Mitsubishi Gas Chemical Company, Inc.

Amcol International Corporation

Kazunobu Maruo

Jun Mitadera

Tomomichi Kanda

Masashi Kurokawa

Koji Yamamoto

Kazunobu Sato

Katsuya Maruyama

Tie Lan

Ying Liang

Hiroka Tanisake

Satoshi Okada

Tomonori Kato

Takeshi Koyama

Tsuneaki Masuda

Tsukasa Toki

Hiroyuki Nanba

Toshizumi Hirota

Scott Omachinski

Shunichi Shinohara

Masahi Kurokawa

There is provided a multilayer bottle including outermost and innermost layers each made mainly of a polyester (A) and at least one barrier layer interposed between the outermost and innermost layers. The polyester (A) is a thermoplastic resin obtained by polymerizing a dicarboxylic acid component containing 80 mol % or more of terephthalic acid with a diol component containing 80 mol % or more of ethylene glycol. The barrier layer is composed of a polyamide (B) and a polyamide (C). The polyamide (B) is obtained by polycondensing a diamine component containing 70 mol % or more of m-xylylenediamine with a dicarboxylic acid component containing 70 mol % or more of an &#x3b1;,&#x3c9;-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. The polyamide (C) has a higher saturation water content than that of the polyamide (B) as measured at 23&#xb0; C. and 50% RH under 1 atm, and a content of the polyamide (C) in the barrier layer is 20% by weight or less on the basis of a weight of the barrier layer. The multilayer bottle hardly suffers from delamination upon dropping or upon exposure to impact and, therefore, is not required to have a shape with less irregularities or less bends for preventing the delamination, and further has a large freedom of design choice.

Multi-layer bottle

Provided are a resin composition which is colored little and has excellent gas barrier properties, transparency and mechanical properties, a method for producing it, and a shaped article. The composition is a polyester resin composition comprising from 2 to 30% by weight of a specific polyamide resin (A), from 69.5 to 97.99% by weight of a specific polyester resin (B) and from 0.01 to 0.5% by weight of a di- and/or tri-polycarboxylic acid compound (c), which satisfies a&#x2266;b, 60 &#x2266;a+b&#x2266;150, 1&#x2266;c&#xd7;Cc&#x2266;20, 1&#x2266;c&#xd7;Cc/(a&#xd7;Ca)&#x2266;12 (wherein a is a concentration of the terminal amino group of the polyamide resin (A), b is a concentration of the terminal carboxyl group of the polyamide resin (A), c is a concentration of the carboxyl group in the polycarboxylic acid compound (C), Cc is a concentration of the polycarboxylic acid compound (C) in the polyester resin composition, and Ca is a concentration of the polyamide resin (A) in the polyester resin composition (g/g). The method is for producing the resin composition; and the shaped article is obtained by shaping the resin composition.

Polyester resin composition, method for producing same and molded body

There is provided a method for filling a multilayer bottle including outermost and innermost layers and at least one barrier layer interposed between the outermost and innermost layers, with a material to be stored therein. In the filling method, the material to be stored is filled in the multilayer bottle having the barrier layer satisfying a specific glass transition point (Tg) and a specific water content as measured by a Carl-Fisher method at 230&#xb0; C. for 30 min. The multilayer bottle obtained by the filling method of the present invention hardly undergoes delamination between the layers owing to dropping or impact, and is applicable to a filling method such as hot filling.

Method for filling into multilayer bottle

There is provided a multilayer bottle comprising a barrel portion including an outermost layer, an innermost layer and at least one barrier layer interposed between the outermost layer and the innermost layer, which satisfies the requirements represented by the following formulae (1) to (3) at the same time:OTR&#x2266;0.2 cc&#xb7;mm/(m&#xb7;day&#xb7;atm)&#x2003;&#x2003;(1)where OTR represents an average oxygen transmission rate of the barrier layer of the barrel portion;20&#x2266;(Average degree of orientation of barrier layer of barrel portion)&#x2266;45; and&#x2003;&#x2003;(2)0&#x2266;&#xd7;100&#x2266;200&#x2003;&#x2003;(3)where 'a' represents an average thickness (&#x3bc;m) of the barrier layer of the barrel portion; and 'b' represents an average thickness (&#x3bc;m) of the barrier layer of a bottom portion of the bottle. The multilayer bottle is free from delamination owing to impact upon dropping even when the bottle is formed with irregularities and bends and therefore exhibits a large freedom of design choice.

