FR2515666A1 - MOLDING THERMOSETTING COMPOSITION, BASED ON POLYURETHANE OLIGOMER, EPOXY OR POLYESTER WITH AT LEAST TWO ACRYLATE GROUPS AND MOLD COATING PROCESS USING SUCH A COMPOSITION, OF A REINFORCED POLYESTER MOLDED COMPOSITION OF FIBERS OF GLASS - Google Patents

Abstract

THE INVENTION RELATES TO A THERMOSETTING MOLD COATING COMPOSITION. IT RELATES TO A COMPOSITION INTENDED TO FORM A COATING OF OBJECTS OF POLYESTER RESIN REINFORCED WITH GLASS FIBERS. THE COMPOSITION CONTAINS A POLYMERISABLE OLIGOMER, FOR EXAMPLE AN OLIGOMER HAVING TWO ACRYLATE GROUPS, A COPOLYMERISABLE MONOMER SUCH AS STYRENE, A ZINC SALT SUCH AS ZINC STEARATE, AN ACCELERATOR OF A PEROXIDYLATE INDUCER, AND POLYVETA INDUCER. . THE COMPOSITION ALSO OPTIONALLY CONTAINS COPOLYMERIZABLE MATERIALS SUCH AS HYDROXYPROPYL METHACRYLATE AND POLYOXYETHYLENEGLYCOL DIMETHACRYLATE, AS WELL AS CALCIUM SALT SUCH AS CALCIUM STEARATE AND CALCIUM STEARENT CHARGE. APPLICATION TO THE MANUFACTURE OF AUTOMOTIVE PARTS WITH AN EXCELLENT APPEARANCE.

Description

The present invention relates to a thermosetting composition of

  mold coating useful for coating a molded, fiberglass molded plastics material, such as a polyester resin or vinyl ester resin molding, or other part, which composition does not require not the combination

  two or more components just before use.

  A major disadvantage of compression-formed glass fiber-reinforced polyester moldings is surface defects such as pits, pores, surface cracks,

  corrugations and indentations The coating process

  to the mold described in the US patent

  No. 4,081,578 generally eliminates these

  by molding a polymerised resin of low visco-

  The composition described in this patent contains free hydroxyl groups as well as isocyanate groups which react with one another at room temperature and thus give a limited time.

  of service (around half an hour) In practice,

  reactive ingredients are kept separate and are not

  than just before the application A double pumping equipment and a precise dosing device are therefore needed and they increase the cost and complexity of

  the installation A coating formed using a single com-

  posing would therefore have a significant advantage.

  The invention relates to the suppression of

  ficultés indicated previously, by use of a method of coating the mold of a glass fiber reinforced polyester molding, using a coating composition

to a single component.

  It also relates to a one-component composition suitable for molding a mold

  of polyester reinforced with glass fibers.

  It also relates to a polymerized piece or molding of polyester reinforced with glass fibers, having a

  adhering coating made to the mold using a

one component.

  Specifically, a glass fiber reinforced polyester molding may be mold coated using a single component composition which is initiated by a free radical forming peroxide and comprising (a) a polymerizable oligomer selected from the group consisting of which comprises (1) a polyurethane oligomer having at least two acrylate groups, (2) an epoxy-based oligomer having at least two acrylate groups and (3) an oligomer

  polyester base having several ethylenically unsaturated groups

  and their mixtures, (b) a monomer copolymer-

  ethylenically unsaturated sand, (c) a zinc salt of

  fatty acid having at least 10 carbon atoms, (d) an

  the inducer of the peroxide inducer, and (e) acetate of

  The composition may further advantageously contain

  (f) a compound having a single unsaturated group and comprising a group -CO and a group -NH 2, -NH and / or -OH, (g) a polymerizable liquid compound having 2 to 4 vinyl groups, free of urethane groups , cycloaliphatic and aromatic compounds and having a molecular weight up to about 1500, (h) a calcium salt of a fatty acid having

  at least 10 carbon atoms, and (i) a charge.

  The composition has a satisfactory fluidity

  and it is stable even for about a week when

  it contains the peroxide It can be molded in a time

  The resulting hardened coating has good adhesion

  different polyester substrates reinforced with glass fibers and accepts finishing

  tie layer is necessary.

  We now consider in detail modes of

  advantageous embodiment of the invention.

  The terminated polyurethane oligomer

  polymerizable or crosslinkable diacrylate may be a diacrylate

  polyesterurethane, polyetherurethane or

  polyesteretherurethane or other polyurethane oligomer

  These materials may be prepared by reaction of a polyetherdiol (for example a polypropylene etherdiol), a polyesterdiol (for example a polyethyleneadipatediol) and / or a polyetheresterdiol (for example a polypropyleneetheradipatediol), or a triol ,

  etc., with a diisocyanate such as toluene diisocyanate

  ethylene oxide, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and the like, in an amount sufficient to form an isocyanate-terminated polyurethane prepolymer which then reacts with a hydroxypropyl or hydroxyethyl acrylate, a hydroxyethyl methacrylate and

  analogous so that it forms the polymer or oligomer of poly-

  The term "acrylate" as used herein refers to methacrylates and ethacrylates as well as mixtures thereof.

  Among these materials, the use of an oligomer

  Polyurethane diacrylate mother is advantageous.

