GB2279352A - Colored polyolefin resin composition - Google Patents
Colored polyolefin resin composition Download PDFInfo
- Publication number
- GB2279352A GB2279352A GB9412626A GB9412626A GB2279352A GB 2279352 A GB2279352 A GB 2279352A GB 9412626 A GB9412626 A GB 9412626A GB 9412626 A GB9412626 A GB 9412626A GB 2279352 A GB2279352 A GB 2279352A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- parts
- acid
- polyolefin resin
- pearl pigment
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A colored polyolefin resin composition being prevented from yellowing comprises 100 parts by weight of a polyolefin resin, from 0.1 to 30 parts by weight of a mica pearl pigment and from 0.01 to 10 parts by weight of an aliphatic polycarboxylic acid. The acid may be fumaric, succinic or malic acid and a phosphite antioxidant may also be present.
Description
COLORED POLYOLEFIN RESIN COMPOSITION
FIELD OF THE INVENTION
This invention relates to a colored polyolefin resin composition for providing a molded article colored with a mica pearl pigment which is prevented from yellowing.
BACKGROUND OF THE INVENTION
There have been used mica pearl pigments in order to pearlize molded polyolefin resin compositions from the viewpoint of design characteristics.
An example of a prior art relating to the improvement of a mica pearl pigment includes JP-A-60-92359 which discloses a weather resistant pearl pigment having a topcoat containing polysiloxane and a rare earth element (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
Further, JP-A-1-292067 discloses a technique for obtaining a pearl pigment with an improved weather resistance which comprises coating a mica pearl pigment with a watercontaining oxide such as water-containing oxide of zirconium, cobalt, manganese or cerium.
However, none of these two prior arts reports about the yellowing of a polyolefin resin composition colored with a mica pearl pigment.
In the production of colored and molded polyolefin articles, there have been employed extrusion molding and injection molding as a method for coloring and molding.
Colored and molded articles including sheets, blow bottles and films are obtained by the extrusion molding method, while molded articles such as household electric appliances and general merchandise are obtained by the injection molding method. These molded articles have been used popularly.
In general, conventional polyolefin resins contain stabilizers such as antioxidants so as to prevent the resins from deterioration due to oxidization.
When phenolic compounds (e.g., 2,6-di-t-butyl-4methylphenol, n-octadecyl-ss-(4'-hydroxy-3',5'-di-t- butylphenyl)propionate, tetrakis [methylene-3- (3' , 5' -di-t- butyl-4-hydroxyphenyl )propionate]methane) contained in antioxidants are present in a polyolefin resin, these phenolic compounds would change their properties due to heat, light, temperature, moisture or nitrogen compounds within a prolonged storage period. As a result, it is sometimes observed that the polyolefin resin or a colored and molded article thereof turns from white into yellow or pink.
Further, there is another problem that when a molded article is colored with a mica pearl pigment, yellowing of the article is strongly accelerated by, for example, titanium by which the surface of mica has been coated.
Furthermore, there is another problem that when a material contained in a molded resin container, which is colored with a mica pearl pigment, contains a phenolic antioxidant, the phenolic antioxidant penetrates into the resin container and thus the molded resin container undergoes a color change for the same reason as the one described above.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a polyolefin resin composition capable of preventing a molded article colored with a mica pearl pigment from yellowing even over a prolonged storage period.
The present inventor has conducted extensive studies in order to prevent a polyolefin resin molded article colored with a mica pearl pigment from yellowing and, as a result, successfully found that yellowing of a colored and molded article can be prevented by blending an aliphatic polycarboxylic acid in the step of coloring a polyolefin resin with a mica pearl pigment.
Accordingly, the present invention provides a colored polyolefin resin composition comprising 100 parts by weight of a polyolefin resin, from 0.1 to 30 parts by weight of a mica pearl pigment and from 0.01 to 10 parts by weight of an aliphatic polycarboxylic acid.
DETAILED DESCRIPTION OF THE INVENTION
To further illustrate the present invention in greater detail, preferred embodiments of the present invention will be given.
The polyolefin resin to be used in the present invention is a polymer of an aliphatic unsaturated hydrocarbon (CnH2n) which has been well known in the art.
