Oxygen-scavenging resin compositions and containers having low haze and related methods
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Expired 25 July 2022, 4.2 years ago.
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44 claims: 6 independent, 38 dependent
- 1膜形成ポリエステル、および 分子酸素と反応することができ る有 効量の酸素除去鉄粒子を含み、その中で寸法25ミクロン未満の粒子が存在するが、その濃度が、式:ppm=512.3×d〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕により定められる濃度を超えない樹脂組成物。
- 2ポリエステルが、直鎖ポリエステルまたは分枝ポリエステルを含む請求項1に記載の樹脂組成物。
- 3ポリエステルが、ポリエチレンテレフタレート、ポリエチレンテレフタレートコポリマー、ポリエチレンナフタレート、ポリエチレンナフタレートコポリマー、ポリブチレンテレフタレート、ポリブチレンテレフタレートコポリマー、ポリトリメチレンテレフタレートまたはポリトリメチレンテレフタレートコポリマーを含む請求項1に記載の樹脂組成物。
- 4酸素除去鉄粒子の有効量が、樹脂の50~2500質量ppmである請求項1に記載の樹脂組成物。
- 5酸素除去鉄粒子が、20~70ミクロンの粒度範囲を有する請求項1に記載の樹脂組成物。
- 6寸法25ミクロン未満の粒子が、0 . 97~2 . 44グラム毎立方センチメートルの見掛け密度を有する請求項1に記載の樹脂組成物。
- 7寸法20ミクロン未満の粒子が、0 . 97~2 . 44グラム毎立方センチメートルの見掛け密度を有し、樹脂の800質量ppmの濃度を超えない請求項1に記載の樹脂組成物。
- 8酸素除去鉄粒子が、吸湿 (hydroscopic) 物質、電解質酸性化剤、非電解質酸性化剤、金属ハロゲン化物、金属硫酸塩および金属硫酸水素塩からなる群から選択される1種またはそれ以上の反応増強剤で前処理されている請求項1に記載の樹脂組成物。
- 9該樹脂組成物から製造されたボトルが、10%またはそれ以下のハンターヘーズ値を有する請求項1に記載の樹脂組成物。
- 10膜形成ポリエステル、および 有効量の酸素除去鉄粒子 を含み、その中で寸法25ミクロン未満の粒子が存在するが、その濃度が、樹脂の1250質量ppmを超えない請求項1に記載の樹脂組成物。
- 11ポリエステルが、直鎖ポリエステルまたは分枝ポリエステルを含む請求項10に記載の樹脂組成物。
- 12ポリエステルが、ポリエチレンテレフタレート、ポリエチレンテレフタレートコポリマー、ポリエチレンナフタレート、ポリエチレンナフタレートコポリマー、ポリブチレンテレフタレート、ポリブチレンテレフタレートコポリマー、ポリトリメチレンテレフタレートまたはポリトリメチレンテレフタレートコポリマーを含む請求項10に記載の樹脂組成物。
- 13鉄粒子の有効量が、樹脂の50~2500質量ppmである請求項10に記載の樹脂組成物。
- 14鉄粒子が、20~70ミクロンの粒度範囲を有する請求項10に記載の樹脂組成物。
- 15寸法20ミクロン未満の粒子が、樹脂の800質量ppmを超えない請求項10に記載の樹脂組成物。
- 16酸素除去鉄粒子が、吸湿 (hydroscopic) 物質、電解質酸性化剤、非電解質酸性化剤、金属ハロゲン化物、金属硫酸塩および金属硫酸水素塩からなる群から選択される1種またはそれ以上の反応増強剤で前処理されている請求項10に記載の樹脂組成物 。
- 17該樹脂組成物から製造されたボトルが、10%またはそれ以下のハンターヘーズ値を有する請求項10に記載の樹脂組成物。
- 18膜形成ポリエステルおよび樹脂の50~2500質量ppmの酸素除去鉄粒子を含み、その中で寸法25ミクロン未満の鉄粒子濃度が、樹脂の1250質量ppmを超えない請求項1に記載の樹脂組成物。
- 19ポリエステルが、直鎖ポリエステルまたは分枝ポリエステルを含む請求項18に記載の樹脂組成物。
- 20ポリエステルが、ポリエチレンテレフタレート、ポリエチレンテレフタレートコポリマー、ポリエチレンナフタレート、ポリエチレンナフタレートコポリマー、ポリブチレンテレフタレート、ポリブチレンテレフタレートコポリマー、ポリトリメチレンテレフタレートまたはポリトリメチレンテレフタレートコポリマーを含む請求項18に記載の樹脂組成物。
- 21鉄粒子が、20~70ミクロンの粒度範囲を有する請求項18に記載の樹脂組成物。
- 22寸法20ミクロン未満の粒子が、樹脂の500質量ppmを超えない請求項18に記載の樹脂組成物。
- 23酸素除去鉄粒子が、吸湿 (hydroscopic) 物質、電解質酸性化剤、非電解質酸性化剤、金属ハロゲン化物、金属硫酸塩および金属硫酸水素塩からなる群から選択される1種またはそれ以上の反応増強剤で前処理されている請求項18に記載の樹脂組成物。
- 24該樹脂組成物から製造されたボトルが、11~16ミル(1ミル=0.0254ミリメートル)の厚みに延伸されたときに、10%またはそれ以下のハンターヘーズ値を有する請求項18に記載の樹脂組成物。
- 25低ヘーズを有する透明品の形成に使用するための、樹脂の50~2500質量ppmの鉄粒子を含む樹脂組成物であって、該透明品が、10%またはそれ以下のハンターヘーズ値を有する請求項1に記載の樹脂組成物。
- 26ポリエステルが、ポリエチレンテレフタレート、ポリエチレンテレフタレートコポリマー、ポリエチレンナフタレート、ポリエチレンナフタレートコポリマー、ポリブチレンテレフタレート、ポリブチレンテレフタレートコポリマー、ポリトリメチレンテレフタレートまたはポリトリメチレンテレフタレートコポリマーを含む請求項25に記載の樹脂組成物。
- 27寸法25ミクロン未満の粒子が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない、請求項25に記載の樹脂組成物。
- 28請求項1に記載の樹脂組成物から形成された物品であって、物品のハンターヘーズ値が10%またはそれ以下である物品。
- 29ボトルである請求項28に記載の物品。
- 30樹脂組成物が、ポリエチレンテレフタレート、ポリエチレンテレフタレートコポリマー、ポリエチレンナフタレート、ポリエチレンナフタレートコポリマー、ポリブチレンテレフタレート、ポリブチレンテレフタレートコポリマー、ポリトリメチレンテレフタレートまたはポリトリメチレンテレフタレートコポリマーを含む請求項28に記載の物品。
- 31物品のハンターヘーズ値が、8%またはそれ以下である請求項28に記載の物品。
- 32分子酸素と反応することができる有効量の酸素除去鉄粒子を準備する工程で、その中で寸法25ミクロン未満の粒子が存在するが、その濃度が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない工程;ポリエステルの溶融相重合;重合後およびペレット化の前;ポリエステルの固相重合;および 押出 のプロセス工程1つまたはそれ以上の間に、該酸素除去鉄粒子をポリエステル樹脂組成物に添加する工程 を含む、多量の酸素除去鉄粒子を低ヘーズで組み込む請求項1に記載の樹脂組成物の製造方法。
- 33酸素除去鉄粒子をポリエステル樹脂組成物に添加する工程が酸素除去樹脂のマスターバッチを製造し、該マスターバッチを追加の樹脂に添加する工程をさらに含む、請求項32に記載の方法。
- 34ポリエステル樹脂が、ポリエチレンテレフタレート、ポリエチレンテレフタレートコポリマー、ポリエチレンナフタレート、ポリエチレンナフタレートコポリマー、ポリブチレンテレフタレート、ポリブチレンテレフタレートコポリマー、ポリトリメチレンテレフタレートまたはポリトリメチレンテレフタレートコポリマーを含む請求項32に記載の方法。
- 35酸素除去鉄粒子の有効量が、樹脂の50~2500質量ppmである請求項32に記載の方法。
- 36寸法25ミクロン未満の粒子が、0 . 97~2 . 44グラム毎立方センチメートルの見掛け密度を有する請求項32に記載の方法。
- 37寸法20ミクロン未満の粒子が、0 . 97~2 . 44グラム毎立方センチメートルの見掛け密度を有し、樹脂の800質量ppmの濃度を超えない請求項32に記載の方法。
- 38酸素除去鉄粒子が、吸湿 (hydroscopic) 物質、電解質酸性化剤、非電解質酸性化剤、金属ハロゲン化物、金属硫酸塩および金属硫酸水素塩からなる群から選択される1種またはそれ以上の反応増強剤で前処理されている請求項32に記載の方法。
- 39該樹脂組成物から製造されたボトルが、10%またはそれ以下のハンターヘーズ値を有する請求項32に記載の方法。
- 40膜形成ポリエステル、および 分子酸素と反応することができる酸素除去鉄粒子を含む粒状物 を含み、その中で寸法25ミクロン未満の粒子が存在するが、その濃度が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない請求項1に記載の樹脂組成物。
- 41膜形成ポリエステル、および 分子酸素と反応することができる有効量の酸素除去鉄粒子 を含み、その中で、25~38ミクロンの寸法範囲内の粒子が存在し、および38~45ミクロンの寸法範囲内の粒子が存在し、並びに寸法25ミクロン未満の粒子が存在し、その濃度が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない請求項1に記載の樹脂組成物。
- 42膜形成ポリエステル、および 分子酸素と反応することができる有効量の酸素除去鉄粒子 を含み、その中で、38~45ミクロンの寸法範囲内の粒子が存在し、および45~75ミクロンの寸法範囲内の粒子が存在し、並びに、寸法25ミクロン未満の粒子が存在し、その濃度が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない請求項1に記載の樹脂組成物。
- 43膜形成ポリエステル、および 分子酸素と反応することができる有効量の酸素除去鉄粒子 を含み、その中で、25~38ミクロンの寸法範囲内の粒子が存在し、および38~75ミクロンの寸法範囲内の粒子が存在し、並びに、寸法25ミクロン未満の粒子が存在し、その濃度が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない請求項1に記載の樹脂組成物。
- 44膜形成ポリエステル、および 分子酸素と反応することができる有効量の酸素除去鉄粒子 を含み、その中で、25~45ミクロンの寸法範囲内の粒子が存在し、および45~75ミクロンの寸法範囲内の粒子が存在し、並びに、寸法25ミクロン未満の粒子が存在し、その濃度が、式:ppm=512 . 3×d 〔式中、ppmは、寸法25ミクロン未満の粒子の、樹脂組成物全体に対する質量ppmの概算濃度であり、dは、寸法25ミクロン未満の粒子の、グラム毎立方センチメートルの見掛け密度である。〕 により定められる濃度を超えない請求項1に記載の樹脂組成物。
Independent claims44
76 paragraphs, as filed
<u style="single">Background of the invention</u> Thermoplastics, such as polyethylene terephthalate (PET), are commonly used to make packaging materials. PET processed under appropriate conditions produces high-strength articles with excellent gas barrier properties. Foods, beverages and medicines can deteriorate or be impaired when exposed to oxygen. Therefore, in order to improve the shelf life and flavor retention of products such as foods, beverages and medicines, the blocking protection provided by PET is often supplemented by the addition of an additional layer of packaging material or an oxygen scavenger. Adding a gas blocking film layer is known as passive blocking packaging. Ethyl Vinyl Alcohol (EVOH), Polybini<u style="single">Ri</u>Dendichloride (PVDC) and nylon MXD6 are examples of films commonly used for this purpose due to their excellent oxygen blocking properties. However, it is not preferable to use separate layers of different substances. This is because it adds cost to the packaging manufacturing and does not reduce the oxygen levels already present in the packaging.
The addition of an oxygen scavenger to the PET resin is known as active blocking packaging. This approach of protecting oxygen-sensitive products has two sides; the packaging prevents oxygen from reaching the product from the outside and also allows some of the oxygen present in the container from there into the polymer matrix. Absorb. In some applications, a parcel or pouch containing an oxygen scavenger is added to the packaging and placed next to the food. Pouches are generally limited to solid foods, in which pouches can be easily removed from foodstuffs and are not accidentally ingested. The annoying nature of manufacturing sachets and introducing them into the packaging results in increased costs.
