FR2461727A1 - CURABLE RESIN COMPOSITIONS CONTAINING TRIHYDRATED ALUMINA AND PROCESS FOR THEIR IMPLEMENTATION - Google Patents

Abstract

HARDENABLE RESINOUS COMPOSITIONS. THEY CONSIST OF TRIHYDRATED ALUMINA, A COMPOUND CONTAINING AT LEAST TWO POLYMERISABLE VINYL GROUPS PER MOLECULE, A POLYDEN POLYMER, AND OPTIONALLY A POLYMERISABLE MONOVINYL COMPOUND. THESE COMPOSITIONS ARE USEFUL FOR MOLDING AND LAMINATION APPLICATIONS.

Description

1. The present invention relates to compositions

  curable resinous products, cured products prepared at

  of such compositions and a process for the preparation of

  such hardened products. The invention relates more particularly to

  curable compositions containing alumina trihydrate, which can be molded or laminated to

  give rise to hardened products with a high degree of

  delayed lifting to the transmission of combustion.

  Curable resinous compositions containing alumina trihydrate are described in U.S. Patent 4,041,008 to Makhlouf and Parker. The resinous component

  of these compositions is an unsaturated polyester resin which is

  resulting from the condensation of alpha-dicarboxylic acids,

  beta-ethylenically unsaturated, such as maleic acid, a-

  with polyols, such as ethylene glycol and propylene

  glycol. The polycondensate is diluted with a vinyl monomer

  like methyl methacrylate to form the resin. Lors-

  that these compositions are hardened, they produce excel-

  slow items delaying the transmission of combustion.

  However, the degree of retardation of the transmission of combustion reached is limited by the increase in viscosity

  as and when the alumina trihydrate is added.

  High viscosities of the resin are unsuitable because of poor handling characteristics for molding and lamination. Increasing the vinyl monomer content to combat the increase in viscosity resulting from the addition of the alumina trihydrate leads to

  cured products with unsatisfactory properties.

  The present invention overcomes these shortcomings

  of the prior art and provides compositions

  with relatively high levels of alumina trihydrate

  ted. In the present invention, the resinous components of the composition have a much lower viscosity than the resinous components of U.S. Patent 4,041,008 and can tolerate higher doses of alumina trihydrate, which

  results in better properties of trans-

  combustion mission without an increase in viscosity

ceptable.

  The present invention thus relates to fundamental-

  2. A curable composition suitable for molding and laminating, comprising: (A) 17 to 95% of a compound containing at least two

  polymerizable vinyl groups per molecule; -

  (B) 1 to 50% of a polydiene polymer;

  (C) 0 to 70% of a polymeric monovinyl compound

  sand, the weight percentage of (A), (B) and (C) being based on the total weight of (A), (B) and (C), and (D) at least 50% by weight of alumina trihydrate, this percentage by weight being based on the total weight of (A),

(B), (C) and (D).

  The invention also relates to a method for

  preparation of hardened resinous articles from the

  described above during curing cycles

  short, namely 30 seconds to 8 minutes, as well as

  hardened keys properly so called. The cured articles have an excellent appearance, they are smooth and shiny and have excellent properties of retarding the transmission of combustion, namely low flame spread,

  low smoke densities and high oxygen levels.

  In addition to the aforementioned U.S. Patent 4,041,008, the prior art that may be considered relevant to the present invention is: U.S. Patents 2,688,009

3313545

3438933

3502338

3912773

  Japanese Patent Application 71.63.766 (Kokai 73.29.832)

  Japanese Patent Application 16.155 / 72 (Kokai 96.640 / 73).

  US Patent 2,688,009 discloses a mixture of a poly-

  liquid polybutadiene mother in combination with at least 1% by weight of a divinyl compound, such as divinyl

  benzene. The mixtures can be combined with a catalyst

  It is free radicals and polymerized to form a product at a temperature of about 21 to 121 ° C. There is no mention in this patent of compositions containing alumina trihydrate. U.S. Patents 3,313,545, 3,438,933 and 3,502,338

24 6 1,727

  3. describe molded golf balls made from a polybutadiene elastomer and a crosslinking monomer, such as butylene glycol dimethacrylate or trimethacrylate

  trimethylolpropane. The compositions can be combined

  with fillers, such as silica and

  glass, and aluminum oxide can also be incorporated into

  re in the compositions. However, it is not reported

  in these composition documents containing triethylated alumina

moisturized.

  U.S. Patent 3,912,773 discloses compositions

  which are suitable for casting, comprising a mixture of

  vinyl and a thermoplastic polymer. The com

  positions are presented as capable of being charged with

  trihydrated mine. There is no mention of the use of

polydiene polymers.

