FR2537149A1 - MOLDING COMPOSITIONS, COOKING UTENSILS MANUFACTURED THEREIN AND USE OF SUCH UTENSILS - Google Patents

Abstract

THE PRESENT INVENTION RELATES TO POLYESTER-BASED MOLDING COMPOSITIONS, TO COOKING UTENSILS MADE FROM THESE COMPOSITIONS AND TO THE USE OF THESE UTENSILS. ACCORDING TO THE INVENTION, THESE MOLDING COMPOSITIONS INCLUDE ABOUT 35 TO ABOUT 65 OF AROMATIC POLYESTER, AND ABOUT 1 TO ABOUT 60 OF A TALC CONTAINING A MINIMUM CONTENT OF HIGH TEMPERATURE DECOMPOSABLE MATERIALS.

Description

"Lage soft compositions, cooking utensils made

  The present invention relates to molding compositions, cooking utensils and the like.

  made of these compositions and the use of

these utensils.

  We know that some plastics have found some applications in the field

  For example, we have used

  polymethylpentene for injection molded trays which can be used for

  preparation of food products The polysul-

  fone has also been used in applications

  used for the preparation of food products.

  However, no satisfactory material was found

  which can be used in the wide range of

  conditions and requirements which are encountered

  in the provision of containers or utensils

  cooking, which can be used either in

  thermal ovens either in microwave ovens

  waves. In addition to the obvious fact that the material must be able to withstand the temperatures encountered in the heat source used for cooking,

  the material must have a unique combination

  a number of other characteristics before the kitchen utensil made from the material can be used successfully in the preparation of food The material must have good electrical properties It must be able to important thermal shocks in that the cooking utensil prepared from it must be able to go from extreme cold conditions to high temperatures on

  relatively short periods of time.

  re must have good hardness and impact resistance and have high tensile and flexural strength. It must also be able to

  resist boiling water, food acids

  and fats and the harmful effects

  immersion in detergents.

  In the case of food-related properties, the material must be capable of conferring

  the cooking utensil made from that

  it is resistant to soiling by a wide range

  due to food material She must present

  a surface with good anti-foam properties

  are easy to remove for food.

  it contains It must not issue -

  to release any volatile matter and it does not

  must not contain any extractable constituent

  In addition to meeting all the above requirements, articles made from this material must

  pleasant and generally uniform so as to

see being marketable.

  We obtain, according to the present invention, kitchen utensils meeting the requirements

  strict rules of the market for cooking vessels in

  baking the cooking utensils from a plastic material based on fully aromatic polyesters, and more particularly oxybenzoyl polyesters. Fully aromatic polyesters

  used according to the present invention are

  characterized by combinations of repeating moieties selected from the group consisting of one or more of the following formulas:

4

I P

  ## EQU1 ## where x represents 0, S ,, NH or SO 2 N is equal to 0 or 1 and and the total of the numbers

  p + q + r + S + t + u in the fragments

  Sents is about 3 to about 800.

  The combinations of the aforementioned fragments

  include the binding of the carbonyl group of

  mules I, II, IV and V with the oxy group of the formulas

  I, III, IV and VI In the most

  In general, all fragments corresponding to the

  the above may be present in a single co-

  The simplest embodiment would be homopolymers of fragments I or IV. Other combinations consist of mixtures of fragments II and III, II and VI, III and

V, V and VI, and I and IV.

  The location of the functional groups is preferably in the para (1, 4) position. They can also be arranged in the ortho (1,2) position with respect to each other. For the naphthalene fragment, the most interesting functional groups are in positions 1,4, 1,5 and 2,6 These groups can

  also be in ortho position

port to others.

  The symbols p, qr, s, t and u are integers and indicate the number of fragments present in the polymer. The total sum of (p + q + r + S + t + u) can vary from 3 to 800 and, when present, the ratios q / r, q / u,

  t / r, t / u, q + t / r, q + t / r + u and t / r + u may

  wind vary from about 10/11 to about 11/10, the most interesting ratio being 10/10.