One way to overcome the shortcomings of sachets is to incorporate the remover directly into the wall of the food packaging. This can be done by placing the remover throughout the remover wall or by placing the remover in only one layer between the layers of the side wall of the container. It should be recognized that the sidewalls and walls also refer to the lid and bottom of the container. Currently, the incorporation of removers throughout the container wall is found in non-transparent trays or packaging films where the remover is invisible to the naked eye. Virtually any remover can be used in this application. Because no remover is found. However, containers that require transparency have traditionally been limited to organic species removers that maintain the transparency of the container when placed in an independent layer within the container wall. The use of organic scavengers in single-layer or single-layer structures is limited by the nature of the organic scavengers or the cost and regulation of removal reactions by by-products.
Part of the cost is the logical problem encountered with the use of organic species removers. In most embodiments, a transition metal catalyst is used to activate the oxidizing polymer. The drawback of this technique is that the polymer begins to react with oxygen as soon as the packaging is manufactured. As a result, the bottle must be filled immediately. Large amounts of remover are used to compensate for the loss of removal capacity between the time the bottle is manufactured and the time the bottle is filled.
In another technique, UV irradiation is used to activate the oxidizing polymer. However, UV activation techniques are relatively expensive and initiators are often not specified for use in food packaging. Packagings designed for beer and juice are specifically designed to prevent UV transmission, and therefore UV activation will not be practical for these containers that block UV.
An alternative to visually acceptable organics is to use removed particles dispersed in the side walls of the vessel, such as powders of reduced metal. Reduced iron powder is commonly used for oxygen removal in food packaging. Iron reacts with oxygen to form iron oxide. For most applications, salts and hygroscopic agents are also used as reaction enhancers to improve the potency of iron powder. Since the reaction usually requires water, the iron removal composition remains inert until it is filled in the packaging and the reaction is activated by the water in the packaging contents. It travels through the polymer and comes into contact with the removal composition.
The use of the removed powder in clear packaging was previously limited aesthetically, especially by haze or color. High loadings of iron powder, typically on the order of 500-5000 ppm, are required to obtain sufficient oxygen absorption. The usual knowledge and prior art teaches practitioners to use the maximum removed surface area possible to improve their efficiency and capacity and minimize the amount of iron added. In practice this means a large number of small particles. Unfortunately, previous attempts to produce resin compositions containing large amounts of small iron particles for use in transparent packaging have resulted in packaging with poor optical properties. This is especially true when the resin composition is stretched or stretched to some extent in forming the final product, eg polyester bottles. Typically, bottles made from such resin compositions are translucent. The haze value of these bottles is generally high and lacks transparency.
Therefore, there remains a demand for packaging materials that have an acceptable visual appearance and that contain an oxygen-removing resin composition. The present invention relates to oxygen scavenging resin compositions useful in packaging and other applications. In particular, the present invention relates to a film-forming, oxygen-removing polyester composition having a low haze. The present invention also relates to a container having an effective oxygen scavenging function and a low haze. The present invention further relates to a method for incorporating large amounts of oxygen scavenging particles into a film-forming polyester resin composition with low haze.
<u style="single">A brief overview of the invention</u> Generally, the present invention contains an effective amount of oxygen scavenging particles containing film-forming polyester and at least one oxygen scavenging element, in which particles with dimensions less than about 25 microns are represented by the formula: ppm = 512.3 × d [in the formula, ppm is the approximate concentration of mass ppm for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ] Provided is a resin composition in which the particles have a particle size distribution that does not exceed the concentration determined by.
The present invention also includes a film-forming polyester and an effective amount of oxygen-removing iron particles, in which the iron particles have a particle size distribution such that the particles having a size of less than about 25 microns do not exceed about 1250 mass ppm of the resin. Includes compositions. The present invention also comprises a film-forming polyester and a resin composition containing about 50 to about 2500 mass ppm of iron particles, wherein the concentration of iron particles having a size of less than about 25 microns does not exceed about 1250 mass ppm of the resin. Including.
The present invention is also a polyester resin composition containing iron particles of about 50 to about 2500 mass ppm of resin for use in the formation of transparent products with low haze, wherein the transparent product is about 10% or more. Includes resin compositions having a hunter haze value below that. The present invention also includes articles formed from a resin composition comprising an effective amount of oxygen-removing particles, wherein the hunter haze value of the article is about 10% or less.
The present invention provides a container containing an effective amount of oxygen-removing particles and having a low haze. In particular, the present invention has at least one wall, the wall comprising a population occupied region, the population occupied region comprising a particle population containing a film-forming polymer and an effective amount of oxygen deficient particles, the number of particles in the population being: Polymer per cubic centimeter (6.0 x 10)<sup>7</sup>Particles ÷ T) [T in the equation is the thickness of the mill in the collective occupied area. ], The wall comprises a container having a permeation hunter haze of up to about 1 percent per mil of the wall of the container.
The present invention also includes a method of incorporating a large amount of oxygen-removing particles into a film-forming polyester resin composition with a low haze, in which the method prepares an effective amount of oxygen-removing particles containing at least one oxygen-removing element. In the formula, the particles with dimensions less than about 25 microns are: ppm = 512.3 × d [in the formula, ppm is the approximate concentration of the mass ppm of the particles with dimensions less than about 25 microns, and d is the dimensions about. An apparent density of cubic centimeters per gram of particles less than 25 microns. ] Steps in which the particles have a particle size distribution that does not exceed the concentration specified by; melt phase polymerization of polyester; after polymerization and before pelletization; solid phase polymerization of polyester; and during one or more process steps of extrusion Includes a step of adding the oxygen-removing particles to the polyester resin composition.