  Japanese Patent Application 71.63.766 (Kogai

  73.29.832) discloses thermosetting resinous compositions

  which are usable liquid compositions are

  both cast and hardenable in the presence of peroxides

  ganic. The compositions comprise the following elements (A) 100 parts by weight of 1,2-polybutadiene with a molecular weight of about 500 to 5000;

  (B) 10 to 80 parts by weight of an acid ester a-

  crylic or methacrylic, such as methyl methacrylate, and (C) 10 to 60 parts by weight of a multifunctional acrylic or methacrylic ester, such as dimethacrylate

  ethylene glycol or trimethylolpropane trimethacrylate.

  This document does not mention

  containing alumina trihydrate.

  Japanese Patent Application 16.155 / 72 (Kd ai 96.640 / 73) discloses compositions comprising: (A) 30 to 70% by weight of an alkyl methacrylate, such as methyl methacrylate, and 70 to 30% by weight; weight of styrene or an alkyl fumarate, and O to 15% by weight (0 to 13% relative to the total weight of the vinyl monomer and the

  polybutadiene) of a polyvinyl compound, such as dimethyl

  ethylene glycol methacrylate, (B) polybutadiene with a molecular weight of 1000-4000, and

(C) alumina trihydrate.

  This document does not refer to

  containing more than 13% by weight of the polyvinyl

  than. Compositions with small amounts of polyvinyl compound require excessively long curing times. For example, the compositions of this Japanese document

  considered are presented as being molded during a period

period of about 1 to 10 hours.

  Although the prior art describes many of the ingredients used in the compositions of the present invention, there is no suggestion therein of a combination of the ingredients according to the method of the present invention to achieve compositions that cure during cycles of the present invention. molding to provide products with an appearance

  and delaying properties of the transmission of

excellent bustion.

  Curable compositions according to the present invention

  are obtained by mixing the compound containing the

  at least two polymerizable vinyl groups per molecule (

  polyvinyl salt) and the polymerizable monovinyl compound (if one is used) with the polydiene polymer to form a low viscosity solution. The solution must

  preferably have a viscosity of less than 3 poises and

  usually between about 0.2 and 1 poise at 300C. A

  vinyl polymerization catalyst and the ingredients

  such as polymerization accelerators,

  promoters or inhibitors, are then added, under a-

  gitation, to the solution. -Only an agitation at a low rate of

  Shearing is usually necessary. After that, the

  trihydrate lumen and optional ingredients, such as

  demoulding agents, fillers and fillers

  forcing, are added by mixing at high shear rate.

  to form the curable compositions.

  The polyvinyl compound is necessary to ensure

  cross-linking and short curing cycles. The polyvinyl compound contains per molecule at least two vinyl groups capable of participating in a polymerization of

  vinyl type. These compounds usually have moderate weights

  5. Examples of polyvinyl compounds are esters having 2 to 5, preferably 2 to 3, ester groups and at least 2, preferably 2 to 3, vinyl polymerization groups, and more preferably less than 400.

  ble. Among these are the di-, tri-, tetra- and penta-

  polyalcohol esters with unsaturated carboxylic acids

  as well as esters of polyacids with alcohols

  saturated. Esters are non-volatile liquids at

  eratures to which they are mixed and preferably contain

  preferably about 6 to 30 carbon atoms, preferably 6 to 22

  carbon atoms. Examples of esters that can be used

  are those resulting from the reaction of a carboxylic acid

  unsaturated with 3 to 16 carbon atoms, such as

  crylic, methacrylic acid and ethacrylic acid, with

  a polyalcohol containing 2 to 16 carbon atoms, preferably

  2 to 6 carbon atoms, such as ethylene glycol, di-

  ethylene glycol, propylene glycol, dipropylene glycol,

  neopentyl glycol, 1,4-butanediol, 1,6-hexanediol,

  methylolpropane, tetramethylolmethane, glycerin,

  pentaerythritol and 2,2-dimethyl-3-h-hydroxypropyl-2,2-dimethyl

thyl-3-hydroxy propionate.

  It is also possible to use

  resulting from the reaction of a polycarboxylic acid having about 4 to 10 carbon atoms, such as malonic, maleic, fumaric, itaconic, succinic and adipic acids, with

  an unsaturated alcohol such as allyl alcohol or methyl alcohol

  thallylique. Polyvinyl compounds can also be used.

  such as an acid acrylate obtained by reaction of

  Acrylic or methacrylic acid with amide alcohols, for example the reaction products of diethanolamine and formic acid.

  The preferred polyvinyl compounds are

  acrylic acid or methacrylic acid with poly-

  alcohols such as ethylene glycol and trimethylolpropane.

  The polyvinyl compound should be about 17

  at 95%, and preferably about 25 to 60%, by weight of the

  resinous condition. Amounts less than 17% by weight are undesirable since the compositions do not harden

246 1727

  6. sufficiently in short times that are commercially desirable and may lead to items endowed with a

  insufficient structural strength. Higher quantities

  95% are not desirable due to the fragility and poor appearance of hardened items. The polydiene polymer contributes to the equality of

  the surface and flexibility of hardened articles. Polydiene

  also gives, in a somewhat surprising way,

  retarding properties of the transmission of combustion.

