide-6, T / 2-MPMDT-copolyamide, polyamide- 6/6-copolyamide and mixtures of the abovementioned polyamides and copolyamides.
Polyamide-6,6, polyamide-6,6 / 6, T, polyamide-6,6 / 6, T / 6, I Polyamide-6, T / 2-MPMDT-copolyamide, polyamide-9, T or polyamide-4,6 or mixtures thereof or copolyamide is selected as the polyamide. Wherein I means isophthalic acid and T means terephthalic acid.
Examples of the raw materials for the polyamide moiety include pyrrolidone, piperidone, caprolactam, enanthrolactam, capryllactam, lauryllactam, glycine,? -Alanine, 4- aminobutyric acid, Aminocaproic acid, malonic acid, succinic acid, adipic acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, cyclohexanedicarboxylic acid,
Hexanedicarboxylic acid, hexanedicarboxylic acid, ethylenediamine, 1,3 (1,2) -diaminopropane, tetraethylenediamine, hexamethylenediamine, nano methylenediamine, undecamethylenediamine, dodecamethylenediamine, Xylylenediamine, and isophoronediamine, and one or more of them may be used.
The polyamide oligomer may be selected to have the same composition as the high molecular weight polyamide resin, or may be selected to have a different composition from each other.
The blending ratio of the polyamide oligomer in the present invention is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the polyamide resin. When the amount is less than 0.001 parts by weight, the fluidity or releasability is less than expected. When the amount exceeds 10 parts by weight, the flowability and mold releasability are improved. However, gas is generated during molding to deteriorate the appearance of the molded article, Which is undesirable.
Bisamides typified by ethylene screwstearyl amide have been conventionally used as mold release agents and lubricants. However, when these bisamides are blended with a polyamide resin and a triamine-based flame retardant, there is a problem that flame retardancy, fluidity and tensile elongation are deteriorated although the releasability is improved.
Examples of the triazine flame retardant used in the present invention include melamine, cyanuric acid, and melamine cyanuric acid. These triazine flame retardants may be used singly or in combination. These compounds will be described in detail below.
A melamine, a melamine derivative, a compound having a structure similar to melamine or a condensate of melamine, and examples thereof include melamine, melamine phosphate, dimelamine pyrophosphate, anomeride, anomerine, hormoguanamine, guanyl Cyanuric acid, isocyanuric acid, and derivatives thereof, and examples thereof include cyanuric acid, isocyanuric acid, isocyanuric acid, (N-propyl) isocyanurate, methyl cyanurate, tri (n-propyl) isocyanurate, trimethyl isocyanurate, triethyl cyanurate, triethyl isocyanurate, Methyl isocyanurate, diethyl cyanurate, diethyl isocyanurate and the like, preferably melamine cyanuric acid.
Melamine cyanuric acids are products of equimolar reaction of melamine and cyanuric acid, but they are not necessarily equimolar, and some of the functional groups may be in a free state or may be substituted with substituents.
The blending ratio of the triazine flame retardant is used in the range of 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the polyamide resin. When the amount is less than 1 part by weight, the effect of flame retardancy is not observed. When the amount is more than 25 parts by weight, the flame retardancy is effective, but gas is generated at the time of molding,
The glass fiber content used in the present invention is 5 to 50 parts by weight, preferably 15 to 45 parts by weight, based on 100 parts by weight of the polyamide resin.
The glass fibers can be used in the form of short glass fibers, long glass fibers or glass fiber mats, which are continuous filaments which form short fibers or nonwoven fabrics of 10 to 250 mm in length, where the fibers and filaments are randomly oriented (Which may be aligned).
However, in order to strengthen the polyamide compound, for example, other types of fibers such as carbon fibers and aramid fibers may be used, but glass fibers are preferably used, and short glass fibers are particularly preferably used.