Examples thereof include low density polyethylene resins, high density polyethylene resins, ethylene-a-olefin copolymers which is a so-called LLDPE, polypropylene resins and polybutene resins. These polyolefin resins may be used either alone or in the form of a mixture of two or more of them. As a polyethylene resin, it is preferable to use those having a specific gravity ranging from 0.91 to 0.97 (more preferably from 0.94 to 0.97) and a melt flow rate (MFR) ranging from 0.05 to 50 g/10 min. (more preferably from 0.1 to 3 g/10 min.). As a polypropylene resin, it is preferable to use those having a specific gravity ranging from 0.89 to 0.92 and an MFR ranging from 0.1 to 50 g/10 min. (more preferably from 0.1 to 3 g/10 min.).
The mica pearl pigment to be used in the present invention comprises fine mica having strata structure as the main component. To further improve the pearly appearance, those obtained by treating mica with titanium or iron, for example, coating a mica foil with titanium dioxide or iron oxide may be used. The average particle size of the mica pearl pigment preferably ranges from 1 to 200 Rm, more preferably from 15 to 60 Rm. Such a mica pearl pigment can easily be obtained commercially and used in the present invention. For example, Mearlin Pearl produced by Mearl Co.
(USA) and Iriodin pearl produced by Merck & Co., Inc.
(Germany) are usable therefor. In addition, those described in JP-B-4-65098 and JP-A-60-92359 may be used in the present invention (the term "JP-B" as used herein means an "examined
Japanese patent publication"). The pearl pigment is used preferably in an amount of from 0.1 to 30 parts by weight, more preferably from 0.1 to 5 parts by weight and furthermore preferably from 0.5 to 2 parts by weight, per 100 parts by weight of the above-mentioned polyolefin resin.
Examples of the aliphatic polycarboxylic acid to be used in the present invention, which is a characteristic feature of the present invention, include dicarboxylic acids and tricarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, methylmaleic acid, itaconic acid, citraconic acid, mesaconic acid, acetylenic acid, malic acid, methylmalic acid, citric acid, isocitric acid and tartaric acid. Among them, dicarboxylic acids, in particular, fumaric acid, succinic acid and/or malic acid, are preferred in the present invention.
Similar to the above-mentioned mica pearl pigment, these aliphatic polycarboxylic acids can be commercially available and used in the present invention. The aliphatic polycarboxylic acid is preferably used at a ratio of from 0.01 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight and furthermore preferably from 0.05 to 0.5 parts by weight, per 100 parts by weight of the abovementioned polyolefin resin. When the content of the aliphatic polycarboxylic acid is smaller than 0.01 part by weight, the aimed effect of the present invention of preventing the molded article from yellowing tends to be deteriorated. When that content exceeds 10 parts by weight, on the other hand, molding and processing of the composition tend to become difficult.In this case, furthermore, there is a tendency that the dispersion of the mica pearl pigment is inhibited and aggregates of the mica pearl pigment are frequently formed, which worsens the appearance of the molded article.
In the present invention it is preferable to use phosphite antioxidants in addition to the above-mentioned components. Examples of the phosphite antioxidants include bis (2, 6-t-butyl-4-methylphenyl ) pentaerythritol diphosphite, bis (2, 6-t-butyl-4-ethylphenyl ) pentaerythritol diphosphite, bis(2,6-di-t-butylphenyl)pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl)pentaerythritol diphosphite, 2,6-di-tbutyl-4-methylphenyl isooctylpentaerythritol-diphosphite, 2,6-di-t-butyl-4-methylphenyl phenylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, dioctylpentaerythritol diphosphite and diphenylpentaerythritol diphosphite.Such a phosphite antioxidant can be used at a ratio of from 0.001 to 5 parts by weight, preferably from 0.05 to 0.3 parts by weight, per 100 parts by weight of the polyolefin resin.
The colored polyolefin resin composition according to the present invention may be produced by an arbitrary method without restriction. For example, the above-mentioned components may be simply mixed together. Alternately, these components may be once molten and kneaded by a known method with the use of, for example, a Banbury mixer or an extrusion molding machine. This composition may be in the form of a mixture obtained by simply mixing these components.
Alternately, it may be granulated and provided in the form of pellets.
When the mica pearl pigment and the aliphatic polycarboxylic acid are used at low contents, the composition can be used as a so-called color compound and subjected to molding as such. When the content of the mica pearl pigment is high (for example, 20 to 30 parts by weight), the composition can be employed as a colored master batch which is to be diluted with an uncolored resin and then used.
In addition to the above-mentioned components, the colored polyolefin resin composition of the present invention may contain known additives such as other arbitrary colorants, antistatic agents, dispersing agents and UV absorbers, if necessary.