Multi-layered bottle

The multilayer container of the present invention comprises an outermost layer, an innermost layer and at least one intermediate layer interposed between the outermost layer and the innermost layer. Each of the outermost and innermost layers is mainly made of a thermoplastic polyester resin A produced by polymerizing a dicarboxylic acid component comprising 80 mol % or higher of terephthalic acid with a diol component comprising 80 mol % or higher of ethylene glycol. At least one of the intermediate layers is mainly made of a mixed resin B of a polyamide resin C and a polyamide resin D in a mixing ratio of 99.5/0.5 to 80/20 by weight. The polyamide resin C is produced by polymerizing a diamine component comprising 70 mol % or higher of m-xylylenediamine with a dicarboxylic acid component comprising 70 mol % or higher of adipic acid. The polyamide resin D has a solubility index satisfying the formula (1):Sa&#x3c;Sd&#x3c;Sc&#x2003;&#x2003;(1)wherein each of Sa, Sb and Sd is a solubility index, calculated by Small method, of the thermoplastic polyester resin A, the polyamide resin C and the polyamide resin D. The polyamide resin D has a glass transition temperature of 130&#xb0; C. or lower which is higher than that of the polyamide resin C. The multilayer container is excellent in gas-barrier property and resistant to delamination even when its shape includes indented and bending portions, allowing a broad design latitude.

Multilayer container

There is provided a multilayer bottle including an outermost layer and an innermost layer which are each made of a thermoplastic polyester resin, and at least one barrier layer interposed between the outermost layer and the innermost layer. The barrier layer contains at least two components including a polyamide obtained by polycondensing a diamine component containing m-xylylenediamine as a main component with a dicarboxylic acid component containing an &#x3b1;,&#x3c9;-linear aliphatic dicarboxylic acid as a main component, and a thermoplastic resin having a lower molecular weight than that of the polyamide. The multilayer bottle hardly suffers from delamination upon impact or dropping and, therefore, is not required to have a shape with less irregularities or less bends for preventing the delamination, and further has a large freedom of design choice.

Multilayer bottle

Intercalates, exfoliates thereof, and nanocomposite compositions are formed by intercalating a layered silicate material, e.g., a phyllosilicate, with an oligomer or polymer intercalant that is a reaction product of at least one diamine with at least one dicarboxylic acid, to form a polyamide oligomer containing a xylylenediamine component. The oligomer or polymer may be formed in-situ by contacting the layered phyllosilicate with polymerizable monomer reactants using conditions to cause reaction and polymerization in the intercalating composition and intercalation of the resulting oligomer and/or polymer, between platelet layers of the phyllosilicate. An amine functionality of the oligomer or polymer is protonated for ion-exchange with interlayer cations of the phyllosilicate to bond the intercalant to the phyllosilicate platelet, at the protonated amine, at a negative charge site previously occupied by the interlayer cations.

Oligomer-modified layered inorganic compounds and their use in nanocomposites

The single-layered structure of the invention comprises (A) 50 to 97% by weight of a polyolefin, (B) 2 to 45% by weight of a polyamide resin comprising a diamine component and a dicarboxylic acid component and (C) 1 to 45% by weight of a modified polyolefin and/or styrene copolymer. The polyamide resin B is dispersed in layers throughout the single-layered structure. With such a dispersion state of the polyamide resin B, the single-layered structure exhibits excellent fuel barrier properties.

Fuel barrier single-layered structure and multi-layered shaped article

A resin composition comprising melt blending a polyamide resin such as nylon MXD6 with a polyphenoxy resin. The polyamide resin and the polyphenoxy resin may be combined prior to or after melting and can be sandwiched between two PET layers in a perform mold to form an article capable of blow molding to form a container with improved delamination resistance. Also, intercalated layered materials are prepared by co-intercalation of an onium ion, an aromatic polyamide oligomer or polymer, e.g., nylon MXD6, and a polyphenoxy oligomer or polymer between the planar layers of a swellable layered material, such as a phyllosilicate, preferably a smectite clay. The co-intercalated layered materials are combined with the aromatic polyamide and polyphenoxy resin to form a nanocomposite composition for sandwiching between PET layers to form containers having improved delamination resistance.