The present invention also includes film-forming polyesters and granules, in which particles less than about 25 microns in size are of the formula: ppm = 512.3 × d [where ppm is the mass of particles less than about 25 microns in size. Approximate concentration of ppm, d is the apparent density of particles less than about 25 microns in size, in centimeters per gram. ] Includes resin compositions in which the granules have a particle size distribution that does not exceed the concentration determined by.
The present invention conveniently overcomes the problems associated with the prior art by providing a thermoplastic resin composition that contains an effective amount of iron or other oxygen scavenger and has acceptable color and haze properties. Iron or other oxygen scavengers are present in sufficient amounts to effectively remove oxygen and provide longer shelf life for oxygen sensitive substances. The particle size of the oxygen scavenger is optimized to provide effective scavenging activity, while reducing dark tinting and haze.
<u style="single">Detailed description of the invention</u> The present invention relates to a film-forming, oxygen-removing resin composition having a low haze. Suitable thermoplastic polymers for use in the present invention include any thermoplastic homopolymer or copolymer. Examples of thermoplastic polymers are polyamides such as nylon 6, nylon 66 and nylon 612, linear polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polyethylene naphthalate, branched polyesters, polystyrene, polycarbonate, polyvinyl chloride. Vinyl, polyvinylidene dichloride, polyacrylamide, polyacrylonitrile, polyvinyl acetate, polyacrylic acid, polyvinyl methyl ether, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, polyethylene, polypropylene, ethylene propylene copolymer, poly (1-hexane), poly Includes (4-methyl-1-pentene), poly (1-butene), poly (3-methyl-1-butene), poly (3-phenyl-1-propene) and poly (vinylcyclohexane). Preferably, the thermoplastic polymer used in the present invention includes a polyester polymer or a copolymer.
A film-forming polymer will be understood to be a polymer that can be formed on a film or sheet. However, the present invention is not limited to films or sheets. The container of the present invention also includes the wall of the bottle, the tray, the bottom or lid of the container. Containers, such as the walls of blow-molded bottles and thermoformed trays, can be thought of as films or sheets formed in the shape of the container, and are therefore also within the scope of the present invention.
The polymers of the present invention can be produced by the polymerization procedures well known and customary in the art. Polyester polymers and copolymers can be produced by melt phase polymerization, which involves the reaction of the diol with a dicarboxylic acid or its corresponding ester. Various copolymers resulting from the use of various diols and diacids can also be used. Polymers with only one repeating unit of chemical composition are homopolymers. Polymers that have two or more chemically different repeating units in the same polymer are called copolymers. The diversity of repeating units depends on the number of different monomer species present during the initiating polymerization reaction. In the case of polyesters, copolymers involve the reaction of one or more diols with a diacid or a variety of diacids and are sometimes referred to as terpolymers.
Suitable dicarboxylic acids include those having about 6 to about 40 carbon atoms. Specific dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 1 , 2-Phenylenedioxydiacetic acid, 1,4-Phenylenedioxydiacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like, but not limited to these. Specific esters include, but are not limited to, phthalates and naphthalates diesters.
These acids or esters are aliphatic diols having about 2 to about 10 carbon atoms, alicyclic diols having about 7 to about 14 carbon atoms, and aromatics having about 6 to about 15 carbon atoms. It can react with group diols or glycol ethers with 4-10 carbon atoms. Suitable diols include, but are not limited to, 1,4-butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, resorcinol and hydroquinone. Polyfunctional comonomer can also be typically used in an amount of about 0.1 to about 3 mol%. Suitable comonomer includes, but are not limited to, trimellitic anhydride, trimethylolpropane, pyromelitonic dianhydride (PMDA) and pentaerythritol. Polyester-forming polyacids or polyols can also be used.
One preferred polyester is polyethylene terephthalate (PET), which is formed from a stoichiometric reaction of terephthalic acid or an ester thereof with ethylene glycol at about 1: 1. Another preferred polyester is polyethylene naphthalate (PEN) formed from a stoichiometric reaction of naphthalenedicarboxylic acid or an ester thereof with ethylene glycol from about 1: 1 to 1: 1.6. Yet another preferred polyester is polybutylene terephthalate (PBT). PET copolymers, PEN copolymers and PBT copolymers are also preferred. Certain copolymers and terpolymers of interest are PET in combination with isophthalic acid or diesters thereof, 2,6-naphthalic acid or diesters thereof and / or cyclohexanedimethanol.
The esterification or polycondensation reaction of a carboxylic acid or ester with a glycol is typically carried out in the presence of a catalyst. Suitable catalysts include, but are not limited to, antimony oxide, antimony triacetate, antimony ethyleneglycolate, organic magnesium, tin oxide, titanium alkoxide, dibutyltin dilaurate and germanium oxide. These catalysts can be used in combination with zinc, manganese or magnesium acetate or benzoate. A catalyst containing antimony is preferred.
Another preferred polyester is polytrimethylene terephthalate (PTT). It can be produced, for example, by reacting 1,3-propanediol with at least one aromatic diacid or an alkyl ester thereof. Preferred diacids and alkyl esters include terephthalic acid (TPA) or dimethyl terephthalate (DMT). Therefore, PTT preferably contains at least about 80 mol% of either TPA or DMT. Other diols that can be copolymerized in such polyesters include, for example, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. Aromatic and aliphatic acids that can be used simultaneously to make copolymers include, for example, isophthalic acid and sebacic acid.
Preferred catalysts for producing PTT include titanium and zirconium compounds. Suitable catalytic titanium compounds include, but are not limited to, titanium alkylates and derivatives thereof, titanium complex salts, titanium complexes with hydroxycarboxylic acids, titanium dioxide-silicon dioxide-co-deposits and hydrated alkali-containing titanium dioxide. .. Specific examples are tetra- (2-ethylhexyl) -titanate, tetrastearyl titanate, diisopropoxy-bis (acetylacetonato) -titanium, di-n-butoxy-bis (triethanolaminoto) -titanium, tributylmono. Includes acetyl titanates, triisopropyl monoacetyl titanates, tetrabenzoic acid titanates, alkaline titanium oxalates and malonates, potassium hexafluoro titanates, and titanium complexes with tartaric acid, citric acid or lactic acid. Preferred catalytic titanium compounds are titanium tetrabutyrate and titanium tetraisopropirate. Corresponding zirconium compounds can also be used. The polymers of the present invention may also contain small amounts of phosphorus compounds such as phosphates and catalysts such as cobalt compounds which tend to impart a blue hue.
Following the melt phase polymerization described above, a crystallization step followed by a solid phase polymerization (SSP) step can be performed to achieve the intrinsic viscosity required for bottle production. Crystallization and polymerization can be carried out in a tumble dryer reaction in a batch system. Instead, crystallization and polymerization can be accomplished in a continuous solid state method, whereby the polymer flows from one container to another after the scheduled treatment within each container.
Crystallization conditions preferably include temperatures of about 100 to about 150 ° C. Solid phase polymerization conditions preferably include temperatures from about 200 to about 232 ° C, more preferably from about 215 to about 232 ° C. Solid phase polymerization can be carried out for a time sufficient to increase the intrinsic viscosity to a desired level depending on the application. The preferred intrinsic viscosity for typical bottle applications is approximately 0.65 to approximately 1.0 deciliter / gram when measured by ASTM D-4603-86 in a mixture of phenol and tetrachloroethane with a mass of 60/40 at 30 ° C. Is. The time required to reach this viscosity can range from about 8 to about 21 hours. In one embodiment of the invention, the film-forming polymers of the invention may include regenerated polyesters or substances derived from regenerated polyesters such as polyester monomers, catalysts and oligomers.
The present invention has at least one wall, the wall of which provides a container containing a mass occupied area. Population occupied areas include membrane-forming polymers and particle populations. There is a technique that can localize a particle population to one area of the vessel wall. For example, if the contact surface of the film or wall is a surface adjacent to the material to be packaged, the oxygen scavenger can be advantageously localized on the contact surface in one area. Examples of these techniques include, but are not limited to, stacking, simultaneous extrusion, simultaneous injection, and the like. Examples of techniques capable of localizing the population are further disclosed in U.S. Pat. Nos. 5,153,038, 6,413,600, 4,525,134, 4,439,493 and 4,436,778, which are referred to herein. Completely incorporate by doing. Large amounts of particles can be incorporated into the film or wall produced by using these techniques. The localized region in which the particle population is substantially arranged is referred to as a population occupied region in the present specification.
The thickness of the mass occupied area is measured cross-sectionally through the container wall, measured from the content side of the packaging wall to the outer edge of the wall, starting with the first particle of the population and ending when 95% of the population is accounted for. The thickness of the mass occupied area in one layer of film or container is the thickness of the film or container wall. In the non-layered container wall, the thickness of the mass occupied area is somewhat thinner than the wall thickness. The thickness of the mass occupied area of the laminated wall is the thickness of the wall layer containing at least 95 percent of the particle population. In multilayer films or walls where the layers fuse at the interface, such as those formed by co-extrusion, the thickness of the population occupied area is the cross-sectional thickness of the layer containing at least about 95 percent of the particle population.