To further illustrate the present invention in greater detail, the following Examples and Comparative
Examples will be given, wherein Iriodin 120 Lustre Satin (a product of Merck & Co., Inc.) was used as a mica pearl pigment unless otherwise noted.
Method for evaluating yellowness index of molded article (1): Each of the colored and molded samples produced in the following Examples and Comparative Examples was introduced into a 2 1 desiccator. After pouring 200 ml of a 28 % aqueous ammonia, the desiccator was sealed while exposing the sample to this ammonia gas atmosphere. Next, the sample was irradiated downward with a fluorescent lamp (illumination at the surface of the sample: about 2,000 lux) and maintained at 400C for 100 hours. Then the colored and molded sample was taken out and the yellowness index (AYI) thereof was determined in comparison with that of a blank sample (a molded article which was not exposed to the ammonia gas atmosphere) with the use of a color-difference meter in accordance with JIS K 7103 (Yellowing of Plastics and Method for Testing Yellowness Index).The term "JIS" as used herein means "Japanese Industrial Standard".
Method for evaluating yellowness index of molded article (2):
Each of the colored and molded samples produced in the following Examples and Comparative Examples was allowed to stand in a room which was conditioned at a high temperature (60 + 50C) and under a high humidity (65 to 75 %) atmosphere for 60 days. Then the colored and molded sample was taken out and the yellowness index (nYI) thereof was determined in comparison with that of a blank sample (a molded article before allowing to stand at the high temperature and under high humidity atmosphere for 60 days as specified above) with the use of a color-difference meter in accordance with JIS KI 7103 (Yellowing of Plastics and Method for Testing Yellowness Index).
Method for evaluatina vellowness index of molded article (3):
Each of the colored and molded samples produced in the following Examples and Comparative Examples was irradiated with a fluorescent lamp at 5,000 lux for 18 days at a temperature of 400C and at a relative humidity of 75 % with the use of a thermo-hygrostat for testing fluorescent light-stability (a product of Nagano Kagaku Co., Ltd.) and the resulting color change was examined. The degree of the color change was determined by comparing the yellowness index (AYI) of the sample with that of a blank (the molded sample before the irradiation) in accordance with JIS K 7103 with the use of GCMS-3 (a product of Murakami Shikisai Gijutsu
Kenkyusho).
EXAMPLE 1
97.9 parts by weight of a polyethylene resin (Sholex 5003, a product of Showa Denko, K.K., specific gravity: 0.944, MFR: 0.3 g/10 min.), 2.0 parts by weight of a mica pearl pigment (average particle size: 20 zm) and 0.1 part by weight of succinic acid were homogeneously mixed in a
Henschel mixer and then extrusion molded with an extrusion molding machine at a temperature of 2000C to give colored pellets.
These pellets were molded into a plate (90 x 50 x 2 mm) with the use of an extrusion molding machine (a product of JSW, 5 oz.) at a temperature of 2300C and a mold temperature of 400C.
Subsequently, the yellowness index of the molded sample was evaluated in accordance with the methods as described above. Table 1 shows the results.
EXAMPLE 2
97.5 parts by weight of a polyethylene resin (Sholex 5003, a product of Showa Denko, K.K., specific gravity: 0.944, MFR: 0.3 g/10 min.), 2.0 parts by weight of a mica pearl pigment (average particle size: 20 Um) and 0.5 parts by weight of succinic acid were homogeneously mixed in a
Henschel mixer and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
EXAMPLE 3
97.9 parts by weight of a polypropylene resin (Mitsui
Noblene JH-G, a product of Mitsui Toatsu Chemicals, Inc., specific gravity: 0.91, MFR: 4 g/10 min.), 2.0 parts by weight of a mica pearl pigment (average particle size: 20 zm) and 0.1 part by weight of succinic acid were homogeneously mixed in a Henschel mixer and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
EXAMPLE 4
97.5 parts by weight of a polypropylene resin (Mitsui
Noblene JH-G, a product of Mitsui Toatsu Chemicals, Inc., specific gravity: 0.91, MFR: 4 g/10 min.), 2.0 parts by weight of a mica pearl pigment (average particle size: 20 Rm) and 0.5 parts by weight of fumaric acid were homogeneously mixed in a Henschel mixer and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
EXAMPLE 5
60.0 parts by weight of a polypropylene resin (Mitsui
Noblene JH-G, a product of Mitsui Toatsu Chemicals, Inc., specific gravity: 0.91, MFR: 4 g/10 min.), 30.0 parts by weight of a mica pearl pigment (average particle size: 20 Rm) and 10.0 parts by weight of fumaric acid were subjected to gelation in a 5 1 Banbury mixer and then kneaded for 1 minute. The kneaded blend was then drawn in the form of a strap of 3 mm in thickness by using an 8 inch mixing roll heated to 1800C.Further, this strap was cut into cubic pellets (3 mm x 3 mm x 3 mm) with a cubic pelletizer. 10 parts by weight of these pellets were homogeneously mixed with 90 parts by weight of the above-mentioned polypropylene resin and molded into a plate (90 mm x 50 mm x 2 mm) by using an extrusion molding machine (a product of JSW, 5 oz.) at a temperature of 2300C and a mold temperature of 400C.