Resin compositions, intercalates, nanocomposites and laminates prepared with aromatic polyamide and polyphenoxy polymers

The thermoplastic resin composition of the invention comprises (A) 50 to 97% by weight of a polyolefin, (B) 2 to 45% by weight of a polyamide resin comprising a diamine component and a dicarboxylic acid component and (C) 1 to 45% by weight of a modified polyolefin and/or styrene copolymer. The polyamide resin is specified by that at least 70 mol % of the diamine component is a constitutional unit derived from m-xylylenediamine and at least 70 mol % of the dicarboxylic acid component is a constitutional unit derived from a C-Cstraight-chain &#x3b1;,&#x3c9;-aliphatic dicarboxylic acid and isophthalic acid in a molar ratio of 3:7 to 10:0. With such a chemical component, the thermoplastic resin composition exhibits excellent fuel barrier properties, heat resistance and moldability.

Fuel barrier thermoplastic resin composition and shaped article

In the process of the present invention, a polyamide A1 and an organized clay B are mixed mainly by dispersive mixing, and after added with a polyamide A2, mixed mainly by distributive mixing in a corotating intermeshing twin-screw extruder so designed as to effect the dispersive mixing and the distributive mixing. The organized clay B is completely and finely dispersed and distributed throughout the resultant polyamide composite material. Shaped articles such as films and sheets made of the polyamide composite material exhibit excellent gas barrier properties and transparency with little malodor mainly attributable to the decomposed products of the organizing agent for preparing the organized clay B.

Process for production of polyamide composite material

The fuel-barrier polyamide resin of the present invention is a product of the polycondensation of a diamine component comprising 70 mol % or higher of m-xylylenediamine and a dicarboxylic acid component comprising 70 mol % or higher of a mixed dicarboxylic acid which comprises a Cto C&#x3b1;,&#x3c9;-linear aliphatic dicarboxylic acid and at least one dicarboxylic acid selected from the group consisting of isophthalic acid and naphthalenedicarboxylic acid in a molar ratio of 30:70 to 95:5. The polyamide resin is excellent in not only fuel-barrier property and heat resistance, but also moldability and recyclability, and therefore suitably used as a barrier material of fuel containers.

Fuel-barrier polyamide resin and multilayer shaped article

The polyamide resin of the present invention is produced by polycondensation of a diamine component comprising 70 mol % or more of m-xylylenediamine and a dicarboxylic acid component comprising 70 mol % or more of a C4-C20 &#x3b1;, &#x3c9;-straight-chain aliphatic dicarboxylic acid in the presence of at least one phosphorus compound selected from the group consisting of phosphinic acid compounds and phosphonous acid compounds and in the presence of an alkali metal compound of a weak acid. The weak acid has a dissociation constant lower than a first dissociation constant of a dicarboxylic acid mainly constituting the polyamide resin. The polyamide resin satisfies the following requirements (A), (B) and (C):14000&#x2266;a&#x2266;40000&#x2003;&#x2003;(A)b&#x2266;1.000&#x2003;&#x2003;(B)0.9930&#x2266;&#x2212;1.1&#xd7;103.2&#xd7;10&#x2266;0.9980&#x2003;&#x2003;(C)wherein a and b are as defined in the disclosure.

Polyamide resin

The polyamide resin shaped article of the present invention is produced by preliminarily melt-kneading a m-xylylene-containing polyamide resin and a layered silicate subjected to a swelling treatment to prepare a resin composition containing the layered silicate in high concentration, melt-kneading the resin composition with another portion of m-xylylene-containing polyamide resin, and then formed into the shaped article. Since the amount of the m-xylylene-containing polyamide resin exposed to the heat history twice in the melt-kneading steps is minimized, the gel formation due to the thermal degradation can be reduced and the lowering of the relative viscosity due to the decrease of the molecular weight caused by the thermal degradation of the m-xylylene-containing polyamide resin is prevented.

Shaped article of polyamide resin and production thereof

A copolyesterimide composed of bis-trimellitimide units, 2,6-naphthalenedicarboxylic acid units, hydroquinone units and p-hydroxybenzic acid units. This copolyesterimide is melt-processable, and excels in heat resistance and mechanical properties.

Growing community of inventors

Kanagawa, Japan

Kazunobu Maruo