  Examples of materials from which

  Fragments of the formula I are hydroxybenzoic acid and its esters, such as phenyl p-hydroxybenzoate,

  p-acetoxybenzoic acid and isobu p-acetoxybenzoate

  tyl substances from which it is possible to obtain

  to hold the fragment of formula II are

  rephthalic, isophthalic acid, diphenyl

  terephthalate, diethyl isophthalate, methyl

  ethyl terephthalate and isobutyl half-ester

  of terephthalic acid

  getting the fragment of formula III,

  mention may be made of p, p'-biphenol, 4,4'-dihydroxy-

  benzophenone, resorcinol and hydroquinone

  will find that these materials are also appro-

  requested to obtain the fragments of formulas VI-

  VIII. Examples of monomers corresponding to formula IV are 2-hydroxy-6-naphthoic acid which,

  6-hydroxy-1-naphthoic acid, 5-acetoxy-

  1-naphthoic acid and 5-hydroxy-1-naphthoate

  Monomers of the formula V are

  1,4-naphthalenedicarboxylic acid, 1,5-

  naphthalenedicarboxylic acid and 2,6-naphthalene

  dicarboxylic acid can also be used

  phenyl esters or dicarbonyl chlorides of these

  Examples of particular monomers are

  Formula VI are 1,4-dihydroxynaphthalene

  not, 2,6-diacetoxynaphthalene and 1,5-dihydroxy-

  naphthalene. Were particularly interesting in the context of the presefite invention the materials

  oxybenzoyl polyesters based plastics.

  A preferred class of oxy-polyesters

  benzoylics are the copolymers of

petitives of formulas VIII and IX:

(VIII) O

  There are (X) o (X) M in which x is -O or -SO 2-, m is 0 or 1, N is 0 or 1, q / r = 10/15 to / 10 , -p / q = 1/100 to 100/1, and p + q + r = 3 to 600 and preferably 20 to 200 The carbonyl groups of the fragment of formula I or III are linked to the oxy groups of a fragment formula I or IV; the oxy groups of the fragment of formula I or IV are linked to the carbonyl groups of the fragment of formula I or III Another group of aromatic polyesters

  that can be used are the aromatic polyesters

  ticks containing repetitive fragments of

  2,6-dicarboxynaphthalene moiety and / or fragment

  of p-oxybenzoyl and the symmetrical dioxy aryl moiety, as well as variants thereof.

  polyesters are described in US Pat.

  United States of America No. 4,067,852, 4,083,829, 4,130,545,

  4,161,470, 4,184,996, 4,219,461, 4,224,433,

  4,238,598, 4,238,599, 4,256,624, 4,265,802,

  4,279,603, 4,318,841 and 4,318,842. The preferred copolyesters include repetitive moieties of the formula: ## STR1 ## The synthesis of these polyesters is described in detail in US Pat. No. 3,637,595, entitled "P-Oxybenzoyl Copolyesters", incorporated in the context of the present invention under

reference title.

  Polyesters used in the context of 2537 i 49 '

  the present invention may also be modified

  chemically by different means, such as

  incorporating into the polyester mono-

  functional groups, such as benzoic acid, or

  Trifunctional or higher functional active agents, such as trimeicated acid The benzynic rings in these polyesters are preferably unsubstituted but may be substituted with

substituents not interfering.

  The oxybenzoyl polyesters of interest

  in the context of the present invention-can-

  can be used with different loads of

  and in quantities that favor or at least

  do not materially modify the properties de-

  Examples of interesting fillers are, among others, glass fibers, crushed glass,

  polytetrafluoroethylene, pigments,

  and combinations of these different elements.

  Although prepa-

  from compositions comprising the poly-

  oxybenzoyl esters and different fillers

  mentioned above satisfy the general requirements

  the above question, they do not have the pleasant, uniform appearance necessary for a product that can be distributed commercially Moreover,

  it has been observed that a large number of charges

  have an excess of bubbles in cooking utensils

its at high temperatures.

  It has been found, according to the present invention

  that a single aspect could be communicated

  form and pleasant to the articles or utensils of

  and remove or minimize the

  unwanted bubbles by the introduction

  in the oxybenzoyl compositions from

  these utensils or articles are molded, talc containing a minimum amount of decomposable material at elevated temperatures, for example up to about 8000 C, such as magnesium carbonate Among the talcs of this

  type, one will quote talcs of high purity, the.

  talcs combined selectively from various

  ores or talcs that have been calcined or

put on an acid treatment.

  The talcs used in the context of the present invention are characterized by a low weight loss to iron 11 ageunefa Ri iron content analyzed in the form of iron oxide and a

  tightly controlled particle size.

  The loss in roasting weight of the appropriate talcs is not greater than about 6% or less at 9500 C and is 2% or less at 8000 C. The iron content, analyzed for iron oxide (Fe 2093 will not be not more than about 1% and that of

  particularly preferred talcs will not be

  than about 0.6% and may be less than

this value.