Subsequently, the yellowness index of the molded sample was evaluated in the same manner as described in
Example 1. Table 1 shows the results.
EXAMPLE 6
70.0 parts by weight of a polypropylene resin (Mitsui
Noblene JH-G, a product of Mitsui Toatsu Chemicals, Inc., specific gravity: 0.91, MFR: 4 g/10 min.), 25.0 parts by weight of a mica pearl pigment (average particle size: 20 Rm) and 5.0 parts by weight of malic acid were kneaded in a
Banbury mixer (5 1) and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
EXAMPLE 7
94.5 parts by weight of a polypropylene resin (Mitsui
Noblene JH-G, a product of Mitsui Toatsu Chemicals, Inc., specific gravity: 0.91, MFR: 4 g/10 min.), 5.0 parts by weight of a mica pearl pigment (average particle size: 20 Rm) and 0.5 parts by weight of fumaric acid were kneaded in a
Banbury mixer (5 1) and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
EXAMPLE 8
97.9 parts by weight of a polyethylene resin (MARLEX 5502LD, a product of Phillips Inc.), 2.0 parts by weight of a mica pearl pigment (average particle size: 20 zm) and 0.1 part by weight of fumaric acid were homogeneously mixed in a
Henschel mixer and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
EXAMPLE 9
97.7 parts by weight of a polyethylene resin (MARLEX 5502LD, a product of Phillips Inc.), 2.0 parts by weight of a mica pearl pigment (average particle size: 20 zm), 0.1 part by weight of fumaric acid and 0.2 parts by weight of bis(2,6t-butyl-4-methylphenyl)pentaerythritol diphosphite were homogeneously mixed in a Henschel mixer and then molded and evaluated in the same manner as described in Example 1.
Table 1 shows the results.
COMPARATIVE EXAMPLE 1
98.0 parts by weight of a polyethylene resin (Sholex 5003, a product of Showa Denko K.K., specific gravity: 0.944,
MFR: 0.3 g/10 min.) and 2.0 parts by weight of a mica pearl pigment (average particle size: 20 Rm) were homogeneously mixed in a Henschel mixer and then molded and evaluated in the same manner as described in Example 1. Table 1 shows the results.
COMPARATIVE EXAMPLE 2
98.0 parts by weight of a polypropylene resin (Mitsui
Noblene JH-G, a product of Mitsui Toatsu Chemicals, Inc., specific gravity: 0.91, MFR: 4 g/10 min.) and 2.0 parts by weight of a mica pearl pigment (average particle size: 20 zm) were homogeneously mixed in a Henschel mixer and then molded and evaluated in the same manner as described in Example 1.
Table 1 shows the results.
COMPARATIVE EXAMPLE 3
98.0 parts by weight of a polyethylene resin (MARLEX 5502LD, a product of Phillips Inc.) and 2.0 parts by weight of a mica pearl pigment (average particle size: 20 Rm) were homogeneously mixed in a Henschel mixer and then molded and evaluated in the same manner as described in Example 1.
Table 1 shows the results.
TABLE 1
Comparative
Example Example 1 2 3 4 5 6 7 8 9 1 2 3
Composition (part by weight)
Polyethylene resin 97.9 97.5 - - - - - 97.9 97.7 98.0 - 98.0
Polypropylene resin - - 97.9 97.5 60.0 70.0 94.5 - - - 98.0
Mica pearl pigment 2.0 2.0 2.0 2.0 30.0 25.0 5.0 2.0 2.0 2.0 2.0 2.0
Succinic acid 0.1 0.5 - - - - - - - - -
Fumaric acid - - 0.1 0.5 10.0 - 0.5 0.1 0.1 - -
Malic acid - - - - - 5.0 - - - - -
Antioxidant* - - - - - - - - 0.2 - -
Yellowness Index (#YI)
Method (1) 0.9 0.6 0.8 0.5 0.3 0.9 1.2 - - 5.0 4.1
Method (2) 1.2 0.9 1.0 0.8 0.5 0.8 1.4 - - 6.5 5.5
Method (3) - - - - - - - 4.7 1.3 - - 7.9 * Antioxidant: bis(2,6-t-butyl-4-methylphenyl)pentaerythritol diphosphite As described above, the present invention can provide a colored polyolefin resin composition suitable for giving a molded article which does not suffer from yellowing.