  Acrylate terminated polyurethane oligomers, for example light-curable, ultraviolet, electric beam and / or infrared beam and the like, are well known and are sometimes considered

  such as polymerizable materials by irradiation or radiation

  ment. The epoxy-based oligomer having at least two acrylate or methacrylate or ethacrylate groups is prepared by reacting acrylic, methacrylic or ethacrylic acid, etc. with an oligomer or an epoxy-based resin such as an epoxy of Bisphenol A, bromine-bisphenol A, novolac

  phenolic, tetraphenylolethane, dicycloaliphatic

  etc. Mixtures of these epoxy-based oligomers may

  Among these materials, the use of an epoxy oligomer of Bisphenol A with a diacrylate terminus

  It is advantageous. These materials are well known.

  additional information on them can be found in the brochures

  "Heat Resistant Vinyl Ester Resin", M B Launikitis, Techni-

  Bull Bulletin, SC: 116-76, Shell Chemical Company, June 1976 and Shell Chemical Company Technical Bulletins SC: 16-76 and

SC: 6 n-78.

  The polyester-based oligomer having several internal ethylenically unsaturated groups may be formed by copolymerization of maleic anhydride and an alkylene oxide having 2 to 4 carbon atoms such as propylene oxide, ethylene oxide, butylene, isobutylene, etc. Propylene oxide and mixtures thereof with ethylene oxide are advantageous. The alkylene oxide can be used with a ratio of

  higher molar than that of maleic anhydride

  a polyester is formed which has terminations which are essentially or wholly of the -OH type, for example a

  polyesterdiol A saturated anhydride such as phthalic anhydride

  or other anhydride or mixture of anhydrides may

  replace up to about 50 mole percent of the maleic anhydride.

  A telogenic compound such as fumaric acid can also

  It is advantageous to use the anhydride

  These unsaturated polyesters can be prepared in benzene, styrene or other solvent with a dual metal cyanide catalyst as described in US Pat.

  U.S. Patent No. 3,538,043 As indicated by

  that patent, an isomerization catalyst such as

  peridine ensures the isomerization of the maleate double bonds of the polyester to fumarate double bonds. It is also possible to use morpholine as an isomerization catalyst as

  described in U.S. Patent No. 3,576,909.

  These polyesters may have molecular weights of between about 800 and 2500 and preferably between about 1000 and 1500. Polyesters formed by reaction of maleic anhydride or of maleic, fumaric, itaconic or citraconic acid with a glycol such as propylene glycol, dipropylene glycol, 1,4-butanediol, Bisphenol A, etc., containing small amounts of phthalic acid or anhydride and other diols and carboxylic acids can be used. The substantially aliphatic polyesters such as fumarates prepared at using catalysts based on double metal cyanide as described

  previously, are advantageously used

  additional requirements for the preparation of polyesters

  saturated appear in the book "Encyclopedia of Polymer Science and Technology", Interscience Publishers, division of John Wiley & Sons, Inc., New York, Vol 11, 1969, pages

129 to 168.

  A free-radical-forming or radical-forming organic inductor (catalyst) such as a peroxide is used for the catalysis of the copolymerization or cross-linking of the ethylenically unsaturated oligomer and the others.

  materials with ethylenic unsaturation Examples of

  radicals are tertiary butyl perbenzoate,

  tertiary butyl peroctoate in dialkylphthalate

  lyl, diacetyl peroxide in dimethyl phthalate, dibenzoyl peroxide, di (chlorobenzoyl) peroxide

  in dibutyl phthalate, di (2,4-dichloroacetate

  benzoyl) with dibutyl phthalate, the di-peroxide of

  lauroyl, methyl ethyl ketone peroxide, peroxide

  cyclohexanone in dibutyl phthalate, 3,5-dihydroxy-

  3,4-dimethyl-1,2-dioxycyclopentane, t-butylperoxy (2-

  ethylhexanoate), caprylyl peroxide, 2,5-dimethyl-

  2,5-di (benzoylperoxy) hexane, 1-hydroxycyclohexylhydro-

  peroxide-1, t-butylperoxy (2-ethylbutyrate), 2,5-

  dimethyl-2,5-bis (t-butylperoxy) hexane, cumyl hydroxyperoxide, diacetyl peroxide, t-butyl hydroperoxide, tertiary dibutyl peroxide, 3,5-dihydroxy

  3,5-dimethyl-1,2-oxacyclopentane, 1,1-bis (t-butylperoxy) -

  3,3,5-trimethylcyclohexane and the like and mixtures thereof It is sometimes desirable to use inductor mixtures in order to take advantage of their speeds and

  different periods of decomposition at different temperatures

  etc. An advantageous indictor is the perbenzoate

  of tertiary butyl The peroxide inducer should be used

  in sufficient quantity to compensate for the effect

  inhibitor and causes crosslinking or polymerisation of the

  of ethylenically unsaturated materials.

  use the peroxide inducer generally in

  up to 5% and preferably 2%

  approximately by weight relative to the weight of

  ethylenic turation used in the coating composition.

mold.

  An accelerator is used for the inductor

  peroxidic material and is a matter such as a

  For example, cobalt octoate Other materials that can be used are zinc, lead, cobalt or manganese naphthenate Soluble salts of Co, Mn and Pb of linoleic acid can also be used.