  Experiments and tests have shown quite clearly that it is essential to use a talc of this type for

  achieve the objects of the present invention.

  The use of other forms of talc does not confer

  satisfactory properties of the molded product

253? 7149

  However, these other forms of talc can be used together with the specified talc in amounts ranging from about 0.05% to about

% of the required forms of talc.

  The talcs containing the minimum amount of decomposable material will be present in amounts ranging from about 1% to about 60% based on the weight of the total composition, the preferred range being from about 35% to about

55%.

  It is also possible to use rutile titanium dioxide in conjunction with the talc-forming material, especially highly refined talc mixtures and other talcs. Rutile titanium dioxide will be present in a proportion of about

  2% to about 20% in relation to the weight of the

  total position The preferred range is

about 5% to about 15%.

  In the molding compositions of the present invention,

  In this invention, the resin will be

  generally about 35% to about 85% of the total

  position and total inert

  65% to about 15% o For results

  optima, the inerts will be

  about 40% to about 55% of the mold compositions.

  Inert materials will

  only about 55% of highly refined talc and

  about 0 to about 10% titanium dioxide.

  Although all the abovementioned resins are of interest in the context of the present invention, it is preferable to use a resin

2537149 '

  wherein the dibasic acid, the hydroxy acid

  aromatic and aromatic diol are present in the molar proportions of about 1/2/1 Other molar proportions may be used and resins in which the molar proportions of terephthalic acid, p-acid and the like are used. Hydroxybenzoic and biphenol are, for example, 1/3/1, 1/5/1, 1/7/1, and 1 / 3.5 / 1 Physical blends of resins

  in which different proportions of reaction

  have been used also prove appro-

requested.

  The compositions of the present invention

  Alternatively, for example, a twin screw extruder can be used by adding the polymer, selected talc and titanium dioxide to the feed neck and adding glass roving at a time. to the passes

aeration and feeding.

  The compositions thus obtained can then be injection molded according to the

  general practice using

  in the field of injection molding.

  The invention is illustrated more specifically by the following Examples, in which

  which all parties and percentages

  are by weight unless otherwise stated.

  These examples illustrate some of the ways in which

  made according to the invention but do not cons-

  under no circumstances constitute a limitation to it.

Example 1

  This example illustrates the synthesis of a

  polyester usable in the context of the present invention. The following quantities of ingredients

  given below are combined as indicated.

  Name Quantity Nation Ingredient gr '-Moles A p-Hydroxybenzoic acid 138 1 B Phenyl acetate 170 1.25 C Therminol 77 500 D Diphenyl terephthalate 318 1 E Hydrochloric acid F Hydroquinone 111 1,101 G Therminol 77,500

  The ingredients A-D are loaded into a bal-

  Four-necked flask equipped with a combined thermometer, stirrer, nitrogen inlet and HCl outlet connected to a flask. Nitrogen is slowly fed through the inlet. The contents of the contents are heated up to 180 ° C., which results in a sparge of HCl in the reaction mixture. The outlet temperature is maintained at 110 ° -120 ° C. by external heating during the reaction.

  of exchange between p-hydroxybenzoic acid and

  ter consisting of phenyl acetate.

  The container and its contents are shaken

   C for 6 hours, after which time

  the release of HCl is stopped, the output head temperature is raised to 180 C-190 'C

  and the mixture is stirred at 220 ° C. for 3.5 hours.

  Until then, 159 g of distillate

  lat in the refrigerant Then add the

  F and gradually raise the temperature

  at 220 ° C. to 320 ° C. over a period of 10 hours (10 ° C./hour). Stirring is continued at 320 ° C. for 16 hours and then for an additional 3 hours at 340 ° C. in order to obtain a paste. of distillate, formed

  of phenol, acetic acid and phenyl acetal

  To 384 g, ingredient G is added and the reaction mixture is allowed to cool to 70 ° C. Acetone (750 ml) is added.

  the pulp is filtered, the solids being ex-

  treated in a Soxhlet with acetone for

  separate ingredients C and G

  lides are dried under vacuum at 110 ° C. overnight, which makes it possible to recover the resulting copolyester (320 g, 89.2% of the theoretical yield)

  in the form of a granular powder.