  It has been found that compositions without polydiene or in

  which other polymers, such as polyesters or

  lyethers, were substituted for polydiene, led to hardened articles giving rise to higher propagations

of the flame.

  Polydiene polymers include polymers

  1,3-diene resins containing 4 to 12, and preferably 4 to 6, carbon atoms. Typical dienes include the

  1,3-butadiene which is the preferred product, 2,3-dimethyl-1,3-

  butadiene, isoprene and piperylene. We can also use

  copolymers of 1,3-butadiene and a copolymer monomer

  lymerisable with 1,3-butadiene, such as isoprene and

  perylene. Other polymerizable monomers, such as methacrylate

  methyl crylate, acrylic acid, styrene and acrylonitrile

  nitrile, can also be used, but these are not

the preferred monomers.

  As mentioned above, polydiene polymers

  preferred are homopolymers of 1,3-butadiene. Polybu-

  tadienes may predominantly contain 1,2-vinyl unsaturation, but polybutadienes containing

  predominantly (ie for more than 50, and preferably

  more than 60%) of 1,4-unsaturation. Polybutadienes u-

  tiles contain about 10 to 30% cis-1,4 unsaturation,

  at 70% unsaturation trans-l, 4 and 10 to 35% insatura-

tion-L1,2-vinyl.

  The polydiene polymers may be terminally

  or terminated with acid groups, hydroxyl groups or ethylenically unsaturated acryloxy groups, as generally described in U.S. Patent 3,652,520. The hydroxyl-terminated polydiene polymers are preferred because of their compatibility with others.

ingredients of the composition.

  The polydiene polymers of the present invention are

  They are normally liquid at room temperature and preferably have number average molecular weights on the order of 500 to 15,000, and more preferably 1,000 to 5,000. Polydienes of lower molecular weight

  at 500 are not desirable because of the physical properties

  unsatisfactory levels of cured products, while polydienes with a molecular weight greater than

  not the preference because of high viscosities.

  Polydiene polymers must constitute approximately

  1 to 50%, preferably about 5 to 20% by weight of the resinous components. Quantities less than 1% in

  weights are not desirable, because of the relative fragility

  the hardened articles and the relatively

  lifting of the flame. Quantities greater than about 50%

  are not desirable because the compositions harden

  with difficulty and may have poor resistance

  structural strength and high viscosities.

  Optionally, the composition may contain up to

  at 70% by weight of a polymerizable monovinyl compound,

  such as an alkyl acrylate or an alkyl methacrylate

  closing up to 6 carbon atoms in the alkyl group.

  As examples, there may be mentioned methyl methacrylate (preferably

  fere), ethyl acrylate, isobutyl acrylate and methyl

  hexyl methacrylate. It is also possible to use acrylates

  or hydroxy-substituted alkyl methacrylates. Examples

  are hydroxyethyl acrylate and hydrogen methacrylate

  droxypropyle. Examples of other vinyl monomers are vinyl acetate and vinyl propionate. The use of the monovinyl compound in amounts greater than 70%

  by weight is not recommended because of the

  sufficient with short curling cycles.

  The resin component of the present invention preferably contains less than 10% by weight of aromatic ingredients such as divinylbenzene, styrene and the like,

  the percentage by weight relating to the total weight of

  resinous ingredients, namely the polyvinyl compound, the

8.

  posed polydiene and the monovinyl compound. The constitution

  The resinous agent should preferably contain less than 5% by weight of aromatic ingredients and preferably be free of added aromatic ingredients other than free radical initiators, accelerators, inhibitors,

  mold release agents or other non-reactive ingredients.

  Alumina trihydrate is also present in the composition. Alumina trihydrate confers properties

  retarding the transmission of combustion, such as

  low flame spread and high oxygen indices as will be described hereinafter. The alumina trihydrate must constitute at least 50%, preferably about 55%, by weight of the curable composition, calculated on the

  total weight of the resinous component and the trihydrated alumina

  ted. Amounts less than 50% by weight, although

  contribute to the achievement of advantageous properties, do not

  not an optimal delay in the propagation of combustion.

  Quantities greater than 90% are not desirable in

because of high viscosities.

  In addition to alumina trihydrate, other fillers or pigments may be included in the formulation of

  resin, although the total content of the

  alumina trihydrate) should not exceed 90% by weight relative to the total weight of

  resin, for viscosity considerations. Examples of

  Other fillers are calcium carbonate, magnesium sulphate, magnesium carbonate, sulphate

  potassium and aluminum, diatomaceous earth and clay.