For two or more separate group occupied areas, the thickness of the group occupied area is reduced by the thickness of one or more unoccupied areas between the inner and outermost group occupied areas. This is the case for the ABA structure in which A contains a population. The thickness of the mass occupied area is the thickness of A + B + AB. In the case of ABAB, the thickness is still A + B + AB. Using the same principle, BABAB has a thickness of A + B + AB. ABABA has a population thickness of 3 x A-2 x B.
Preferably the number of particles in the mass occupied area is 6 x 10 per cubic centimeter of polymer.<sup>7</sup>Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed. More preferably, the number of particles in the mass occupied area is 3 x 10 per cubic centimeter of polymer.<sup>7</sup>Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed. More preferably, the number of particles in the mass occupied area is 1.5 x 10 per cubic centimeter of polymer.<sup>7</sup>Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Concentration does not exceed. The particle population includes deoxygenated particles and any other container component as discussed herein, which are present in the form of dispersed particles.
The oxygen-removing resin composition of the present invention further contains oxygen-removing particles. Suitable oxygen scavenging particles contain at least one oxidizable substance capable of reacting with molecular oxygen. Desirably, select a substance that reacts with oxygen too quickly and does not make the handling of the substance infeasible. Therefore, stable oxygen scavengers that do not easily explode or burn in contact with molecular oxygen are preferred. Low toxicity substances are preferred from a food safety standpoint, but are not limited by appropriate precautions. Particles should not adversely affect the sensory acceptability of the final product. Preferably the oxygen scavenging particles are calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium and these. Contains oxygen scavenging elements selected from the combination of. More preferably, the oxygen scavenging particles contain an oxygen scavenging element selected from calcium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc or tin. More preferably, the oxygen-removing particles contain iron. It will be appreciated that these oxygen scavenging elements can be present as a mixture in compounds such as oxides and salts, or can be combined with other elements. However, the condition is that the oxygen scavenging element can react with molecular oxygen. Alloys containing at least one oxygen scavenging element are also suitable. Oxygen-removing particles may contain impurities that do not affect the practice of the present invention.
In the art, it is known that certain substances enhance the oxygen scavenging reaction. In a preferred embodiment of the present invention, the oxygen-removing particles are pretreated with one or more reaction enhancers that promote the oxygen removal reaction. Any reaction enhancer known in the art can be used. In one embodiment of the invention, the oxygen scavenging particles include iron particles. Iron reacts with oxygen as an oxygen scavenger in its function. Iron metals or alloys or mixtures containing iron metals can be used. Furthermore, it should be understood that iron metals may contain impurities that do not affect the practice of the present invention.
At least three types of iron metal powders: electrolytic iron, sponge iron and carbonyl iron are available. Electrolytic iron is produced by electrolysis of iron oxide and is available, for example, from OM Group, Inc. in annealed and unannealed forms. Sponge iron is available, for example, from North American Hoeganaes, Inc. At least two types of sponge iron: hydrogen-reduced sponge iron and carbon monoxide-reduced sponge iron are present. Carbonyl iron powder can be obtained, for example, from Reade Advanced Materials. It is manufactured using the carbonyl degradation method.
Depending on the type of iron selected, the particles can vary widely in purity, surface area and particle shape. The following non-limiting examples of typical features contained herein illustrate variants that may be encountered. Electrolytic iron is known for its high purity and high surface area. The particles are tree-like. The carbonyl iron particles are substantially uniform spheres and can have a purity of up to about 99.5 percent. Carbon monoxide reduced sponge iron is typically about 95 square meters per kilogram (m)<sup>2</sup>It has a surface area of (/ kg), while hydrogen-reduced sponge iron typically has a surface area of about 200 m.<sup>2</sup>It has a surface area of / kg. Iron sponge may contain small amounts of other elements such as carbon, sulfur, phosphorus, silicon, magnesium, aluminum, titanium, vanadium, manganese, calcium, zinc, nickel, cobalt, chromium and copper.
Oxygen-removing particles are present in an effective amount for sufficient oxygen-removing capacity. If too few oxygen-removing particles are present, a large amount of oxygen can pass through the vessel wall without being removed. The amounts required for sufficient oxygen scavenging capacity include the application, the type of polymer used, the desired amount of gas blocking protection, the type of scavenging particles, the particle size of the scavenging particles and the moisture content of the packaged material. It depends on the factors. Preferably, the oxygen scavenger of the present invention contains at least about 50 mass ppm of oxygen scavenging particles of the resin. More preferably, the container of the present invention contains at least about 100 mass ppm of oxygen-removing particles of the resin. More preferably, the container of the present invention contains at least about 500 mass ppm of oxygen-removing particles of the resin. More preferably, the container of the present invention contains at least about 1000 mass ppm of oxygen-removing particles of the resin.
We have found that containers containing oxygen-removing particles up to about 12,000 mass ppm (1.2 mass percent) of resin, such as films or bottles, can have acceptable haze properties. It will be appreciated that the amount of deoxygenated particles or other particles can be quite large for applications where haze is not an important issue. Further features of the particle population required for the practice of the present invention are given below.
The compositions of the present invention, optionally, may further comprise one or more reaction enhancers known in the art to facilitate the oxygen scavenging reaction. Examples of known reaction enhancers are discussed in US Pat. Nos. 5,744,056 and 5,885,481, which are fully incorporated by reference herein. Suitable agents are variously described as hydroscopic substances, electrolyte acidifying agents, non-electrolyte acidifying agents, metal halides, metal sulfates, metal hydrogen sulfates and salts. Reaction enhancers can be added to the polymer melt or during extrusion.
The compositions of the present invention, if desired, include toughening agents, mold release agents, denesting agents, stabilizers, crystallization aids, antioxidants, UV absorbers, catalyst activators, colorants, nuclei. It may further comprise one or more components selected from the group consisting of agents, acetaldehyde reducing agents, reheat reducing agents, fillers, branching agents, foaming agents, accelerators and the like. If any of the above components retain distinct properties in the resin, it will be understood that they are part of a particle population as defined herein.
The present invention further relates to a method of incorporating a large amount of particles into a polyester resin composition with a low haze. The particles can be mixed with thermoplastic polymers, polymer melts or molded powders or pellets during or after polymerization, from which injection molded articles are formed or films or sheets are cast. Thus, the particles can be added during any process step, eg, during melt phase polymerization, after melt phase polymerization (after polymerization), before pelletization, during solid phase polymerization and during extrusion. Alternatively, a masterbatch of oxygen scavenging resin can be made and then mixed or blended with additional resin. Preferably the masterbatch contains a relatively large amount of particles and the desired particle concentration in the product polymer is achieved by mixing or blending the masterbatch with an additional amount of resin.
The oxygen-removing polyester resin of the present invention has both an effective oxygen-removing function and an acceptable optical property when formed in a container. The optical properties of a polymer are related to both the degree of crystallinity and the actual polymer structure. Transparency is defined as a state in which an object can be recognized by passing through a sample. Transmission is transmitted light. Transparency is measured as the amount of unbiased light. In other words, transparency is the original intensity of the incident light minus all the light lost by absorption, scattering or any other method. While many polymers are transparent, polymers that are transparent to visible light can become opaque as a result of the presence of additives such as fillers, stabilizers, flame retardants, moisture and gas. The opacity is due to the light scattering process that occurs in the material. Light scattering reduces the contrast between the light and dark areas of the object seen through the material, and between other colored areas, resulting in emulsion or haze in the transmitted image. Haze is a measure of the amount of light that deflects at least 2.5 degrees from the direction of light transmission.
The color and lightness of the polyester product can be visually observed and can be quantitatively measured with the HunterLab ColorQuest Spectrometer. This device is a color and lightness 1976 CIE a<sup>*</sup>, B<sup>*</sup>And L<sup>*</sup>Use symbols. a<sup>*</sup>The coordinates define the axis of color, in which positive values are on the red side of the color spectrum and negative values are on the green side. b<sup>*</sup>The coordinates define the second axis of color, in which positive values are on the yellow side of the spectrum and negative values are on the blue side. High L<sup>*</sup>The value indicates the enhanced brightness of the substance. In general, the acceptable turbidity of an article, such as a bottle or film, is visually defined. However, the HunterLab ColorQuest Spectrometer can quantitatively indicate the haze of an article or resin. This quantitative measurement value is referred to herein as a permeation hunter haze.
In this technique, it is known that stretched films will often have a higher haze than their unstretched counterparts. Therefore haze measurements were obtained on the stretched and unstretched vessel walls, as well as through the bottle itself. The container wall of the present invention may include an unstretched film or sheet. The production of films and sheets is known in the art, and any of many suitable techniques can be used to produce the film.
The container of the present invention may also include a bottle developed from a premolded article. A premold is a molded structure that is developed to form a bottle in a mold. Alternatively, the container may include a film, pouch or other packaging material. Generally, polyester bottles are manufactured by a blow molding method, in which the premold is heated above the glass transition temperature of the polyester, the heated premold is placed in a mold of the desired bottle form and into the premold. This is done by injecting air, pressing the premolded part into the shape of the mold, and pushing the molded bottle out of the mold onto the conveyor belt.