Example 2

  518 parts of isophthalic acid 1557 parts of terephthalic acid, 5175 parts of para-hydroxybenzoic acid, 6885 parts of year

  acetic acid and 2325 parts of p, p'-bis-

  phenol are mixed together and heated at

  reflux for 17 hours, at the temperature of

  180 C, after which the refrigerant is replaced

  at reflux by a distillation head and the

  ve the temperature up to 345 C over a period of

  1 1/4 hours The reaction mixture is stirred for

  During the entire heating period, this mixture of

  reaction etan, particularly intimately

  During the period during which the temperature is raised to 345 ° C. The polymer production is 8020 parts and 8010 parts of distillate are recovered. The contents of the reaction vessel are removed, cooled and milled.

  particle sizes entering the gam-

  0.83 mm to 0.095 mm. The resulting resin has a molecular weight in the range of 5000 to 20000,

  an average weight corresponding to about one

  their in the middle of this range It is estimated that the

  product is crystalline at about 50 Yo.

  The resin particles are, for example, kept under vacuum at a high temperature and at an absolute pressure of about 100 mm Hg for 8 hours and recovered as a

granular powder.

Example 3

  The following quantities of ingredients

  following are combined as shown.

  Name Quantity Nation Ingredient gr Moles A Terephthalic acid 291 1.75 B p-Hydroxybenzoic acid 483 3.50 C p, p'-biphenol 325 1.75 D Acetic anhydride 755 7.40 The ingredients A-D are heated to

   C and heated at reflux overnight.

  The reflux condenser is removed and replaced

  this by a distillation head

  stirring at a rate of 20 C / hour

2537 I-49 '

  at 300 C and remove the contents of the reactor.

  At this point, about 92-94% of the total

  theoretical acetic acid The prepolymer is ground

  and treated as in Example 2, using a temperature of about 250-3750C.

Example 4

  Name Quantity Nation Ingredient gr Moles A p-hydroxybenzoic acid 276.0 (2.00) B Terephthaloyl chloride 203 1.0 C Triazineic acid 8.4 0, 040 D Therminol 66 1274 E p, p'-biphenol 186 1, 0 F Acetic anhydride 224, 6 2.2 The ingredients AD are heated to C and kept there for 1 hour The reaction is exothermic and care must be taken to maintain the temperature at 130 C. The contents are heated to 155 ° C. C. for 1 hour and at 180 ° C. for 4 hours. The mixture is then cooled to 150 ° C. and ingredient E is added, the temperature being

  then lowered again to 140 C.

  Then the ingredient F is heated at reflux this mixture for 1 hour at 155 C and replaced the

  reflux condenser by a distillation column

  While distilling the acetic acid formed, the reactor contents are heated to 330 ° C. and kept there for 3 hours.

* the polymer in suspension up to 250 C and filtered

  The solid material is treated with trichlorethylene to separate the heat transfer fluid. The dried powder is

  then treated under vacuum as in Example 2.

Examples 5, 6 and 7

  The procedure of Example 3 is repeated in use.

  reading the following quantities of the indicated ingredients. Denomination Quantity in mole nation Ingredient Ex 5 Ex 6 Ex 7 A Terephthalic acid 1 1 1 B p-Hydroxybenzoic acid 3 4 5 C p, p'-biphenol 1 1 1 D Acetic anhydride

Example 8

  268 parts of biphenol, 396 parts of para-hydroxybenzoic acid, 693, 40 parts

  of acetic anhydride and 238 parts of

  phthalic acid are mixed and heated to a

  at 3150 ° C. over a period of 5 hours at a rate of temperature rise of 30 ° C. per hour.

  during the heating period When the temperature

  When 315 ° C is reached, the polymer contents are separated from the reaction vessel and ground.

  at a particle size of 0.83 mm to 0.074 mm.

  The resin particles are introduced into an oven and gradually brought to a temperature

  354 C over a period of 16 hours and recovered

  in the form of a granular powder.

Example 9

  A molding composition is prepared from the polymer of Example 8 by extruding a mixture of 257.5 parts of the polymer of the Example

25371149 '

  8.30 parts of rutile titanium dioxide and 212.5 parts of a high purity talc having the

  Platelet structure of natural talcum, one person.

  2% by weight, an iron content analyzed for Fe 203 of 0.5% and a particle size distribution in which

  more than 95% of the particles are less than 40 microns.

  The resulting mixture is injection molded to form molded bowls of

  pleasant, uniform, which do not present any

  blow molding at minimum temperatures

the about 2600 C.