  It is sufficient that small quantities of accelerating

  In general, it is used in quantities

  between about 0.05 and 2 parts by weight for

  parts by weight of polymerizable oligomer.

  A small amount of a zinc salt of a fatty acid having at least 10 carbon atoms is also used in the composition and it appears to act as a release agent and a secondary accelerator of the invention. Polymerization Fatty acids are well known, as described for example in "Organic Chemistry", Fieser and Fieser, DC Heath and Company, Boston, 1944, pages 88, 381-390, 398 and 401 and "Hackh's Chemical Dictionary", Grant, McGraw Hill Book Company, New York 1969, page 261 Mixtures of zinc salts of fatty acids may be used Examples of certain zinc salts are palmitate, stearate, ricinoleate and the like It is preferable to use the zinc salt of a saturated fatty acid, such as zinc stearate Also available is "Whittington's Dictionary of Plastics", Whittington, Technomic Publishing Co., Inc., Stamford, Conn, 1968, pp. 35, 102, and 261. Zinc salt is used in general in an amount of about 0.2 to parts by weight per 100 parts by weight of the polymerizable oligomer. Small amounts of a calcium salt of a fatty acid having at least 10 carbon atoms

  for example 0.2 to 5 parts by weight of calcium salt

  The fatty acids are well known in the composition as mold release agents and for the control of the polymerization rate. The fatty acids are well known, as indicated above. Mixtures of calcium salts of the fatty acids can be used

  examples of such calcium salts are stearate, palmitate

  tate, oleate and the like It is advantageous to use the calcium salt of a saturated fatty acid such as stearate

of calcium.

  Polyvinyl acetate is used as

  low shrinkage or low profile adjuvant in the composition

  It also improves the adhesion of paints to the coating.

  Polyvinyl acetate is used in small quantities.

  By weight, relative to the total weight of the ethylenically unsaturated materials of the composition and sufficient for the paints to adhere. In general, polyvinyl acetate is used in an amount of between 40 and parts by weight per 100 parts by weight of the composition.

the polymerizable oligomer.

  An ethylenically unsaturated copolymerizable monomer is used in an amount at least sufficient for it to copolymerize with the polymerizable oligomer and to crosslink the polymerizable oligomer, this monomer being, for example, the

  styrene (preferably), alphamethylstyrene, vinyl

  toluene, t-butylstyrene, chlorostyrene, methacrylate,

  methylate, diallyl phthalate (with styrene or methyl methacrylate and the like), cyanurate

  of triallyl, triallyl isocyanurate, divinyl

  benzene, methyl acrylate and the like and their

  The unsaturated monomer is used gener-

  between 80 and 150 parts

  by weight per 100 parts by weight of the polymeric oligomer

  sand. It is also possible to use, but advantageously, in the coating composition in order to

  to increase copolymerization and crosslinking and to improve

  to improve the hardness of the resulting coating, a compound at a

  only ethylenic unsaturation and having a group -CO-

  and a group -NH 2, -NH and / or -OH Examples of such monomeric compounds are hydroxypropyl methacrylate (preferably), hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl crotonate, hydroxypropyl acrylate, hydroxypolyoxypropylene acrylate, hydroxypolyoxypropylene methacrylate, methacrylate

  of hydroxypolyethylene, acrylamide, methacrylamide,

  N-hydroxymethylacrylamide, N-hydroxymethylmethacrylate

  These compounds can generally be used in amounts of from about 0 to about 120 parts by weight per 100 parts by weight of the polymerizable oligomer.

  One can also possibly use but.

  advantageously, in place of a part of the polymerizable oligomer, a copolymerizable or crosslinkable liquid compound of an acrylate having 2 to 4 vinyl groups, free of urethane, cycloaliphatic and aromatic groups and having an average molecular weight which can reach 1500

  Examples of such compounds are trifethanol

  trimethylolpropane crylate, trimethylol triacrylate

  propane, pentaerythritol tetraacrylate, diacrylate

  triethylene glycol, tetraethylamine diacrylate

  glycol, tetraethylbene glycol diacrylate, dimetha-

  tetraethylene glycol crylate, 1,3-diacrylate

  butyleneg 4 Volt polyethylene glycol diacrylate, polypropylene glycol diacrylate, dimethacrylate

  polyethylene glycol, or polyoxyethylene dimethacrylate

  glycol (preferably) -, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, dimethacrylate

  polypropylene glycol, polyethylenepropylene diacrylate

  Glycol and the like and mixtures thereof As some of the reactive polyfunctional monomers may be formed by reaction of alcohols and unsaturated acids, they may contain certain OH and / or COOH groups. Polyfunctional reactive monomers may be used in a controlled manner.

  in quantities between about 0 and 120

  by weight per 100 parts by weight of the polymerizable oligomer. The unsaturated materials indicated above are thus used in sufficient quantities that, after polymerization (this term refers in this example to both polymerization and copolymerization).

  and / or crosslinking), they form a cured composition.

  The monoethylenically unsaturated compound having a CO group and having a group -NH 2, -NH and / or -OH (such as hydroxypropyl methacrylate) or the copolymerizable liquid acrylate compound having 2 to 4 vinyl groups and lacking cycloaliphatic urethane groups

  and aromatics (such as polyethylene dimethacrylate)

  glycol) or both compounds should be used in the

  coating composition when, after polymerisation,

  tion, the composition must be painted with a system based on

aqueous.