Two factors that must be taken into account when measuring haze accurately and comparing haze values are the thickness of the article being measured and the blow window. A blow window graph is constructed to establish an appropriate temperature and processing time to obtain the lowest haze value by the polyester resin crystallization method alone. Blow window graphs show haze as a function of heat exposure time of the premold. The graph is usually constructed by creating isotherms and heating each premold at the same temperature for different lengths of time. The heated premold is then stretched and haze measurements are taken at the stretched portion. Several different temperatures are selected. Generally, the resin has the best temperature that produces the lowest haze value, which temperature is used to perform the rest of the evaluation. In the work described here, select one temperature and change the time parameter<u style="single">To</u>I let you.
Granular additives can reduce transparency and increase haze if the polyester has excellent optical properties even when crystallized by strain curing (stretching). The number and particle size of the particles affect the haze of both stretched and unstretched films and articles. Those skilled in the art will recognize that the thermoplastic resins disclosed herein vary considerably in density. In addition, the density of particle populations can change. Therefore, the preferred concentration of particles in the resin and the population of removed particles is expressed as the number of particles per resin volume.
It will be understood that not all particles in every particle population have the same size and include a particle size range. In addition, the particles in the population may or may not have a uniform and well-shaped shape. A particle population or any part of the population can be described with an average particle size as measured by any standard technique known in the art. These techniques include measurement of the equilibrium rate at which particles settle in the liquid under the influence of gravity, resistance pulse counters, optical blockage counters, image analysis, laser diffraction spectroscopy and photon correlation spectroscopy. Statistical values commonly used to describe the particle size of a particle population are (1) the geometric mean dimension (which is the average particle size calculated on the log basis) and (2) the arithmetic mean (which is the linear basis). Includes (3) median dimension (which is the 50th percentile of the distribution), and (4) mode dimension (which is the most predominant particle size of the distribution).
In addition, the sample may be described by a particle size range or below a predetermined particle size. These can be defined by sieving techniques known in the art or other techniques. Therefore, any given particle population will have a particle size distribution that is a description of the particle size range and the amount of particles in each dimension. Techniques for particle size measurement are further described by Paul Webb and Clyde Orr in Analytical Methods in Fine Particle Technology, Micromeritics Instrument Corp. (1997), and James PM Syvitski in Principles, Methods, and Applications of Particle Size Analysis, Cambridge University. Discussed within the Publishing and Publishing Office (1991), both of which are fully incorporated by reference here.
We have found that various parameters are desirable for particle size within the particle population. It will be recognized that significant amounts of such large particles should be avoided, for example particles larger than the thickness of the vessel wall can create a rough surface. The particle size is generally preferably in the range of about 1 to about 70 microns, more preferably about 10 to about 70 microns, even more preferably about 15 to about 70 microns. More preferably, the particle size is in the range of about 20 to about 70 microns. These preferred ranges are given only as a general guide, and a few particles may be outside these ranges that do not affect the essential characteristics of the resin, and therefore they are of the present invention. It will be understood that it is within the range. Large amounts of particles can be added to the polymer as described above, and the effect on haze is minimized by selecting the particle size distribution of the particle population and controlling the total number of particles to remain below a certain maximum. To. This maximum value is related to the thickness of the mass occupied resin, which is described above.
In some applications, it may be desirable to further control the particle size distribution of the particle population to minimize haze. Such desirability may depend on factors including container type, processing conditions and draw ratio. Manufactured by using an iron-containing thermoplastic resin composition when the oxygen-removing particles contain iron and the particles with an iron particle size distribution of about 25 microns or less do not exceed about 1250 mass ppm of the resin. Bottles and other packaging materials have been advantageously found to have acceptable color and haze properties. Preferably, iron particles less than about 20 microns do not exceed about 800 mass ppm of the resin. More preferably, particles smaller than about 20 microns do not exceed about 500 mass ppm of resin. More preferably, particles less than about 20 microns do not exceed about 100 mass ppm of resin. Desirably, iron particles smaller than about 10 microns do not exceed about 800 mass ppm of resin. More preferably, iron particles smaller than about 10 microns do not exceed about 500 mass ppm of resin. More preferably, iron particles smaller than about 10 microns do not exceed about 100 mass ppm of resin. Preferably, iron particles of about 5 microns or less do not exceed about 500 mass ppm of the resin. More preferably, iron particles of about 5 microns or less do not exceed about 100 mass ppm of the resin.
Therefore, it is understood that the statement "less than about 25 microns" in the specification and claims includes smaller iron particle sizes of 20 microns, 10 microns, 5 microns and less than 5 microns, depending on the preferred dimensions. It should be. Similarly, the statement "does not exceed about 1250 ppm" includes lesser amounts of 800 ppm, 500 ppm and 100 ppm, depending on the preferred amount. Particles larger than the thickness of bottles and other packaging materials produced by using the polyiron thermoplastic resin composition can create a rough surface, so significant amounts of such large particles should be avoided. That will be recognized.
More generally, the favorable particle size distribution of deoxygenated particles is defined as a function of the apparent density of the particles. The density of metal powder particles is not necessarily the same as the density of the material from which they are made, due to the internal pore space of the particles. Apparent density refers to the mass of a unit volume of loose particles, usually cubic centimeters per gram (g / g /<u style="single">c</u>m<sup>3</sup>). The characteristics of the powder that determine its apparent density are discussed in Peter K. Johnson, "Powder Metallurgy", Kirk Othmer Encyclopedia of Chemical Technology, §§4.1, 4.2 (1995). The apparent density values typical of iron particles reported by Johnson range from about 0.97 to about 3.4 grams per cubic centimeter. When using particles containing iron or other substances, the advantageous particle size distribution of the particles is determined by the following formula.
Preferably, the particle size distribution of the deoxidized particles is such that particles of about 25 microns or less have the formula: ppm = 512.3 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 25 microns, d. Is the apparent density of cubic centimeters per gram of particles less than about 25 microns in size. ] Does not exceed the concentration specified by. The constant 512.3 in the above equation was derived from a calculation based on a particle size distribution such that particles of about 25 microns or less do not exceed a concentration of 1250 mass ppm, in which the particles have an apparent density of about 2.44 grams per cubic centimeter.
More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 20 microns or less have the formula: ppm = 327.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 20 microns. d is the apparent density of cubic centimeters per gram of particles less than about 20 microns in size. ] Does not exceed the concentration specified by. The constant 327.9 was determined by the same method as the above equation, as in each of the following equations. More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 20 microns or less have the formula: ppm = 204.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 20 microns. d is the apparent density of cubic centimeters per gram of particles less than about 20 microns in size. ] Does not exceed the concentration specified by. It is preferable that the particle size distribution of the oxygen-removing particles is about 20 microns or less. ppm = 41.0 × d [In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 20 microns in size, and d is the apparent density of particles less than about 20 microns per gram per cubic centimeter. ] Does not exceed the concentration specified by.
Desirably, the particle size distribution of the oxygen-removed particles is such that particles of about 10 microns or less have the formula: ppm = 327.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 10 microns, d. Is the apparent density of cubic centimeters per gram of particles less than about 10 microns in size. ] Does not exceed the concentration specified by. More preferably, the particle size distribution of oxygen-removing particles is such that particles of about 10 microns or less have the formula: ppm = 204.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 10 microns. d is the apparent density of cubic centimeters per gram of particles less than about 10 microns in size. ] Does not exceed the concentration specified by. More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 10 microns or less have the formula: ppm = 41.0 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 10 microns. d is the apparent density of cubic centimeters per gram of particles less than about 10 microns in size. ] Does not exceed the concentration specified by.
Preferably, the particle size distribution of the oxygen-removed particles is such that particles of about 5 microns or less have the formula: ppm = 204.9 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 5 microns, d. Is the apparent density of cubic centimeters per gram of particles less than about 5 microns in size. ] Does not exceed the concentration specified by. More preferably, the particle size distribution of the oxygen-removing particles is such that particles of about 5 microns or less have the formula: ppm = 41.0 × d [in the formula, ppm is the approximate concentration of ppm by mass for particles with dimensions less than about 5 microns. d is the apparent density of cubic centimeters per gram of particles less than about 5 microns in size. ] Does not exceed the concentration specified by.
The present invention also includes film-forming polyesters and granules, in which particles less than about 25 microns in size are of the formula: ppm = 512.3 × d [where ppm is the mass of particles less than about 25 microns in size. Approximate concentration of ppm, d is the apparent density of particles less than about 25 microns in size, in centimeters per gram. ] Provided a resin composition in which the granules have a particle size distribution that does not exceed the concentration determined by. The granules may or may not contain an oxygen scavenging element. Suitable granules include, but are not limited to, ceramics, plastics and metal granules, molecular sieves and the like.