  Examples of pigments are TiO 2, transparent iron oxide,

  and phthalocyanine pigments.

  The compositions of the present invention are

  by means of a vinyl addition polymerization.

  This polymerization is initiated by free radicals and suitable free radical addition polymerization initiators are benzoyl peroxide, tert-butyl perbenzoate, tert-butyl peroctoate, hydroperoxide, and the like.

  tert-butyl, cumene hydroperoxide, azobis (isobutyro-

  nitrile), methyl ethyl ketone peroxide and the like. The catalyst is generally used at a rate of about 0.1 to

246 1727

9.

  2% by weight relative to the total weight of the ingredients

  the quantities varying according to the activity and the quantity of the accelerator and the inhibitor

  be used in the softwood system.

  Examples of accelerators that are used to

  decrease the hardening temperature are salts of co-

  balt, such as cobalt octoate or co-naphthenate

  balt. The amount of accelerator used can vary widely, but usually ranges from 0.1 to

  1% by weight relative to the total weight of the ingredients

nous.

  To avoid any tendency to premature gelation

  In addition, a gelling inhibitor may be incorporated into the resin system. Suitable inhibitors are selected from quinone and phenolic compounds and include

  para-benzoquinone, hydroquinone and 4-tert-butylcatar

  chol. The amount of inhibitor needed in the mix

  may vary within wide limits, but is preferably

  from 0.001 to about 0.1% by weight of

weight of resinous ingredients.

  The compositions according to the present invention are

  usually reinforced with fiberglass and

  other common reinforcing agents, such as

  boron fibers, wood and plant fibers.

  For reasons of strength and price, however, it is preferred to use fiberglass reinforcement. Glass fibers for reinforcement are well known to those skilled in the art and

  the detailed description of various types of glass fibers

  is not considered part of the description

* Detailed of the present invention. For such a description

  detailed description, please refer to Reinforced Plastics, Theory and Procedure, by Mr.W. Gaylord, reproduction reserved

  in 1969, by Koppers Co., Inc., pages 47-72.

  In general, when the compositions of the present invention are reinforced with glass, about 5 to 70% by weight of

  relative to the total weight of the hardened composition

ble including glass.

  In addition to the ingredients mentioned above,

  10. very materials can be added to the composition. Examples include mold release agents, such as

  zinc stearate, or stabilizers with regard to

  Ultraviolet light, such as o-hydroxyphenylketones and 2- (2hydroxyphenyl) benzotriazoles. The quantities of these

  additional constituents are very small and do not exceed

  usually not mixed about 3% by weight of the poicd

  total of the curable composition.

  The compositions of the present invention are

  cies at a high temperature of about 121 to 1770C for

  as short as 30 seconds to 30 minutes, in

  tick from 30 seconds to 8 minutes or more depending on

  the hardening process, the resin system, the thick-

  the size and shape of the produced object.

  The curable compositions described herein can

  used for premix, pre-mix and

  mage or mat molding, as well as for lamination,

  as is well known to those skilled in the art.

  In the case of premix molding, the resinous component

  is intimately mixed with the alumina trihydrate and usually

  lemient with cut fiberglass and other ingredi-

  ents, such as a mold release agent and

  lymerization, in a mixing apparatus with a high rate of

  shear, such as a Sigma blade mixer. The mass

  The resulting machine is easily handled and is loaded in weighed quantities into an adjusted metal mold maintained at an elevated temperature of 121 to 170 ° C. and a pressure of 3.5 to 70 kg / cm 2 for a period of 30 seconds to 15 minutes.

  to harden the resin in order to obtain an article

  gide which is ejected hot from the mold.

  When mixing, in preform or mat, the composition

  The curable composition containing the resin, the alumina trihydrate, the release agents and the polymerization initiators is cast on the mat of preformed cut glass fibers or on the mat of continuous glass fibers, and introduced into an adjusted metal mold. occurs flow

  of the resinous product and where a hardening reaction takes place

  under the conditions of temperature and pressure

mentioned. he.

  During lamination, the hardened composition

  containing the resin, the alumina trihydrate, the release agent and the polymerization initiators is contacted with the glass reinforcement to form a composite layer between two plastic cover sheets to obtain a laminate . We adjust the thickness of the

  deposited layer and the resin content by exerting a

  on the squeeze rollers through which the laminate passes. The laminate is then passed through a heating zone by a suitable pulling mechanism. The cures are generally carried out at elevated temperatures, i.e. between about 49 and 1210C, and the time

  hardening is usually between about 30

condes and 20 minutes.

  As mentioned above, composi-

  curable compositions of the present invention possess excellent

  slow retarding properties of the transmission of

  bustion. The test protocols used to measure the flame retardance are the Underwriters' Tunnel Test (ASTM E-84) and the laboratory scale test.

  referred to as the Monsanto Tunnel Test, as well as the

  it's oxygen and smoke density.