  The inhibitors are added in a desired amount to the composition or are placed in the raw materials before use so that the ethylenically unsaturated materials do not undergo premature gelation and the service life or storage is extended.

  Examples of inhibitors are hydroquinone, benzo

  quinone, p-t-butylcatechol and the like, and mixtures thereof. The mold coating composition can additionally receive a filler or adjuvants giving it the desired viscosity and flow properties so that

  it can be molded and the hardened coating

  Both have the desired physical properties. Fillers can also increase adhesion. Examples of such fillers or blend ingredients are fillers such as clay, talc, Ig, Mg (OH) 2, CaC 03, and the like. silica, other release agents, red iron oxide, Ti O 2,

  especially conductive carbon black, colored pigments

  res, anti-degradant adjuvants, ultraviolet absorbing agents, calcium silicate, paraffin wax hollow glass or resin microspheres, thickening agents, other shrinkage reducing additives and the like. advantageous is talc which can be used in the proportion of about 50 to 150 parts

  by weight per 100 parts by weight of the polymerization oligomer

  The use of an electrically conductive filler such as conductive carbon black, allows the painting of the coating by using conventional techniques.

  of electrostatic painting Such a conductive carbon black

  It can be used in amounts between about 15 parts and weight per 100 parts by weight of the polymerizable oligomer. These fillers and the mixed ingredients should be used in sufficient amounts.

  satisfactory results. However, pre-

  caution must be taken when using quantity

  high loads because they can give viscosities

  are high and present difficulties of flow and

  It is not desirable to use in the composition

  according to the invention, materials such as carboxylated styrene-butadiene block copolymers or phosphates

of fatty alcohols.

  Materials such as polyvinyl acetate can be dissolved in a reactive monomer such as styrene so that handling is facilitated. The viscosity of the oligomers can be reduced by dilution with styrene and the like. The ingredients of the composition should be easily mixed and treated at room temperature or

  temperatures below the polymerization temperature

  The ingredients can be heated or reheated before or during mixing, and gradually mixed so that a mixture, a dispersion and a

  Pushed solution of the ingredients is easy.

  Through the use of the catalyst or induc-

  The composition has a shelf life at room temperature (about 25 ° C.) of about one week.

  and, in the absence of the inductor, it has a duration of

  The inductor is advantageously added to the composition and mixed

  carefully just before molding.

  All the ingredients of the composition must

  must be kept dry and must have a minimum

  moisture content, or the moisture content must be reduced so that the results obtained are reproducible and

does not form pores.

  The mixture of the ingredients of the composition must be pressed. An injection or compression molding or injection molding machine or apparatus may be used for the formation of the coating. U.S. Patent No. 4,076,780 , 4,076,788, 4,081,578, 4,082,486, 4,189,517, 4,222,929, 4,245,006, 4,239,796 and

  4,239,808 disclose apparatus and methods of molding.

  Reference may also be made to the papers "Proceedings of the Second Annual Conference Reinforced Plastics / Composites Institute", SPI, Washington, DC, February 1977, Griffith et al, Section 2-C, pp 1-3 and 33rd Annual Technical Conference 1978 Reinforced Plastics / Composites Institute of the Plastics Industry, Inc. ", SPI,

  Ongena, Section 14-B, pages 1-7 The composition of

  mold can be applied to the substrate and polymerized

  at a temperature of about 143 to 1540 C, and at a pressure of

  about 7 106 Pa for 0.5 to about 3 minutes.

  The processes and products according to the invention can be used for the manufacture of automobile parts, in particular calenders and spotlights, hoods, bumpers, door panels and pavilions as well as

  in the manufacture of food trays, access to

  and electrical components, furniture, safety devices and machine covers, bathroom elements, support panels and the like. Fiberglass reinforced plastic material such as polyester resin or vinyl ester and the glass fiber-based composition substrate to which the molding composition is applied may be a sheet or plate molding material or a bulk material or other thermosetting reinforced material and a resistance molding material high or thick material The polyester substrate

  Armed can have about 10 to 75% by weight of glass fibers.

  The molding material in sheet or plate usually contains

  25 to 30% by weight of glass fibers whereas the molding material of high strength can contain about 60% by fiberglass fibers The fiber-reinforced plastic substrate can be made of fiberglass

  be rigid or semi-rigid (and may contain a

  wrinkling such as an adipate group in the polyester

1 - 2515666

  substrate may also contain other softening polymers

  elastomers and plastomeres such as cop-

  styrene-butadiene-type block copolymers Hardened, fiberglass-reinforced unsaturated polyesters are already known, as described, for example, in "Modern Plastics Encyclopedia", 1975-1976, October 1975, Vol 52, N 1 OA McGraw-Hill , Inc., New York, pp. 61, 62 and 105-107; "Modern Plastics Encyclopedia", 1979-1980, October 1979, Volume 56, Number 1 OA, pages 55, 56, 58, 147 and 148 and "Modern Plastics Encyclopedia", 1980-81, October 1980, Volume 57, Number O 10 A, pp. 59, 60 and 151-153, McGraw-Hill, Inc., New York, NY. The above-mentioned brochures are also available. The Shell Chemical Company Technical Bulletins

  which give information on vinyl ester resins

c.