Prepare the particle population, select the particle size distribution of the population to include the appropriate number of particles within the preferred dimensional range, melt phase polymerization of the polymer, after polymerization and before pelletization, solid phase polymerization of the polymer and During one or more of the extrusion process steps, the particle population is added to the polymer to form a mixture of polymer and particles, and the mixture of polymer and particles is used to make a container with at least one wall. By forming, a large amount of particles can be incorporated into the container wall with low haze. As described above, the particle population can be localized to one or more population-occupied regions of the vessel wall by various techniques. In this embodiment, the mass-occupied region comprises a mixture of polymers and particles, and the method of assembling the mixture further combines the mixture with additional polymer to form a wall having the mass-occupied region and at least one other region. Including the process of The additional polymer can be a different polymer or the same polymer in the absence of a remover.
The low-haze oxygen-removing resin of the present invention can be cast onto unstretched films or sheets of any thickness typically used in polymer film technology. In a preferred embodiment, the film has a thickness of at least about 0.5 mil and a transmission hunter haze number of preferably less than about 10 percent, more preferably less than about 8 percent, even more preferably less than about 5 percent. Although higher than the number of haze in polyester samples that do not contain deoxygenated particles or other particles, these haze values are well within the acceptable range for many commercial applications.
The low-haze oxygen-removing resin of the present invention can be stretched into bottles, wherein the side walls of each bottle are about 9 to about 35 mils, preferably about 11 to about 25 mils, more preferably about 14 mils. ~ Has a thickness of about 21 mils. In a preferred embodiment, the sidewalls of each bottle have a thickness of about 14 to about 21 mils, and the bottle is preferably less than about 10 percent, more preferably less than about 8 percent, even more preferably less than about 5 percent. It has a hunter haze number under optimal blow window conditions. Although higher than the iron or other particle-free polyester samples of the oxygen scavenging composition, these haze values are well within the acceptable range for many commercial applications.
The maximum preferred particle concentration described above was defined for unstretched films with a crystallinity of less than about 1 percent. Generally, as the crystallinity of the polymer resin increases, the haze increases. Therefore, it will be appreciated that the highest preferred particle concentration will be lower in polymer compositions with higher crystallinity. To illustrate the practice of the present invention, the following examples were prepared and tested as described in the General Experiments section disclosed below. However, the examples should not be considered as limiting the scope of the invention. The claims play a role in defining the present invention.
<u style="single">General experiment (GENERAL EXPERIMENTATION)</u><u style="single">Preparation of Examples Nos. 1-26</u> PET copolymer resins were prepared according to the teachings of US Pat. No. 5,612,423, which is fully incorporated by reference herein. Iron particle samples with various particle sizes were obtained. Hydrogen-reduced sponge iron from Pyron was used for Examples 1-10. Carbonyl iron powder obtained from ISP Technologies was used for Examples 11-26. The iron particles used in Example 3 had a particle size range of about 25 to about 38 microns. It will be appreciated that such samples can be prepared using, for example, a sieve. Iron particles were added to the polyester resin by using a metered feeder with a twin-screw screw extruder to form a resin masterbatch containing 2.5% by weight of the iron-containing resin composition. This masterbatch was blended with the base resin to give the desired concentration. The base resin / iron mixture was dried under reduced pressure at 325 ° F (163 ° C) for 18 hours. Dry resin, Novotec of Nissei ASB 50T Injection Blow-Molding machine Transferred to a dry hopper. The hopper was heated to 325 ° F (163 ° C) and set for a dew point of -40 ° F (-40 ° C).
In a two-step process, bottle premolds were produced and blown into bottles. First, the premold was manufactured on a Mini-jector or Nissei machine. The bottle was then blown from the premolded article on a Cincinnati Milacron Reheat Blow Lab (RHB-L) injection molding machine. Premolds were manufactured in a Mini-jector with a cycle time of 45 seconds and an injection time of 15 seconds at a rear heater temperature of 270 ° C, a front heater temperature of 275 ° C and a nozzle heating of 275 ° C. The injection pressure was between about 1000-1500 psig. The oven temperature at Milacron RHB-L ranged from about 163 to about 177 ° C. The exposure time was about 31 to about 52 seconds.
Haze measurements were made through the side wall of the bottle, which is the thinned stretched portion. Since these measurements were made for the entire bottle, the thickness effectively has two sidewalls. We used the HunterLab ColorQUEST Sphere Spectrophotometer System with an IBM PS / 2 model 50Z computer, an IBM Proprinter II dot matrix printer, a categorized specimen holder, green, gray and white calibration tiles, and an optical trap. HunterLab The Spectrocolorimeter integrating sphere sensor is a color and appearance measuring instrument. Light from the lamp was diffused by an integrating sphere and traveled from the subject to the lens through either (transmission) or reflection (reflectance). The lens collects the light and directs it to the grating, which disperses it to its component wavelengths. The dispersed light is reflected by the silicon diode array. The signal from the diode travels through the amplifier to the converter and is processed to produce data. Haze data is provided by the software. It is a calculated ratio of light transmission to diffuse light transmission multiplied by 100, resulting in a "haze%" (0% is transparent and 100% is opaque). Samples made for either transmittance or reflectance must be clean and free of surface scratches or wear. The sample size must match the geometry of the spherical opening, and in the case of transmittance, the sample size is limited to the size of the compartment. Each sample is tested at four different locations, such as the side wall of the bottle or a typical film area.
A Panametrics Magna-Mike 8000 Hall Effect Thickness Gauge was used to measure the thickness of the side wall of the bottle. Place a small steel ball on one surface of the test material and place the magnetic probe down. The distance between the sphere and the probe is measured by a Hall effect sensor. In particular, we used the Magna-Mike 8000 with a DPU-411 thermal printer (Type II), remote footswitch, target ball kit and Standard 801PR Probe. The measurements were taken twice and averaged. Tables 1 and 2 summarize the iron particle concentration, the average grain size of iron, and the haze values under constant sample thickness of about 11 to about 13 mils and optimum blow window conditions. Comparative Examples 1, 6 and 11 did not contain iron particles. The particle size of the iron particles reported in Table 1 was provided by the supplier. The particle size of the iron particles in Table 2 was measured as a geometric mean based on volume.
<tables num="1"><img file="JP4166151B2_D0001.tif" /></tables>
<tables num="2"><img file="JP4166151B2_D0002.tif" /></tables>
<u style="single">Creation of Examples 27 to 32</u> Examples 27 to 32 are also stretched film samples produced as described above. The results are shown in Table 3. The type of iron used for Examples 27-29 was unannealed electrolytic iron with a volume-based geometric mean particle size of approximately 10.84 microns. The iron used for Examples 30-32 was carbon monoxide reduced sponge iron with a geometric mean particle size of about 18.61 microns based on volume. The number of parts of iron per cubic centimeter of polymer can be compared, but the number of particles per cubic centimeter of polymer increases as the particle size decreases, and so does the permeation hunter haze per mil of film thickness. It should be noted that for Examples 27-32, haze measurements were made only on the side wall of the bottle and not through all the bottles.
<tables num="3"><img file="JP4166151B2_D0003.tif" /></tables>
<u style="single">Creation of Examples 33 to 44</u> Films were made using a Haake mixer to determine the optimum concentration of particles of various sizes in the unstretched resin. 2500.0 grams of HiPERTUF 89010 copolyester resin was weighed into each of several 1 gallon cans and dried overnight at approximately 100 ° C under full decompression in a vacuum oven. The decompression was returned to atmospheric pressure with nitrogen. An appropriate amount of carbonyl iron powder (manufactured by ISP Technologies) was weighed under nitrogen in vials at different desired concentrations. The nominal particle size range of iron provided by the supplier was about 7 to about 9 microns. The geometric mean particle size based on the volume of this iron powder was about 7.891 microns. Iron was added to the resin just before removing the thermoplastic from the oven, the vials were sealed and the mixture was blended on a roller mill for about 5 minutes.
The blended mixture was added to the feed hopper of the Haake Polylab extrusion system for film production. The resin was melted in an extruder and extruded from the die in the form of a flat sheet. A thin, uncoated, substantially amorphous film was fed through a temperature controlled three-roll polishing stack and quenched to minimize crystallinity to give a final polished surface. The cooling film was wound around the core. Table 4 shows the measured film thickness (mil), permeation hunter haze (%) and haze (%) / mil of a typical film sample with a constant iron concentration. The iron concentration in Examples 33 and 34 was about 0.9659 × 10 particles per cubic centimeter of polymer.<sup>6</sup>In Examples 35-37, the number of particles is about 2.8978 × 10 particles per cubic centimeter of polymer.<sup>6</sup>It is an individual. It can be seen that the haze increases as the film thickness increases, but the haze per mil of film thickness remains constant. In Examples 38-44, the film thickness was kept constant at about 11 mils and the number of particles per cubic centimeter of polymer was varied. It can be seen that as the particle concentration increases, the haze per mil thickness increases.
<tables num="4"><img file="JP4166151B2_D0004.tif" /></tables>
<tables num="5"><img file="JP4166151B2_D0005.tif" /></tables>
As shown in Table 1, when the iron particle size is greater than about 25 microns, haze values of less than 10% are obtained even at iron levels of 2500 ppm. At 1250 ppm iron and 2500 ppm iron, maximum haze values were obtained when the average particle size was about 25 microns or less, i.e. in Examples 2 and 7, respectively. Nevertheless, when the iron particle size was less than about 25 microns, less than 10% haze values were obtained at iron levels up to about 12500 ppm. As shown in Table 2, when the iron particle size is less than about 9 microns, a haze value of less than 10% is obtained at iron levels up to about 800 ppm. Further, when the iron particle size is about 5 microns or less, a haze value of less than 10% is obtained at iron levels up to about 500 ppm.