  The Underwriters' Tunnel Test and Monsanto Tunnel

  Test measure the propagation characteristics of flam-

  of the cured compositions of the present invention. according to

  the ASTM manual, the Underwriters' Tunnel Test assesses the

  combustion characteristics and applies to any type

  of material. The purpose of the test is to determine the characteristics

  comparative combustion rates of the material under control

  by evaluating the spread of the flame on its surface.

  The test chamber is a horizontal pipe 44.5 cm wide, 31.8 cm high and 7.6 m long. Red oak is the stallion

  and it is arbitrarily attributed the value of 100.

  their O is attributed to asbestos. Other materials are

rated in proportion.

  It was suggested to adopt the following classification:

  te for the various notations of propagation of the flame.

  12. Flame Spread Classification 0-25 Class A, Non-Combustible

-75 Class B, delay in trans-

  combustion mission 75 and beyond Class C, fuel The Underwriters' Tunnel Test is a good measure of flame spread; however the test is of a

  expensive conduct and realization.

  There is a laboratory scale test that gives an indication of the spread of the flame. The test

  at the laboratory scale is referred to as Monsan-

  Tunnel Test and is described in the Journal of Paint Techno-

  logy, 39, (511), 494 (August, 1967). In the Monsanto Tunnel Test, a 61 x 9.5 cm sample is tilted at an angle

  about 450 to the horizontal. A source of

  their specified causes combustion at the bottom of the sample

  and then the sample is burned for four minutes.

  your. We note the propagation of the flame or the distance

  to which extends the flame on the sample. The components

  cured versions of the present invention correspond to the

  class A flame propagation

  determined by the Monsanto Tunnel Test.

  The oxygen index is determined according to ASTI D-2863.

  In general terms, the oxygen index of a material is the percentage by volume of oxygen in the atmosphere necessary to maintain the combustion of the material. For example, the air contains 21% by volume of oxygen. If a material is burned in the air, it has an oxygen index of 21 or lower. More

  the oxygen index of the material is high, the more difficult it is

  to ignite the sample. It is in this sense that the oxygen index is a measure of the delay in the transmission of combustion.

  of the sample. Hardened resinous materials

  of the invention containing hydrated alumina have

  these oxygen of at least 50, and preferably at least 70 that is easily obtained when the resin contains about

  at 90% by weight of alumina trihydrate.

  The amount of smoke produced by the combustion of the cured compositions of the invention can be measured by the smoke density according to a modified version of the standard 13.

  ASTM D-2843. In short, the test protocol consists of introducing

  to obtain a hardened test specimen of precise

  mined inside a smoke chamber NBS Aminco. The

  chamber is substantially airtight and contains one

  photoelectric lule in the top and a standard light source in the floor, which cooperate with each other to measure the optical transmission through the height of

  bedroom. The test piece is then exposed to a flame or-

  green and burnt or, according to another aspect of the test, the

  The specimen may be exposed to a source of radiant heat and subjected to slow combustion. According to both aspects of the test, the specimens are subjected to combustion and the smoke generated is collected in the chamber during

  the test, which usually lasts about 20 minutes, trans-

  optical mission being recorded continuously and the value

  nimal being taken as the measure of the density of smoke. The

  density of smoke is a logarithmic function of the trans-

  optical mission, as shown in the following table Maximum Smoke Density (D) m

  Conversion of transmission percentage to smoke density.

Percentage of Dm transmission

16

42 50

17.5 100

3,0,201

0.52 301

0.090 401

0.016 501

0.0028 601

0.00049 701

  The cured compositions of the present invention,

  when subjected to combustion as described above

  above, have densities of about 200 or less,

150 or less.

Examples 1 and 2

  The following two examples are modes of

  preferred embodiments of the invention. Examples show

  curable compositions prepared from the mixture of

  14. following ingredients: Ingredients

A - ethylene dimethacrylate

glycol

B-dimethacrylate trimer

thylolpropane

C - hydroxy methacrylate

  propyl D - methyl methacrylate

E - polybutadiene at

  hydroxyl salt F - alumina trihydrate G - zinc stearate (release agent)

H - tert-butyperbenzoate

the (initiator of

  free cals) I - tert-butyl peroctoate (free radical initiator) J - glass mat2 1Available in parts by weight (% by weight) Example 1! Example 2

57.5 (57.5) 4 -

, 4 (5,4) 4!

23.2 (23,2) 4!

13.9 (13.9) 4

3503 (77.8) 5;

32 (32

6 (6)

47 (47)

0, 0.67 (15)

(77,8J

, 0 0.67

0.67! 0.67

152.0 (25) 6! 152.0 (25)

Trade with Arco Polymers

  Inc. under the name R45-HT with a molecular weight of

yen in number of 2800.

  Two folds of glass mat M-86PP; 2 ounces, available

  from Owens Corning Fiberglas Corporation.