The polyamide compound of the present invention is a polyamide compound having remarkably excellent mechanical properties by further containing glass fiber as a reinforcing material while further improving flame retardancy, fluidity and releasability. The polyamide compound is used as a switch, a micro slide switch, a DIP switch, A motor housing, a gear cam, a dancing pulley, a motor housing, a housing of a connector, a connector shell, an IC socket, a coil bobbin, a bobbin cover, a relay, a relay box, a condenser case, A housing of a terminal, an intake and exhaust pipe, a bearing retainer, a cylinder head cover, an intake manifold, an air cleaner-case air conditioner fan, a housing of a terminal, a spacer, an insulator, a caster, a terminal block, Fold, water pipe infer, clutch release bearing hub, heat resistant container, microwave parts, It is useful for electrical and electronic parts, semi-auto components, printer ribbon guide, etc., automobile and automobile parts, home and office electrical parts, computer parts, facsimile and copier related parts, machine parts and other various applications. .
<Examples>
sample preparation
Prepare the following materials for the examples.
Polyamide resin: polyamide 6 (BASF), molecular weight = 40,000
Polyamide oligomer: Polyamide 6 (BASF), Molecular weight = 2,000
Flame retardant: melamine phosphate (DSM), nitrogen content 42-44%, phosphorus content 12-14%
Glass fiber: Vetrotex yarn, 4.5 mm long, short glass fiber
The raw materials and compounding ratios used in the examples according to the present invention are shown in Table 1 below with respect to 100 parts by weight of the polyamide resin.
Manufacture of polyamide compounds
The polyamide compound according to this example was prepared by melt mixing the components on a Werner & Pfleiderer ZSK-40 twin-screw extruder using a flat temperature profile of 300 ° C. The constituents were fed through the hopper and the glass fibers were added via a side feed. The throughput was 60 kg / h and the screw speed was 250 rpm.
After degassing the polymer melt at the end of the extruder, the melt was extruded into strands, cooled and chopped into granules. The flame retardance and mechanical properties of the compound were measured using a test bar after injection molding of the test bar and UL 94 test according to the ISO 527 / 1A multipurpose specimen of 0.8 mm thickness and the test results were summarized in Table 2 below .
Measurement of physical properties
Tensile strength: measured at 23 ° C and 5 mm / min according to ISO 527.
Extension at break: measured at 23 ° C and 5 mm / min according to ISO 527.
Flammability: Flame retardancy: Underwriters Laboratories Test Method UL94 according to UL 94, conditioned at 23 ° C, 50% relative humidity for 48 hours, and conditioned at 0.8 ° C for 168 hours at 70 ° C.
(Without polyimide 6 oligomer: very poor)
As shown in the test results of Table 2, the flame retardant, the oligomer and the glass fiber according to an embodiment of the present invention are included in the compound, so that the polyamide resin has flame retardancy, releasability and excellent mechanical strength, , The actual strand formation is very good and the glass fiber is included as the reinforcing material, so that the tensile strength is more than 115 Mpa and the excellent mechanical properties are obtained. Also in the UL 94 combustibility test due to the influence of the flame retardant It can be confirmed that the combustion time results are excellent within the reference value.
The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (5)
The polyamide resin or the polyamide oligomer may be at least one selected from the group consisting of polyamide-6, polyamide-11, polyamide-12, polyamide-4,6, polyamide-4,8, polyamide- 12, polyamide-6,16, polyamide-6,9, polyamide-6,10, polyamide-6,12, polyamide-10,10, polyamide- , Polyamide-6, T, polyamide-6, T / 6,6-copolyamide, polyamide-6, T / 6-copolyamide, polyamide- Amide-6,6 / 6, T / 6, I-copolyamide, polyamide-6, T / 2-MPMDT- copolyamide, polyamide-9, T, polyamide- , Polyamide-6/11-copolyamide, polyamide-6,6 / 11-copolyamide, polyamide-6,6 / 12-copolyamide, polyamide- , Polyamide-6,6 / 6,10-copolyamide, polyamide-4,6 / 6-copolyamide, polyamide-6 / 6,6 / 6,10- terpolyamide The glass fiber reinforced flame-retardant, characterized in that which is selected as at least one polyamide compound.
Wherein the triazine flame retardant is a melamine or cyanuric acid or a mixture thereof.
Wherein the glass fibers are continuous filaments which form short fibers or nonwoven fabrics having a length of 5 to 250 mm.