  The compositions according to the invention may have

  good pumping and flow properties in the mold.

  They can give a fast hardening, as short as 90 seconds at 150 C In addition, they have good adhesion for paints and can be used

  not only in a mold coating, but also

  defects, but also as a good electrically conductive coating during electrostatic painting or as a bonding layer for most finishing systems to be painted, such as soluble acrylic lacquers,

  lacquers based on acrylic dispersion, acrylic enamels

  water based acrylic enamels in solution with a high solids content, non-acrylic

aqueous and urethanes.

  The following examples illustrate the invention

  in a manner particularly useful to those skilled in the art.

  In these examples, the parts are by weight except

otherwise stated.

Example 1

  The following ingredients are mixed:

13 2515666

Ingredient Parts by weight

A B C D E

"LP 90" 150 150 150 150 225

"UVITHANE 783" 150 180 180 225 150

"CHEMLINK 600" 180 90 90

  Hydroxypropyl methacrylate 90 90 180 Styrene 90 135 51 90 45 2% Benzoquinone in styrene 13.5 15 9 12 15 The following ingredients are then mixed: Zinc stearate 1.62 1.3 1.08 1.53 1.89 Cobalt octoate 0.54 0.6 0.36 0.51 0.63 (12% Co in a mineral oil) The following ingredients are then mixed: Carbon black "VULCAN" 27 30 18 25, 3175 Talc (630) 159 180 Then, to each composition, 1 part by weight of the inducer TBPB is added to 100 parts by weight of the total composition (the nature of the different ingredients is indicated in more detail in FIG. The composition obtained has the following properties: Gelation time 7.3 / 146 9, I / 179 4.5 / 158 7.7 / 159 14.4 at 110 ° C., min / temp.

  C Brookfield viscosity 8800 6200 16000 8400 760 l at 30 ° C., spindle No. 7 at rpm The above compositions for the coating of conventional hardened and molded substrate substrates of the polyester-styrene-fiber type are then used.

  glass (approximately 25% O of glass fibers) containing in

  in addition, a styrene-carboxylated block copolymer

  butadiene, at 7 106 Pa and 149 C for about 2 minutes.

  The overall results obtained for the hardened mold coating compositions are as follows: Hot Resistance (Mold Open Delamination) Substrate Adhesion Phase Separation Marginal Fit Yes (Low) Marginal Marginal Fair Marginal At Best Yes (Low) marginal marginal to passable non marginal passable yes (surface continuity or coating appearance) Conductivity (reading at 160-165 "Ransberg")

Unsatisfactory pencil hardness

nable

ASTM D 3363-74 B

* Finishing properties (paint acceptability) good * Versus acrylic paints based

+ 150-160 155 165 +

  suitable suitable suitable

HB 2 H 2 H HB

good bad * good good

  Aqueous Good vis-à-vis acrylic lacquers.

Ln n, 0%, 0%

Example 2

  The process of this example is similar to that

  of Example 1, except for the modifications indicated.

  The results obtained during the coating of the mold are satisfactory.

  The following ingredients are mixed -

  Parts by weight Ingredient F G "LP 90" 75 l O O

"UVITHANE 783" 100 75

"CHEMLINK 600" 25

  Hydroxypropyl methacrylate 30 Styrene 2 Benzoquinone 2 in styrene The following ingredients are then mixed: Zinc stearate 0.675 0.675 0.225 cobalt octoate 0.225 (12 Co in mineral oil) Calcium stearate 0.675 0.675 then mix the following ingredients: Carbon black "VULCAN" 1 i 11 Talc 70 70 Add 1 part by weight of TBPB inducer

  to each composition, per 100 parts by weight of the

total.

  The resulting compositions F and G satisfy all the tests indicated for compositions A to E of

Example 1 above.

Example 3

  This example corresponds to an advantageous method of preparing the coating composition before molding and curing. The ingredients are mixed in the order indicated: "LP 90" 100.0 parts by weight "CHEMLINK 600" 25.0 parts by weight hydroxypropyl methacrylate 20.0 parts by weight 2% benzoquinone in styrene 5.0 parts by weight 1 These materials are charged to the reactor and

they are mixed.

  Styrene Zinc stearate - Calcium stearate Calcium octoate (12% Co in mineral oil), 0 parts by weight) 6.55 parts by 0.675 parts by weight) Weight 0.675 parts by weight 0.200 parts by weight)

  2 The preceding materials are premixed and

  charge in the reactor After adding the charge

  indicated, it is heated to 44 C while mixing.

  "UVITHANE 783" (preheated to 49 ° C) 75.0 parts by weight

  3 "UVITHANE 783" material is added to the reaction

  and mix until the material is uniform.

It is cooled to 38 C.

  Carbon black "IVULCAN 1" 11.0 parts by weight 4 The carbon black is added to the reactor and mixed for 30 minutes.

38 C.

  Talc ("BEAVER WHITE 200" l) 70.0 parts by weight

  Talc is added to the reactor and mixed for 1 hour while maintaining the temperature at 38 C. The sample is removed. 6 We check the gel time If it is

  less than 8 minutes, 1 part by weight of benzo-

  2% quinone in styrene and mixed for 30 minutes.