While the invention has been described in detail and with reference to specific embodiments thereof it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (7)
1. A colored polyolefin resin composition comprising 100 parts by weight of a polyolefin resin, from 0.1 to 30 parts by weight of a mica pearl pigment and from 0.01 to 10 parts by weight of an aliphatic polycarboxylic acid.
2. A colored polyolefin resin composition comprising 100 parts by weight of a polyolefin resin, from 0.1 to 30 parts by weight of a mica pearl pigment, from 0.01 to 10 parts by weight of an aliphatic polycarboxylic acid and from 0.001 to 5 parts by weight of a phosphite antioxidant.
3. A colored polyolefin resin composition as claimed in claim 1 or 2, wherein said aliphatic polycarboxylic acid is fumaric acid, succinic acid and/or malic acid.
4. A colored polyolefin resin composition as claimed in claim 2, wherein said phosphite antioxidant is bis(2,6-t-butyl4methylphenyl)pentaerythritol diphosphite and said aliphatic polycarboxylic acid is fumaric acid, succinic acid and/or malic acid.
5. A composition as claimed in claim 1, substantially as hereinbefore described in any one of examples 1 to 8.
6. A composition as claimed in claim 2, substantially as hereinbefore described in Example 9.
7. An article when moulded from a composition as claimed in any preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17855993 | 1993-06-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9412626D0 GB9412626D0 (en) | 1994-08-10 |
| GB2279352A true GB2279352A (en) | 1995-01-04 |
| GB2279352B GB2279352B (en) | 1997-02-26 |
Family
ID=16050608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9412626A Expired - Fee Related GB2279352B (en) | 1993-06-28 | 1994-06-23 | Colored polyolefin resin composition |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1101056A (en) |
| GB (1) | GB2279352B (en) |
| HK (1) | HK1000013A1 (en) |
| TW (1) | TW304199B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748840A1 (en) * | 1995-06-07 | 1996-12-18 | Ciba-Geigy Ag | Stabilization of polymers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5801463B1 (en) * | 2014-11-26 | 2015-10-28 | 大日精化工業株式会社 | Resin coloring masterbatch and method for producing colored resin molding |
| CN108641170A (en) * | 2018-03-27 | 2018-10-12 | 苏州通产丽星包装科技有限公司 | A kind of pearly-lustre fisheye and preparation method thereof for cosmetic package |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1029190A (en) * | 1962-12-28 | 1966-05-11 | Monsanto Co | Ethylene polymer compositions |
| US4544415A (en) * | 1983-09-24 | 1985-10-01 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Weathering-resistant pearlescent pigments |
| EP0328967A1 (en) * | 1988-02-03 | 1989-08-23 | E.I. Du Pont De Nemours And Company | Process for rendering polymer resistant to discoloration in the presence of TiO2 pigments |
-
1994
- 1994-06-23 GB GB9412626A patent/GB2279352B/en not_active Expired - Fee Related
- 1994-06-27 TW TW83105814A patent/TW304199B/zh active
- 1994-06-28 CN CN 94107685 patent/CN1101056A/en active Pending
-
1997
- 1997-07-10 HK HK97101530A patent/HK1000013A1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1029190A (en) * | 1962-12-28 | 1966-05-11 | Monsanto Co | Ethylene polymer compositions |
| US4544415A (en) * | 1983-09-24 | 1985-10-01 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Weathering-resistant pearlescent pigments |
| EP0328967A1 (en) * | 1988-02-03 | 1989-08-23 | E.I. Du Pont De Nemours And Company | Process for rendering polymer resistant to discoloration in the presence of TiO2 pigments |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748840A1 (en) * | 1995-06-07 | 1996-12-18 | Ciba-Geigy Ag | Stabilization of polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2279352B (en) | 1997-02-26 |
| TW304199B (en) | 1997-05-01 |
| CN1101056A (en) | 1995-04-05 |
| GB9412626D0 (en) | 1994-08-10 |
| HK1000013A1 (en) | 1997-10-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20040623 |