  380% by weight of alumina trihydrate of a size of

  particles of 3 to 10 microns, available from Alcoa Com-

  pany under the name C331 and 20% by weight of tri-alumina

  hydrated particle size less than 3 microns, available from Alcoa Company under the name H710,

  the weight percentage being based on the total weight of aluminum

do not trihydrate.

  4Compared to the total weight of (A), (B), (C), (D)

summer).

  In relation to the total weight of (A), (B), (C), (D),

(E) and (F).

  6Report to the total weight of (A), (B), (C), (D),

(E), (F), (G), (H), (I) and (J).

  In the examples above, polybutadiene has been

  dissolved with stirring in a mixture of the vinyl monomers

  ! ! ! ! ! 15. ques. Alumina trihydrate and zinc stearate have been

  then added by mixing with a shear rate of

  lifted, by means of an air motor and a propeller-shaped stirring blade, to form a uniform composition. The viscosities of the composition are given below. The

  composition was then cast on the glass mat and char-

  in a metal mold coated with chrome. Compositions

  were cured at 149 ° C. at 70 kg / cm 2 for 3 minutes.

  by providing hardened and smooth white articles

  seducing the physical properties listed below.

  Physical properties Example 1 Example 2

Brookfield viscosity in

  poises, axis n 7, 25 C 2 rpm 380,000 360,000 rpm 80,000 64,000 Notation of flame spread Monsanto O 2 Oxygen index 10010 100 Dm flame 121 76 Dm slow combustion 39 61 Hardness Barcol7 40-42 18 -30 Gloss to 60 8 77-80 78-82 Surface polish9 64 66 7The Barcol hardness is determined using a 934

  Impressor. It is a measure of hardness comparable with a

  value range from 0 to 100. The higher the value, the more

the material is hard.

  8Brilliant determined with a glossmeter at 60 C

  manufactured by Hunter Labs, model n D48D.

  n determines the surface polish by crossing the surface of the molded article with a profile (Surfanalyzer

  ) manufactured by Clevite Company, Gould Indus-

  tries, which measures the roughness of the surface. The roughness of

  surface area is expressed in micro-inches of undulation for a

  2 inches lay (1 inch = 2.54 cm). The higher the numerical value

  The higher the surface, the rougher the surface.

  The test tube did not maintain its own fuel

100% oxygen.

  Example 1 is preferred because of its excellent properties retarding the transmission of combustion 16. (flame propagation rating O). We prefer

  example 2 because of its excellent retardation properties

  the transmission of combustion, its low viscosity

  cosity and its good handling characteristics.

Examples 3 and 4.

  The following two examples illustrate composi-

  curable compositions with small amounts of monomer vi-

  nyl and without vinyl monomer. The compositions were prepared from the following Ingredients ingredients. Parts by weight (% by weight)

Example 3

Example 4

Ethylene dimethacrylate

glycol

Hydroxypropyl methacrylate

  Poly terminated polybutadiene of Examples 1 and 2

Alumina trihydrate e

  xamples 1 and 2 Zinc stearate Tert-Butyl Perbenzoate Tert-Butyl Peroctoate Glass Mat Examples 1 and 2 The compositions were as it is generally

267.1 (80.7)

17.9 (5.4)

46 (13.9)

(86.1)

46 (13.9)

993 (75) 993 (75)

16.7 16.7

2.2 i 2.2

2,2 2,2

441 (25)! 441 (25)

  have been prepared, processed and

described in Examples 1 and

  2 and smooth and shiny panels were obtained with respect

  Monsanto flame propagation ratings of, 4 and 10.7.

Examples 5-8.

  A series of experiments identical to that of the e-

  xample 2 was done, but with decreasing amounts

  trimethylolpropane trimethacrylate and, accordingly,

  with increasing amounts of methyl methacrylate. The

  curable compositions have been prepared from

following criteria -

  I: sueGpa2ul sutAins, p seautugm sap JTJud v sagadgid 959% uo suoi. Tsoooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo L aldeaxa, l4zueacd SC -ai ug xnon2n.i 4uema% 4% xa xnueuued sep 4uao; qo uo 'oooado -toPl q9mtJ op% X04 og% 9, a% y oppTod ua% l ap snossp -nV ea4uestnsuT uoElno7% 9g aun j enp ai4 friendsa uo, I enb eoujans ep Tiod ep% a 4uulllaq ep ', aeanp ep aead aun aud 4TnptJ% es enbiXuIAouou 9sodmoo ap 9;% Tutnb uz ep% uuuod Oú -saJoOD 4ueUssss! OJaOo an OGAE enb1IXuTASiod qsodmoo ap P%!% -Uenb ul ep uoTnuiup l anb% ueaiuomu saldmewaxe sar SLZ'I i Z i 6u i 9T j aeojans ep TtOd 0-0u i 09-S9 i 6L-úL i g8-8L i 009 V aUUIIFJa 01 i l -01i09 0 i ZZ i ao; ai% aJnj Sg 8 'xi LXa i 9' XS iS9JTaO! D: sae4uzAns sg: TadoJd slet% utzX xuellu1d sap nuaeqo u uo% a 'zg a I saldmaxa salt has been added to the price. ! ozpp% sa IF watero sapLnoU 4a sopTle4 sagaudgjd 959% uo saelqzssoanp suol4% sodmoo sar oz (Sg) Ipth (Sg) Ipth (g5) lip (Sg) Ippi z% a I salduexa i The SI