  The gel time is checked again. The operation is repeated until the gelation time is

between 8 and 10 minutes.

  7 Subtract the total number of parts by weight

  of 2% benzoquinone in styrene from the previous additions

  dentes, of the number 5, and the difference is added in the form of styrene is mixed for 30 minutes, degassed during

  timed and filtered with a 0.25 mm orifice sieve.

It is kept at 7 C.

  The Brookfield viscosity at 30 ° C., with an N 7 spindle and at 100 rpm, is between 13,000 and 15,000. The gel time, at 110 ° C., is 8 to 10 minutes, with 1.0 part by weight. TBPB per 100 parts by weight of

  total composition During the preparation of the

  During the verification of the gelation time, 100.0 g of the total composition is weighed and 1.00 g of TBPB is added and then thoroughly mixed before running.

run the gelation test.

Example 4

  The method used in this example is analogous

to that of the previous examples.

Parts Ingredient

"LP-90"

"EPOCRYL 370"

"CHEMPOL 4825"

"UVIMER 580"

"ALTAC 382 E"

"CHEMLINK 600"

Hydroxy methacrylate

  Propyl Styrene 2% Benzoquinone in Styrene Zinc Stearate Calcium Stearate Cobalt Octoate (12% Co O in Mineral Oil) Carbon Black "VULCAN" Talc "BEAVER WHITE 200" HI by Weight JK 0.675 0.675 0.225 Added 1 part in each composition, per 100

total.

Gelification time 5.75 / 1 '

at 110 C

0.675 0.675 0.225

25

  0,675 0,675 0,225 0,675 0,675 0,225 weight of TBPB inducer

parts by weight of the composition

56 8.3 / 163 15.9 / 161 8.7 / 162

  Brookfield Viscosity at 30 C, spindle N 7 at rpm

12,800 10,200

  The properties of the mold coating are determined

2515666.

  of molded and cured polyester-styrene-glass fiber substrates. Resistance to hot Adhesion to the substrate (scalpel, severe test) Demoulding Phase separation Conductivity (reading at the "Ransberg" device)

Example 5

The process of c

previous examples.

good marginal good

suita

ble ble venable

molding

defective,

bad news

and

bad luck

no no no no

-165,165

  and example is analogous to that Ingredient

"LP-90"

"UVITHANE 893"

Polyester UVIMER 530 "

"NUPOL 46-8012"

"CHEMLINK 600"

Hydroxy methacrylate

  Propyl Styrene 2% Benzoquinone in Styrene Zinc Stearate Calcium Stearate Cobalt Octoate (12% Co in Mineral Oil) Carbon Black "VULCAN" Talc "BEAVER WHITE 200" Parts by Weight L

0, 675

0.675 0.225 M N O

25 25

0.675 0.675 0.225 0.675

0, 675

  0.225 l 70 0 675 0.675 0.225 1 part by weight of the inducer TBPB is added

  to each composition, per 100 parts by weight of the

total.

  Gelation time 14.9 / 153 6.1 / 161 7.5 / 169 25.3 / 120

at 110 C

  Brookfield Viscosity at C, NI Spindle 7 at RPM 17,600 14,400 The properties of the mold coating formed on polyesterstyrene-cured and molded glass fiber substrates are as follows: Hot resistance good marginal good bad Adhesion to substrate suitable -convena non-convex (with a scalpel, test nable ble nable severe) Demoulding convenaconvena convena m ble ble ble ble e de dé-

tectuous -

polymerisation

inadequate

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  Separation of the phases Conductivity (reading with the apparatus "Ransberg") no yes excessive Of the examples 4 and 5, the compositions H, I

and L are the best.

  Notes for Examples "LP-90" refers to "BAKELITE LP-90", having 40% by weight of polyvinyl acetate in styrene, with

  viscosity of 1800 centipoise at 25 C, determined by viscosity

  Brookfield type LVT N4 spindle measuring at 60 rpm,

  the density 20/20 C (H 20 = 1) being 1.008 and the temperature

  solidification of 5 C (Union Carbide Corp).

  "UVITHANE 783" is an oligomer or a poly-

  This viscous liquid (1.3 kg / l at 25 ° C.) having a viscosity of 600 to 2000 poise at 49 ° C. and 50 to 110 poise at the end of the reaction was obtained from the urethane-based meriform prepolymer. C, having an unsaturation of from 0.17 to 0.205 equivalents / 100 g and an isocyanate content of not more than 0.3% Thiokol / Chemical Division, Thiokol Corporation. "CHEMLINK 600": or "CL 600" dimethacrylate

  polyethylene glycol 600 Molecular weight ca.

  C 36 H 66017 (The Ware Chemical Corp.).

  17 - "VULCAN" XC'-72 B N 472 Conductive carbon black

in the oven (Cabot Corp).

  Talc silicate magnesium hydrate.

  TBPB tertiary butyl perbenzoate.