  Some of the molded articles are

  put in a soil test in which

  get a spoonful of roasting sauce on the

  bottom of the molded container The container is then

  placed in a preheated oven at 1770 C during

  1 hour At this time, the sauce is thick,

  and has a structure in cro Qte After

  cooling, the vessel is washed with

  von and water using a scrunge pad.

  The container is examined for deficiencies

  lures and note the difference in color between

  soil or stains and non-soiled areas

  The difference observed is very slight.

  Some other samples are submitted to

  a fall test during which the

  five samples on their outer perimeter

  higher up from gradually increasing heights to determine their fitness

  to withstand the shock of the fall without significant damage.

237149 '

  The average for these samples is 101.6 cm.

  The results of these tests show all

  the ability of molded articles to be used

  me cooking container for food.

  EXAMPLE 10 A molding composition is prepared from a polymer obtained according to Example 8,

  by extruding a mixture of 271 parts of polymer

  and 10 parts of the talc used in Example 9.

  The resulting mixture is injection molded

  at a screw speed of 100 revolutions per minute,

  at an injection pressure of 13.6 M Pa and at

  temperature of 3550 C in zone 1, 3601 C in zone 2 and 3451 C in zones 3 and 4. Molded articles of an

generally pleasant.

  Examples 11 to 18 In these examples, 257.5 parts of the resinous products of Examples 1 to 8 are mixed with 202.5 parts of the talc used in Example 9, with 40 parts of rutilated titanium dioxide.

  passing them through a twin-screw extruder

  The reinforced resinous compositions obtained from

  naked are shaped by injection molding.

  The molded articles obtained have a satisfactory appearance

  and resistance to cracks and

  satisfactory blistering at high temperatures.

Claims (13)

  1 molding composition based on poly-   ester, characterized in that it comprises about   about 65% of aromatic polyester, and about   1 to about 60% of a talc containing a   minimum temperature decomposable material high erase.   2 molding composition according to the invention   1, characterized in that the polyester   aromatic is an oxybenzoyl polyester.   3 Composition according to one or the other   claims 1 and 2, characterized in that   contains about 2 to about 20% rutile titanium dioxide, particularly about 5 to about 15%.   4 Composition according to any one   Claims 1 to 3, characterized in that   talc is of a type with a loss in   the mesh weight, which is not greater than   6% to 950, and an iron content, analyzed   for iron oxide, which is not greater than viron 1%.   Composition according to any one   Claims 1 to 4, characterized in that   the amount of talc in this composition is about 35 to about 55% o.   6 Composition according to any one of   Claims 1 to 5, characterized in that the   talc is selected from the group consisting of high purity talcs, highly refined talcs,   calcined talcs and talcs treated with acid.   7 Molding composition based on poly-   ester according to any one of claims   1 to 6, characterized in that the polyester comprises   repetitive fragments selected from the group consisting of one or more of the following formulas: ## STR1 ## IV   in which x represents 0, S, 9 -, NH or SO 2 and N is 0 or 1, and the total of the integers p + q + r + S + t + u in the fragments   present is from about 3 to about 800.   8 Molding composition according to one or   the other of claims 7 and 8, characterized in that   what the ratios q / r, q / u, t / t, t / u, q + t / r,   q + t / r + u and t / t + u are about 10/10 to about 11/10, in particular 10/10.   9 Molding composition based on poly-   Ester according to Claim 2, characterized in that the oxybenzoyl polyester contains repetitive fragments of each of the formulas I, II and III: p O   where x is O or 502-; m is 0 or 1; N is 0 or 1; q / r = 10/15 to   15/10; p / q = 1/100 to 100/1; p + q + r = 3 to 600, in par-   In particular, the carbonyl groups of the moiety of formula I or II are linked to the oxy groups of the moiety of formula I or III, and the oxy groups of the moiety of formula I or III are linked to the carbonyl groups of the moiety of formula I or III. II.   Molding composition based on poly-   Ester according to Claim 9, characterized in that the oxybenzoyl polyester contains repetitive fragments of the formula: I   11 Cookware that can be used   in repeated ways, characterized in that   is made of a soft polyester composition   according to any one of claims 1 -20 to lo.   12 Process for preparing food in   a permanent cooking vessel, capable of   to be used in repeated ways, in which   the food in the container is heated   up to a temperature   vir, characterized in that it consists in putting   the food in a molded utensil according to sales 11.   13 Process for the preparation of food   Claim 12, characterized in that the heat source is a thermal source or microwave.