(SL) 0'U66. (SL)

  i Z'Z i Zz i i Zz i (St) The 6P i (Qt) i (L9) 8igzi i (g9) i

(9) 6'61. (9)

  i (g ') The 6C. (LI) 8 * i L 8 x.a i L i The IQ

0 '66,

at the SI

(SL) 0'U66

  i Z'Z; L z'6f (QI) i 6'61 i (l9) i i 'I' GOgI (LG) i 6'61 i (9) i ú'9. (gg) ixa At xfIi 9 g'Zg g'g The 6 'The 881 6'61 gxa i sap azeA ap 4% m The SI. ouz ap aetaC: 9s i (SL) 0'ú66. ## EQU1 ## agtUInt3 Sl z'g zj alnq -g.zaz-; ap eocooad g'oiz 9p 661alO q.axo 8 & ap a $ nozuaqaad (QI) The 68 i zoa I ii saedmaxa sap atXx 01 oJpXt & uosp.uzu.mI. zii 4V auaTpe4nqXod: (ZS) I 'ZuIi Xa i ep ae% uaOzqm i (9) 6'61 i zdodXxogp it; .a4P t &.! ToDutj; m S (LZ)' 6S. Suzdo.Xd ii ae4% t & JDtlDN49r.Jx i S * 'xi suaop.JzP uI LI (Sptoct ua%) SPTOct ue 5al4au1d 0001-E' They & H uoTzuTmou9p? I snos elqTuodSTp 'u- .-% in $% suI, P% 51% to 9'I- uoT4% nzusuTp% b g8% ueoooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo! .-eJnesu, p% GI% g '! - uoTJansu!, p% g8 4.ueuuoD' oo OO eq udom ee aeTulnDolom spTod a, p eGlxoqJuo uosT.uTmje%. uu punqXlodt 00OC-0 qUSjAH uoluîwTmougp el snos elqTuodsFp ' uAi-uo! ansuT., p% gS% e g'I-uoa: nzçsuFp% 8% umueauoo 'o0oO eqqe eeqe eeXe eJTilnogiom spTod a, p'eiaxo.púq uosTulmae% ç eugipunqxlod Cu "ao * 000O - E rS uo.oUu.umu9p vI snosg sIveomeqD JoedosTqDO ep sQ.dne elqTuods.p 'P'luoTeanwsuT.p% 01% e g'l- uo! EjnesuTp% 06% ueueuoo.e O00u ap e. What is the best way to do this? Do you know how to do this? Do you know how to do it? elqTuods.p '0009 eqe ee ee.eino9ioom spTod an eDaAe ei-uIoIJneusuTp% 9g; e 0'I-uoT% n.esuT & p% GS% uueuGuoo eilTe uos.FeuTm%; e UTpznqSlod i i L9'O i ú9'O i

(6'e: I) ç6'E: I

  (s'cg) Z'sz (G'tg) g'jg9 i (SZ) Ls1i g. G i

(9 'L) Ois.

  ## EQU1 ## where ## EQU1 ##

(6'úI) ú6'9I

  (g'gg) g'Ecg (7'úG) t'úg (G'Lg) g'LS (SZ) LEIi ig (9'SL) Oisú L9'0 i 9 'i ú91O i (6'ú1) z6 'ú1 (Z'g) Z'gZ (' LGS) g'Lg

(LSSLS

i (Z) the 9Ii

LZ '91;

* (GL) O'u66.

Z'Z i

L9'0Z;

(6'ú1)

(CI: 9)