  "EPOCRYL 370" diacrylate-ester of a Bisphenol A liquid epoxy resin, nonvolatile, having a viscosity of 9000 poises at 25 C (100% resin), an acidity of 0.007 equivalents / 100 g, a degree of equivalent epoxide per gram of 0.02, a Gardner color number of 4, a density of 1.197, a flash weight of greater than 204 ° C. and a Gardner VY viscosity at 25 ° C. (80% by weight of resin in xylene). Shell Chemical Co: "CHEMPOL 4825" (19-4825) solvent-free acrylate and epoxy resin containing active acrylic unsaturation on the polymer molecule. It has an acid number of 3 to 10, a color of 1 to 4, a viscosity of 4000 to 6000 centipoises at 60 C and 1400 to 1800 centipoises

  at 71 C, as well as a density of 1,174-1,198.

  hold at most 2% by weight of free acrylic acid.

(Freeman Chemical Corp).

  "UMIVER 580" o Highly reactive ethylenically unsaturated liquid jigomer in a radical polymerization Amber liquid at room temperature, having a characteristic sweet odor Its viscosity (Gardner Holdt) is Z 6 -Z 7 (200-500 poises), its color (Gardner Holdt) of up to 3, its density of 1.15 + 0.12 and its flash point (closed cup) of about 99 C (Polychrome Corporation). "ATLAC 382 E" I 1 is a polyester resin

of Bisphenol A (ICI Americas Inc).

  "UVITHANE 893" Polymerizable urethane oligomer in the form of a viscous liquid Its APHA color is of maximum, its sweet smell, its density of 1.198 at 25 C, its viscosity of 900 to 2200 poises at 49 C, from 80 to 180 poise at 71 C and 30 to 80 poise at 82 C, its unsaturation is 0.150 to 0.175 equivalents / 100 g and its isocyanate content

  0.2% maximum (Thiokol Corporation).

  Polyester I 1 is a polyester formed by copolymerization of propylene oxide, ethylene oxide,

  of maleic anhydride, fumaric acid and phthalic anhydride

  with a metal cyanide catalyst.

  It has undergone isomerization, has terminal

  OH sounds and has a molecular weight of about 1200.

  "UVIMER 530" ethylenically unsaturated liquid oligomer having an extremely high reactivity in a radical polymerization Its viscosity (Gardner-Holdt) is Z 7 -Z 8 (375-600 poises), its color (Gardner-Holdt) from 5 to maximum, its density of 1.174 + 0.06, and its closed cup flash point of about 99 C (Polychrome

Corporation).

  "NUPOL 46-8012" 70% blend of a polymer

  with acrylate termini, 28% styrene and 2 methacrylate

hydroxyethyl late.

Claims (8)