As shown in Table 3, when the particle population is a constant number of parts per cubic centimeter of polymer, the number of particles per cubic centimeter of polymer decreases as the particle size increases. As shown in Table 4, the total permeation hunter haze increases as the sample thickness increases, but the haze per mil thickness remains relatively constant. As shown in Table 5, hunter haze values of less than 1.0% per mil of container wall are per cubic centimeter of polymer (6 x 10).<sup>7</sup>Particles ÷ T) [In the equation, T is the thickness of the mill in the mass occupied area. ] Can be obtained with particle concentrations up to.
As will be appreciated, the present invention overcomes the problems associated with the prior art by providing a thermoplastic resin composition containing an effective amount of oxygen-removing particles and having acceptable color and haze properties. The resulting resin can be used to form clear bottles, films and other container and packaging materials. These materials contain oxygen-removing particles in sufficient amounts to effectively remove oxygen, providing a longer shelf life for oxygen-sensitive materials. In addition, these materials have acceptable haze properties.
Although the best modes and preferred embodiments of the present invention have been shown in accordance with the Patent Statutes, the scope of the invention is not limited thereto, but rather is defined by the appended claims. The scope of the present invention therefore includes any modifications and modifications within the scope of the claims.<u style="single">Suitable embodiments of the present invention include:</u><u style="single">[1] Film-forming polyester and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">There are particles in it that are less than about 25 microns in size, but that is the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition in which particles have a particle size distribution that does not exceed the concentration determined by.</u><u style="single">[2] The resin composition according to the above [1], wherein the polyester contains a linear polyester or a branched polyester.</u><u style="single">[3] The above-mentioned [1], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[4] Oxygen-removing elements include calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium or The resin composition according to the above [1], which comprises a combination thereof.</u><u style="single">[5] The resin composition according to the above [1], wherein the oxygen removing element contains iron.</u><u style="single">[6] The resin composition according to the above [1], wherein the effective amount of oxygen-removing particles is about 50 to about 2500 mass ppm of the resin.</u><u style="single">[7] The resin composition according to the above [1], wherein the oxygen-removing particles have a particle size range of about 20 to about 70 microns.</u><u style="single">[8] The resin composition according to the above [1], wherein particles having a size of less than about 25 microns have an apparent density of about 0.97 to about 2.44 grams per cubic centimeter.</u><u style="single">[9] The resin composition according to the above [1], wherein particles having a size of less than about 20 microns have an apparent density of about 0.97 to about 2.44 grams per cubic centimeter and do not exceed a concentration of about 800 mass ppm of the resin.</u><u style="single">[10] The resin composition according to the above [1], wherein the oxygen scavenging particles are pretreated with one or more reaction enhancers.</u><u style="single">[11] The resin composition according to the above [1], wherein the bottle produced from the resin has a hunter haze value of about 10% or less.</u><u style="single">[12] Film-forming polyester and</u><u style="single"> Effective amount of iron particles</u><u style="single">A resin composition in which iron particles have a particle size distribution such that particles having a size of less than about 25 microns are present therein, but the particle size distribution does not exceed about 1250 mass ppm of the resin.</u><u style="single">[13] The resin composition according to the above [12], wherein the polyester contains a linear polyester or a branched polyester.</u><u style="single">[14] The above-mentioned [12], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[15] The resin composition according to the above [12], wherein the effective amount of iron particles is about 50 to about 2500 mass ppm of the resin.</u><u style="single">[16] The resin composition according to the above [12], wherein the iron particles have a particle size range of about 20 to about 70 microns.</u><u style="single">[17] The resin composition according to the above [12], wherein particles having a size of less than about 20 microns do not exceed about 800 mass ppm of the resin.</u><u style="single">[18] The resin composition according to the above [12], wherein the oxygen scavenging particles are pretreated with one or more reaction enhancers.</u><u style="single">[19] The resin composition according to the above [12], wherein the bottle produced from the resin has a hunter haze value of about 10% or less.</u><u style="single">[20] A resin composition containing iron particles of about 50 to about 2500 mass ppm of film-forming polyester and resin, and the concentration of iron particles having a size of less than about 25 microns does not exceed about 1250 mass ppm of resin.</u><u style="single">[21] The resin composition according to the above [20], wherein the polyester comprises a linear polyester or a branched polyester.</u><u style="single">[22] The above-mentioned [20], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[23] The resin composition according to the above [20], wherein the iron particles have a particle size range of about 20 to about 70 microns.</u><u style="single">[24] The resin composition according to the above [20], wherein particles having a size of less than about 20 microns do not exceed about 500 mass ppm of the resin.</u><u style="single">[25] The resin composition according to the above [20], wherein the oxygen scavenging particles are pretreated with one or more reaction enhancers.</u><u style="single">[26] The resin composition according to the above [20], wherein the bottle produced from the resin has a hunter haze value of about 10% or less when stretched to a thickness of about 11 to about 16 mils.</u><u style="single">[27] A polyester resin composition containing iron particles of about 50 to about 2500 mass ppm of a resin for use in forming a transparent product having a low haze, wherein the transparent product is about 10% or less. A resin composition having a hunter haze value of.</u><u style="single">[28] The above-mentioned [27], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. Resin composition.</u><u style="single">[29] Particles with dimensions less than about 25 microns have the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">The resin composition according to the above [27], wherein the iron particles have a particle size distribution that does not exceed the concentration determined by.</u><u style="single">[30] An article formed from a resin composition containing an effective amount of oxygen-removing particles, wherein the hunter haze value of the article is about 10% or less.</u><u style="single">[31] The article according to [30] above, which is a bottle.</u><u style="single">[32] In the above [30], the resin composition comprises polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. The article described.</u><u style="single">[33] The article according to [30] above, wherein the hunter haze value of the article is about 8% or less.</u><u style="single">[34] In the process of preparing an effective amount of oxygen-removing particles containing at least one oxygen-removing element capable of reacting with molecular oxygen, there are particles having a size of less than about 25 microns. formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A process in which the particles have a particle size distribution that does not exceed the concentration determined by; </u><u style="single"> Molten phase polymerization of polyester;</u><u style="single"> After polymerization and before pelletization;</u><u style="single"> Solid-phase polymerization of polyester; and</u><u style="single"> Extrusion</u><u style="single">The step of adding the oxygen-removing particles to the polyester resin composition during one or more of the process steps of</u><u style="single">A method for producing a film-forming polyester resin composition, which incorporates a large amount of oxygen-removing particles in a low haze.</u><u style="single">[35] The method according to [34] above, wherein the step of adding the oxygen-removing particles to the polyester resin composition further comprises a step of producing a masterbatch of the oxygen-removing resin and adding the masterbatch to the additional resin.</u><u style="single">[36] The above [34], wherein the polyester resin contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. the method of.</u><u style="single">[37] Oxygen-removing particles are in oxidizable forms of calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum, antimony, germanium, silicon, lead. , Cadmium, rhodium or a combination thereof, according to the method according to [34] above.</u><u style="single">[38] The method according to the above [34] or [35], wherein the oxygen scavenging element contains iron.</u><u style="single">[39] The method according to [34] above, wherein the effective amount of oxygen-removing particles is about 50 to about 2500 mass ppm of the resin.</u><u style="single">[40] The method of [34] above, wherein particles less than about 25 microns in size have an apparent density of about 0.97 to about 2.44 grams per cubic centimeter.</u><u style="single">[41] The method according to [34] above, wherein the particles having a size of less than about 20 microns have an apparent density of about 0.97 to about 2.44 grams per cubic centimeter and do not exceed a concentration of about 800 mass ppm of resin.</u><u style="single">[42] The method according to [34] above, wherein the oxygen-removing particles are pretreated with one or more reaction enhancers.</u><u style="single">[43] The method according to [34] above, wherein the bottle made from the resin has a hunter haze value of about 10% or less.