  ('úg) (t' S) 19lP 'iL (g'Lg) ú'06IJ i g e I seald -maxe sap 9aaA 3p% m DUOIZ op a4ete; s z a9 I selexime sap e9ep nT; eu.runml oI $ nq -4; .e ep eo;% ooead aeIXnq -%. a9 ep aeozuoqJed euT. xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx; ep epozueqaed (SZ) 00z TOIexoqo uosTuU. mjao ç uQTptnq & Iod (L) 99 elq4u ap% el [Dq & 3 o (91) 0Z1 z 4a I SeTldaxa sep GlIxoJp -Xq uosuTu.mJxe4 Q euQTPUnqXlod 90 (9) 8g aedod xoaptp a4Tflq4ipm (Lú) 9Lu eaudo dIo -iKqmFl ap oaI & oqamT ( spTod ua%) spTod ua SaTi.% fl sua.pd.tMJI: S4UmAtns suaP9.j2uT OC -, p aoulgm npix4.% d Q, adgid 9% z 91 aIdmzxaI s4utITaJq 49 sass.I xnvauuud sep nuaqo v uo 49 ' Z 40 I sold -maxe ground suup aluagu9f Oa.juUM op 4.JTogp% sa I omMooD sa9gnuO 49 sa94Tzt4 'sagauBdgd 9% 9 (SZ) 0'I1pi (SZ) 1TV iZ (5L) 0'966 i (SL) 0 'ú66 iii

6'61 6'61

Z'Z; Z'Z;

(Zl ') 6u1 () 991 i i (OZ) Z99

- (9) 6'61

(96) 9'9IC (Zú) 6'901

i i.

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(9g) L19.

(IL) g'LZ8i (9L) C66i i

6'61 6'61

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(SL) 00ú;

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glass mat of exem-

  1 and 2, 133 (25); 133 (25); 133 (25) 1 unsaturated low molecular weight polyester resulting from the

  condensation of maleic anhydride, adipic acid, propylene

  ethylene glycol and ethylene glycol in a molar ratio of 3/7/3/9 to an acid value of 22.8 and a viscosity

  Gardner-Holdt G of a 75% solution in 2-ethoxy

ethanol.

  2 polypropylene glycol with a molecular weight of 2000 available

  from Wyandotte Chemical Company under the name

PPG 2010.

  3 polycaprolactone diol with a molecular weight of 7000

  Union Carbide Corporation under the name

PCL-300.

  In preparing, treating and molding the compositions as generally described in Example 2, glossy and smooth panels were obtained with the following Monsanto flame spread ratings: Example 21 Example 22 Example 23

32.1 64.2 42.8

  As can be seen, these ratings of

  paging of the Monsanto flame are much higher than

  those obtained for the compositions of the present invention.

tion. 23.

Claims (14)

CLAIMS.   1. Curable composition, characterized in that it comprises: (A) 17 to 95% of a compound containing at least two polymerizable vinyl groups per molecule; (B) 1 to 50% by weight of a polydiene polymer;   (C) O to. 70% of a polymeric monovinyl compound   sand, the percentage by weight of (A), (B) and (C) being   brought to the total weight of (A), (B) and (C), and (D) at least 50% by weight of alumina trihydrate, this percentage by weight being based on the total weight of (A), (B), (C) and (D).   2. Composition according to claim 1, characterized   in that (A) is an acrylic or methacrylic ester   of a polyhydric alcohol containing 2 to 5 hydroxyl groups.   3. Composition according to claim 2, characterized   in that the polyhydric alcohol contains 2 to 10 carbon atoms. bone.   4. Composition according to claim 1, characterized   in that the polydiene polymer is a 1,3-butadiene polymer.   5. Composition according to claim 1, characterized   in that the polydiene polymer is a polybutadiene hydroxy terminated.   6. Composition according to claim 1, characterized   in that the polydiene polymer has a moderate weight   average number of about 500 to 15,000.   7. Composition according to claim 1, characterized   in that (C) is a lower alkyl ester of acrylic acid or methacrylic acid containing 1 to 4 carbon atoms; carbon in the alkyl group.   8. Composition according to claim 1, characterized   in that it contains 55 to 85% by weight of tri-alumina moisturized.   9. Composition according to claim 1, characterized   inasmuch as it is essentially free of aromatic aromas.   10. Composition according to claim 1, characterized   in that it contains 5 to 70% by weight of glass fibers, the percentage by weight   curable composition, including glass.   11. Composition according to one of claims 1   or 10, characterized in that it is in the cured state as a molded article. 12. Process for the preparation of a hardened resinous article containing alumina trihydrate, characterized in that it comprises the steps of: (1) preparing a composition comprising:   (A) 17 to 95% of a compound containing at least two groups of   polymerizable vinyl pes per molecule; (B) 1 to 50% of a polydiene polymer; (C) 0 to 70% of a polymerizable monovinyl compound, the weight percent of (A), (B) and (C) being based on the total weight of (A), (B) and (C), and (D) at least 50% by weight of alumina trihydrate, this percentage by weight being based on the total weight of (A), (B), (C) and (D); (2) to heat this composition to a temperature   from about 121 to 177 C for about 30 seconds to 8 minutes then (3) cooling this composition.   13. Process according to claim 12, characterized in that the composition (1) is combined with fibers of glass before the heating step.   14. Method according to one of claims 12 or   13, characterized in that the heating phase is carried out in a mold at a pressure of about 3.5 to 70 kg / cm 2.