Wherein the melamine is at least one selected from the group consisting of melamine, melamine phosphate, dimelamine pyrophosphate, ammercid, anmerine, guanylmelamine, cyanomelamine and arylguanamine, wherein the cyanuric acid is selected from the group consisting of cyanur At least one member selected from the group consisting of an acid, an isocyanuric acid, a methyl cyanurate, a diethyl cyanurate, trimethyl cyanurate, methyl isocyanurate, diethyl isocyanurate, tricyanurate and triisocyanurate ≪ / RTI > wherein the glass fiber reinforced polyamide compound is selected from the group consisting of glass fiber reinforced flame retardant polyamide compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140005938A KR20150085936A (en) | 2014-01-17 | 2014-01-17 | Glass fiber-reinforce flame retardant polyamide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140005938A KR20150085936A (en) | 2014-01-17 | 2014-01-17 | Glass fiber-reinforce flame retardant polyamide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150085936A true KR20150085936A (en) | 2015-07-27 |
Family
ID=53874895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140005938A KR20150085936A (en) | 2014-01-17 | 2014-01-17 | Glass fiber-reinforce flame retardant polyamide compound |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20150085936A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170071896A (en) * | 2015-12-16 | 2017-06-26 | 주식회사 엘지화학 | Flame retardant electromagnetic wave shielding and heat radiating carbon-composite composition and molded article manufactured using same |
-
2014
- 2014-01-17 KR KR1020140005938A patent/KR20150085936A/en active Search and Examination
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170071896A (en) * | 2015-12-16 | 2017-06-26 | 주식회사 엘지화학 | Flame retardant electromagnetic wave shielding and heat radiating carbon-composite composition and molded article manufactured using same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102460868B1 (en) | Polyamide moulding compounds with flame-retardant properties and very good long-term heat-ageing resistance | |
| KR102189978B1 (en) | Polyamide resin composition and molded article produced therefrom | |
| US7723411B2 (en) | Flameproof polyamide moulding materials | |
| KR101932808B1 (en) | Flame-retardant polyamide resin composition | |
| JP3792722B2 (en) | Flameproof PA molding material containing melamine cyanurate and pretreated fibrous filler | |
| US20070299171A1 (en) | Fireproof Composition Based on Thermoplastic Matrix | |
| JP6130400B2 (en) | Method for preparing halogen-free flame retardant polyamide composition | |
| US20130217814A1 (en) | Halogen-free flame retardant polyamide composition | |
| JP2009041016A (en) | Flame retardant mixture for thermoplastic polymer, and flame retardant polymer | |
| CN114790330B (en) | Flame-retardant polyamide glass fiber composition and preparation method thereof | |
| KR20110033257A (en) | Flame resistant semiaromatic polyamide resin composition including zinc stannate, and articles therefrom | |
| ES2259416T3 (en) | COMPOSITION IGNIFUGA OF POLYAMIDE. | |
| KR20200036020A (en) | Flame retardant polyamide composition with high glow wire ignition temperature and use thereof | |
| US20150191593A1 (en) | Flame-retardant polymer compositions and molded articles comprising the same | |
| US20100025643A1 (en) | Flame-retardant mixture for thermoplastic polymers, and flame-retardant polymers | |
| JPH05214246A (en) | Flame-retarding polyamide resin composition | |
| JP6521953B2 (en) | Process for the preparation of semiaromatic copolyamides with high diamine excess | |
| CN110964315B (en) | Polyamide composition, method for producing same, and molded article | |
| KR20150085936A (en) | Glass fiber-reinforce flame retardant polyamide compound | |
| KR101600618B1 (en) | Eco-environmental flame retardant polyamide resin composition comprising clay | |
| JPH0517683A (en) | Polyamide resin composition | |
| JPH0753863A (en) | Polyamide resin composition | |
| CN117730114A (en) | Flame retardant polyamide composition | |
| CA3229749A1 (en) | Flame-proof, partially aromatic polyamides | |
| CN117363003A (en) | Halogen-free flame-retardant polyamide composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment | ||
| AMND | Amendment | ||
| E801 | Decision on dismissal of amendment |