</u><u style="single">[44] Film-forming polyester and</u><u style="single"> Granules containing oxygen-removing particles that can react with molecular oxygen</u><u style="single">There are particles in it that are less than about 25 microns in size, but that is the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition in which the granules have a particle size distribution that does not exceed the concentration determined by.</u><u style="single">[45] It has at least one wall, the wall contains a group occupied area, and the group occupied area is</u><u style="single"> Membrane-forming polymer, and</u><u style="single"> Particle population containing an effective amount of oxygen-removing particles</u><u style="single">The number of particles in the population is</u><u style="single"> Polymer per cubic centimeter (6 x 10)</u><sup><u style="single">7</u></sup><u style="single">Particles ÷ T)</u><u style="single">[In the formula, T is the thickness of the mill in the mass occupied area. ]</u><u style="single">A container having a permeation hunter haze of up to about 1 percent per mil of the container wall, not exceeding the concentration of.</u><u style="single">[46] The container according to [45] above, wherein the polymer contains polyester.</u><u style="single">[47] The container according to the above [46], wherein the polyester contains a linear polyester.</u><u style="single">[48] The above-mentioned [47], wherein the polyester contains polyethylene terephthalate, polyethylene terephthalate copolymer, polyethylene naphthalate, polyethylene naphthalate copolymer, polybutylene terephthalate, polybutylene terephthalate copolymer, polytrimethylene terephthalate or polytrimethylene terephthalate copolymer. container.</u><u style="single">[49] The container according to [45] above, wherein the polyester is made from one or more polyfunctional comonomer.</u><u style="single">[50] The container according to [49] above, wherein the polyfunctional comonomer is selected from the group consisting of pyromelitoic dianhydride and pentaerythritol.</u><u style="single">[51] The container according to [45] above, wherein the effective amount of oxygen-removing particles is at least about 50 mass ppm of the polymer.</u><u style="single">[52] Oxygen-removing particles include calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium or The container according to any one of [45] to [48] above, which comprises at least one of these combinations.</u><u style="single">[53] The container according to any one of the above [45] to [48], wherein the oxygen-removing particles contain iron.</u><u style="single">[54] The container according to [45] above, wherein the oxygen-removing particles contain iron and the oxygen-removing particles are present in an amount of about 50 to about 12,000 mass ppm of the resin.</u><u style="single">[55] Polymers are strengthening agents, mold release agents, denesting agents, stabilizers, crystallization aids, antioxidants, UV absorbers, catalyst activators, colorants, nucleating agents, acetaldehyde reduction. The container according to [45] above, further comprising one or more components selected from the group consisting of agents, reheat reducing agents, fillers, branching agents, foaming agents and accelerators.</u><u style="single">[56] The container according to [45] above, wherein the particle population further comprises reaction-enhancing particles.</u><u style="single">[57] The above-mentioned [56], wherein the reaction-enhancing particles include a hydroscopic substance, an electrolyte acidifying agent, a non-electrolyte acidifying agent, a metal halide, a metal sulfate, a metal hydrogen sulfate, or a mixture thereof. container.</u><u style="single">[58] The container according to [45] above, wherein the oxygen-removing particles are pretreated with at least one reaction enhancer.</u><u style="single">[59] The container according to any one of [45] to [48] above, which is a stretched bottle having a side wall thickness of about 11 to about 25 mils and a hunter haze value of about 10% or less.</u><u style="single">[60] The container according to the above [45], wherein the collective occupied area constitutes a stack of container walls.</u><u style="single">[61] The container according to the above [45], wherein the mass occupied area constitutes a simultaneous extrusion layer of the container wall.</u><u style="single">[62] The container according to the above [45], wherein the thickness of the collective occupied area is equal to the thickness of the container wall.</u><u style="single">[63] The container according to the above [45], wherein the thickness of the collective occupied area is thinner than the thickness of the container wall.</u><u style="single">[64] The container according to [45] above, which is a tray.</u><u style="single">[65] Film-forming polyester and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 25 to about 38 microns and particles in the dimensional range of about 38 to about 45 microns are present, and Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u><u style="single">[66] Film-forming polyester and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 38 to about 45 microns and particles in the dimensional range of about 45 to about 75 microns are present. Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u><u style="single">[67] Film-forming polyester, and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 25 to about 38 microns and particles in the dimensional range of about 38 to about 75 microns are present, and Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u><u style="single">[68] Film-forming polyester, and</u><u style="single"> Effective amount of oxygen scavenging particles containing at least one oxygen scavenging element capable of reacting with molecular oxygen</u><u style="single">The particles have a particle size distribution such that particles in the dimensional range of about 25 to about 45 microns and particles in the dimensional range of about 45 to about 75 microns are present. Particles with dimensions less than about 25 microns, the formula:</u><u style="single"> ppm = 512.3 × d</u><u style="single">[In the formula, ppm is the approximate concentration of ppm by mass for particles less than about 25 microns in size, and d is the apparent density of particles less than about 25 microns in size per gram cubic centimeter. ]</u><u style="single">A resin composition that does not exceed the concentration determined by.</u>
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| KR20040060915A | Republic of Korea | A | |
| BR0211671A | Brazil | A | |
| BR0211672A | Brazil | A | |
| US6780916B2 | United States of America | B2 | |
| AR036243A1 | Argentina | A1 | |
| AR036244A1 | Argentina | A1 | |
| US2004178386A1 | United States of America | A1 | |
| CN1556831A | China | A | |
| CN1558926A | China | A | |
| MXPA04000708A | Mexico | A | |
| MXPA04000709A | Mexico | A | |
| HU0402040A2 | Hungary | A2 | |
| HUP0402040A2 | Hungary | A2 | |
| PL368369A1 | Poland | A1 | |
| JP2005507955A | Japan | A | |
| PL368583A1 | Poland | A1 | |
| JP2005509049A | Japan | A | |
| HRP20040187A2 | Croatia | A2 | |
| HRP20040188A2 | Croatia | A2 | |
| ZA200401543B | South Africa | B | |
| ZA200401544B | South Africa | B | |
| RU2004105601A | Russian Federation | A | |
| RU2004105600A | Russian Federation | A | |
| EP1423456A4 | European Patent Office (EPO) | A4 | |
| EP1430089A4 | European Patent Office (EPO) | A4 | |
| EP1001718B1 | European Patent Office (EPO) | B1 | |
| AT304329T | Austria | T | |
| ATE304329T1 | Austria | T1 | |
| HU0500593A2 | Hungary | A2 | |
| HUP0500593A2 | Hungary | A2 | |
| DE69831575D1 | Germany | D1 | |
| EP1598032A2 | European Patent Office (EPO) | A2 | |
| EP1598032A3 | European Patent Office (EPO) | A3 | |
| DE69831575T2 | Germany | T2 | |
| US6997945B2 | United States of America | B2 | |
| HU0500593A3 | Hungary | A3 | |
| HUP0500593A3 | Hungary | A3 | |
| US2006100691A1 | United States of America | A1 | |
| CN1789328A | China | A | |
| CN1800243A | China | A | |
| UA77198C2 | Ukraine | C2 | |
| UA77199C2 | Ukraine | C2 | |
| CN1304464C | China | C | |
| CA2288044C | Canada | C | |
| AU2002324540B2 | Australia | B2 | |
| AU2002355294B2 | Australia | B2 | |
| US2007098936A1 | United States of America | A1 | |
| US2007100050A1 | United States of America | A1 | |
| US7244779B2 | United States of America | B2 | |
| RU2307846C2 | Russian Federation | C2 | |
| RU2307847C2 | Russian Federation | C2 | |
| JP2008156000A | Japan | A | |
| JP4166151B2This record | Japan | B2 | |
| JP4166152B2 | Japan | B2 | |
| KR100868469B1 | Republic of Korea | B1 | |
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| US7485130B2 | United States of America | B2 | |
| JP2009082739A | Japan | A | |
| KR100898890B1 | Republic of Korea | B1 | |
| IL195082A0 | Israel | A0 | |
| IL195082D0 | Israel | D0 | |
| CN100558797C | China | C | |
| CN100591711C | China | C | |
| US7687124B2 | United States of America | B2 | |
| PL205234B1 | Poland | B1 | |
| IL160021A | Israel | A | |
| IL160024A | Israel | A | |
| US7740926B2 | United States of America | B2 | |
| CA2455583C | Canada | C |
24 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
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| Receipt of annual feesJAPANESE INTERMEDIATE CODE: R250R250 | R250 | |
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| Written notification of registration of transferJAPANESE INTERMEDIATE CODE: R350R350 | R350 | |
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| Certificate of patent or registration of utility modelJAPANESE INTERMEDIATE CODE: R150R150 | R150 | |
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Numbers
- Publication
- 4166151
- Publication, DOCDB
- 4166151
- Publication, EPODOC
- JP4166151B
- Application
- 2003515583
- Application, DOCDB
- 2003515583
- Application, EPODOC
- JP20030515583
Titles2
- Japanese
- 酸素除去樹脂組成物および低ヘーズを有する容器および関連方法
- English
- Oxygen-removing resin compositions and containers with low haze and related methods
Classification
- CPC, 16
- C08K3/34
- B65D81/266
- C08J3/226
- C08J2467/00
- C08K3/22
- B29C55/02
- C08J3/203
- C08K3/08
- C08J2367/02
- C08K2201/005
- B29C48/288
- B29C48/023
- Y10T428/1355
- Y10T428/1359
- Y10T428/1397
- Y10T428/1352
- IPC, 23
- C08L67 02
- C08K3 08
- C08K9 00
- C08J3 20
- B01J20 26
- B65D1 34
- B65D1 00
- B65D1 09
- B65D30 02
- B65D65 02
- B65D65 40
- B65D81 24
- B65D81 26
- C08G63 78
- C08J3 22
- C08J5 00
- C08K3 00
- C08K3 10
- C08K3 22
- C08K3 24
- C08K3 34
- C08K5 34
- C08L67 00