  1 Useful composition in the form of a composition   thermosetting molding, characterized in that it   contains (a) a polymerizable oligomer selected from the group consisting of (1) a polyurethane oligomer having at least two acrylate groups, (2) an oligomer based on   epoxy having at least two acrylate groups, and (3) an oligomer   polyester-based mother having multiple unsaturation groups   internal ethylenic mixture and mixtures thereof, (b) a monomer   lymerizable ethylenically unsaturated, (c) a zinc salt of a fatty acid having at least 10 carbon atoms, (d)   an accelerator of a peroxide inducer, and (e)   polyvinyl acetate in a smaller amount by weight than the polymerizable materials and sufficient to promote the adhesion of the paints and, possibly, (f)   a copolymerizable material with a single ethylenic unsaturation   having a group -CO and a group -NH 2, -NH and / or   -OH or more of these groups, optionally (g) a   copolymerizable liquid material for partly replacing the polymerizable oligomer (a) and having two to four vinyl groups, free of urethane, cycloaliphatic and aromatic groups and having a molecular weight less than or equal to about 1500, optionally (h) a salt of calcium of a fatty acid having at least 10 carbon atoms, and   possibly (i) a load, the materials having a   ethylenic saturation being present in sufficient quantities   health so that they cause the formation of a composition cured after polymerization.   2 Composition useful as a thermosetting composition   molding composition, characterized in that it contains (a) parts by weight of a selected polymerizable oligomer   in the group comprising (1) a poly-based oligomer   urethane having at least 2 acrylate groups, (2) an oligo-   epoxy-based mother having at least 2 acrylate groups, and (3) a polyester-based oligomer having a plurality of internal ethylenically unsaturated groups and mixtures thereof, (b)   to about 150 parts by weight of a copolymerizing monomer   ethylenically unsaturated, (c) from 0.2 to 5 parts by weight of a zinc salt of a fatty acid having at least carbon atoms, (d) from 0.05 to 2 parts by weight of accelerator of a peroxidic inducer, and (e) 40 to 80 parts by weight of polyvinyl acetate, the composition optionally also containing (f) 0 to 120 parts by weight.   by weight of a single-component copolymerizable material   ethylenic saturation having a group -CO and a group -NH 2, -NH and / or OH or more of these groups, optionally (g) O to 120 parts by weight approximately of a liquid material   copolymerizable to partially replace the oligomer   polymerizable mother (a) and having 2 to 4 vinyl groups,   urethane, cycloaliphatic and aromatic groups and having a molecular weight less than or equal to 1500, optionally (h) 0.2 to 5 parts by weight of a calcium salt of a fatty acid having at least 10 carbon atoms.   carbon, and possibly (i) a charge.   Composition according to Claim 2, characterized   in that it also contains a peroxidic inducer or-   free radical in quantities of 5% or less   by weight in relation to the weight of ethylenic turation.   Composition according to Claim 2, characterized in that   oligomer (a) is a liquid polyester urethane   diacrylate-terminated or a diacrylateester of a liquid epoxy resin of Bisphenol A, the monomer (b) is styrene, the zinc salt (c) is the zinc sterate, the accelerator (d) is the octoate of cobalt, the copolymerizable material (f) is hydroxypropyl methacrylate,   the copolymerizable material (g) is a dimethacrylate   polyoxyethylene glycol salt having a molecular weight of about 770, the calcium salt (h) is calcium stearate, the filler (i) is talc, in an amount between 50 and 150 parts by weight, and black of conductive carbon in an amount of between about and about 15 parts by weight. A composition according to claim 4, characterized in that it further contains not more than about 2% by weight of tertiary butyl perbenzoate, based on   weight of ethylenically unsaturated materials.   6 Method of coating a composition with a mold   molded cured polyester resin and ester resin   hardened nylon reinforced with glass fiber, containing about   at 75% by weight of glass fibers, using a   thermosetting position of mold coating, under pressure, at a temperature and for a time sufficient for the polymerization of the coating composition to the mold   and forming a hardened coating adhering to the composition   cured resin molded resin composition, said method being characterized in that the coating composition   mold contains (a) a selectable polymerizable oligomer   if in the group which comprises (1) an oligomer based on   polyurethane having at least 2 acrylate groups, (2)   epoxy-based gomer having at least 2 acrylate groups and (3) a polyester-based oligomer having more than one ethylenically unsaturated group, and mixtures thereof, (b) an ethylenically unsaturated copolymerizable monomer, (c) a zinc salt of a fatty acid having at least 10 carbon atoms, (d) an accelerator of a peroxidic inducer, and (e) polyvinyl acetate in a low pondetal amount relative to that of the polymerizable materials and sufficient to that it promotes the adhesion of paints,   the composition optionally containing (f) a copious material   lymerisable to a single ethylenic unsaturation having a group -CO and a group -NH 2, -NH or -OH or more-de   these groups, possibly (g) a liquid copoly-   merizable to partially replace the polymerizable oligomer (a) and having 2 to 4 vinyl groups, free of urethane, cycloaliphatic and aromatic groups and   having a molecular weight of up to 1500, possibly   (h) a calcium salt of a fatty acid having at least carbon atoms, optionally (i) a filler, the ethylenically unsaturated materials being present in an amount sufficient to form a cured composition after polymerization, and j) a radical organic peroxidic inducer in an amount of up to about 1% by weight based on the weight of the materials to be ethylenic unsaturation.   7 Method of coating a composition with a mold   molded of hardened polyester resin or vinylester resin   liquefied hardened fiberglass, containing about 10   to 75% by weight of glass fibers, using a   thermosetting coating to the mold, under pressure, at a temperature and for a time sufficient for the polymerization of the coating composition to the mold and the formation of a cured coating adhering to the composition   molded resin reinforced fiberglass, said pro   characterized in that the mold coating composition contains (a) 100 parts by weight of a polymerizable oligomer selected from the group consisting of (1) a polyurethane oligomer having at least two acrylate groups, (2) an epoxy-based oligomer having at least two acrylate groups, and (3) a polyester-based oligomer having multiple internal ethylenically unsaturated groups and mixtures thereof, (b) 80 to 150 parts by weight of a monomer   copolymerizable with ethylenic unsaturation, (c) 0.2 to 5 parts   about 30% by weight of a zinc salt of a g-ras acid having at least 10 carbon atoms, (d) from about 0.05 to 2 parts by weight of an accelerator of a peroxide inducer,   and (e) from about 40 to about 80 parts by weight of polyvinyl acetate.   vinyl, the composition optionally also containing (f) O to 120 parts by weight of a copolymerizable material   with a single ethylenic unsaturation having a group -CO-   andan -NH 2, -NH or -OH group or more than one of these groups, optionally (g) 0 to about 120 parts by weight of a copolymerizable liquid material intended to replace in part (the polymerizable oligomer (a) and having four-group vinyl groups, no urethane, cycloaliphatic groups   aromatic and with a molecular weight of up to   about 1500, (h) 0.2 to 5 parts by weight of a calcium salt of a fatty acid having at least 10 carbon atoms, optionally a charge, and (j) a radical organic peroxidic inducer in amount may be up to 5% by weight based on the weight of the materials with ethylenic unsaturation.   Process according to Claim 7, characterized   in that the polymerizable oligomer (a) is a polyester-   diacrylate-terminated liquid urethane or a diacrylate   ester of a liquid epoxy resin of Bisphenol A, the monomer (b) is styrene, the zinc salt (c) is zinc stearate, the accelerator (d) is cobalt octoate, the copolymerizable material ( f) is hydroxypropyl methacrylate, the copolymerizable material (g) is polyoxyethylene glycol dimethacrylate with a molecular weight of about 770, the calcium salt (h) is calcium stearate, and the filler (i) is talc in an amount of between about 50 and 150 parts by weight and conductive carbon black in an amount of   between about 5 and 15 parts by weight.   Process according to claim 8, characterized in that the inducer is tertiary butyl perbenzoate and is used in an amount of up to about 2% by weight. Product, characterized in that it is prepared by carrying out the process according to any one of Claims 6 to 9.