Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-08-04
2002-03-12
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S444000, C524S445000, C524S442000, C524S447000, C524S448000, C524S450000
Reexamination Certificate
active
06355717
ABSTRACT:
FIELD OF INVENTION
The present invention relates to polyamide-based resin compositions with good gas barrier properties.
BACKGROUND OF THE INVENTION
Polyamide resins have good heat resistance, gas barrier properties, transparency, oil resistance, shrinkability, and are broadly employed, e.g. for food packing material and automobile components. Recently, demands for a high degrees of food shelf stability, such as retort pouch treatment, have increased, and in particular demands for high gas barrier properties, slidability, and tear strength under high temperature conditions are required. However, the gas barrier properties of polyamide resins alone are not satisfying in comparison with ethylene-vinyl alcohol copolymers (EVOH), polyvinylidene chloride (PVDC), etc. Polyamide resins with better gas barrier properties are desirable.
SUMMARY OF THE INVENTION
It is the object of the present invention to find a solution to the above, and in particular to provide polyamide resin compositions with good gas barrier properties, hot water shrinkage, moulding shrinkage, slidability and tear strength.
It is an object of the present invention to provide polyamide resin compositions exhibiting good gas barrier properties even during water absorption, and moulded articles thereof. The present invention provides polyamide resin compositions with good gas barrier properties, good hot water shrinkage and good moulding shrinkage by the use of layered silicates that are subjected to a certain treatment with positively charged organic compounds.
The present invention provides barrier composite resin compositions and moulded bodies, comprising (A) aromatic polyamide resins or polyamide resin compositions containing at least one aromatic polyamide resin, and (B) a layered silicate modified by a triazine compound derivative.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Aromatic polyamide resins employed in (A) aromatic polyamide resins or polyamide resin compositions containing at least one aromatic polyamide resin of the present invention, include polyamide resins with at least one aromatic ring at the backbone chain. They may be polyamide resins produced by polycondensation of aliphatic, cycloaliphatic, aromatic diamine compounds, such as hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexyl)methane, m- or p-xylylene, diamine and aliphatic, cycloaliphatic, aromatic dicarboxylic acid compounds, such as adipinic acid, suberic acid, sebacic acid, cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, 1,3-phenylenedioxyzine acetic acid, or by polycondensation of or under addition of amino carboxylic acid compounds, such as &egr;-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, lactam compounds, such as &egr;-caprolactam, enanthlactam, &ohgr;-laurolactam.
Concrete examples are polyamide 6T, polyamide MXD6, polyamide 6I, and polyamide 6T/6I. Polyamide 6T, polyamide 6I and polyamide 6T/6I are preferable. Polyamide 6T is obtained by polycondensation of hexamethylene diamine and terephthalic acid (T). Polyamide MXD6 is obtained by polycondensation of m-xylylene diamine (MXD) and adipinic acid. Polyamide 6I is obtained by polycondensation of hexamethylene diamine and isophthalic acid (I). Polyamide 6T/6I is polyamide resin obtained by polycondensation of hexamethylene diamine and terephthalic acid (T) and hexamethylene diamine and isophthalic acid (I).
One or many kinds of said aromatic polyamide resin may be employed; a mixture with any proportion of aliphatic polyamide resin, such as polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, is employable. If a higher gas barrier property is required, a proportion of aromatic polyamide resin in the polyamide resin composition of at least 50% by weight is preferable. The manner of blending is not particularly limited to one method. Suitable manner of blending, includes, but is not limited to, melt blending, solution blending, blending during polymerization, etc.
Layered silicate modified by a triazine compound derivative (B) of the present invention is obtainable by ion-exchange reaction of layered silicate and triazine compound derivatives.
The layered silicate are classified as phyllosilicates in mineralogical terms, and in particular 2:1 phyllosilicates made of two tetrahedral layers and one octahedral layer, and 1:1 phyllosilicates made of one tetrahedral layer and one octahedral layer. Examples of minerals for 2:1 phyllosilicates include smectite, vermiculite, mica, chlorites, and for examples of 1:1 phyllosilicates include kaolin, serpentine, etc. Examples of the smectite group include saponite, hectorite, sauconite, montmorillonite, beidellite, nontronite, and stevensite, etc. Examples of the vermiculite group include trioctahedral vermiculite and dioctahedral vermiculite, etc. Examples of the mica group include compositions such as phlogopite, biotite, lepidlite, muscovite, paragonite, chlorite, margarite, taeniolite, tetrasilicic mica, etc. All of the phyllosilicates in accordance with the present invention may be natural products, or synthetic ones produced using a suitable method, including hydrothermal method, melting method, solid phase method, etc.
The triazine compound derivatives in accordance with the present invention are reaction products of triazine compounds and Lewis acids.
Triazine compounds are compounds with a six-membered ring containing 3 nitrogen atoms; for example melamine compounds, cyanuric acid compounds, and melamine cyanurate compounds, etc.
Melamine compounds are compounds of the following chemical formula. In the formula, R
1
and R
2
which may be the same or different stand for hydrogen atom, methyl group, ethyl group, methylene group, ethylene group, phenyl group, benzyl group or halogenophenyl group, etc. More particular examples include melamine, N-ethylene melamine, and N,N′,N″-triphenyl melamine, etc.
Cyanuric acid compounds are those of the following chemical formulae. In the following formulae, R
3
which may be the same or different stand for hydrogen atom or a lower alkyl group. In the present invention, hydrogen atom as R
3
is preferable. More particular examples of cyanuric acid compounds include cyanuric acid, isocyanuric acid, trimethylcyanurate, trismethylisocyanurate, triethylcyanurate, trisethylisocyanurate, tri(n-propyl)cyanurate, tris(n-propyl)isocyanurate, diethylcyanurate, N,N′-diethylisocyanurate, methylcyanurate, methylisocyanurate, etc.
Melamine cyanurate compounds are equivalent mol reaction products of melamine compounds and cyanuric acid compounds. They can, for instance, be produced by mixing an aqueous solution of melamine and an aqueous solution of cyanuric acid, and then stirring the mixture at a temperature of ca. 90 to 100°C. The generated precipitate is then filtered off. The product is white solid, and can be crushed into fine powder for use. Alternatively, commercial product may be used as is or in crushed form.
Lewis acid compounds are electron pair acceptors. Examples are hydrogenic acids, such as hydrochloric acid, hydrogen sulfide, etc.; oxoacids, such as sulphuric acid, nitric acid, acetic acid and phosphoric acid; thioacids, such as ethylxantogen acid, etc.; alkyl halides; and acid halides. The amount of Lewis acid employed is in the range of 0.01 to 3 mo vis-À-vis mol of triazine compounds.
Various methods can be used for mixing said layered silicates and triazine compound derivatives to obtain the layered silicate modified by a triazine compound derivative of the present invention. For example, suitable methods include bringing the layered silicates and triazine compound derivatives into contact via a medium with affinity to both, and methods of directly mixing them without the use of a medium. For the case where a medium is used, components can be dispersed in a solvent to homogenize them, then they can be subsequently mixed with stirring, and the solvent
Ebata Tsuguo
Inoue Hirofumi
Nakamura Jun-ichi
Noguchi Masayuki
Tamura Kenji
Banner & Witcoff , Ltd.
EMS-Chemie AG
Rajguru U. K.
Seidleck James J.
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