JPS58125762A - Mold inside coating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes polyester resins or vinyl ester resins (FRP) that do not require combining two or more components immediately before use.
) Thermosetting in-mold coating compositions useful for in-mold coating of molded glass fiber reinforced thermoset plastics, such as molded articles or parts.

Shrink molded thermosetting glass fiber reinforced polyester (
The major drawbacks of FRP molded products are surface defects such as dents, porosity, surface cracks, corrugations, and sink marks. The in-mold coating method of US Pat. No. 4,081,578 overcomes these deficiencies by generally molding a low viscosity thermoset onto the FRP surface in a second molding operation. The compositions described in U.S. Pat. No. 4,081,578 contain free hydroxyl and isocyanate groups that co-react at room temperature, resulting in a limited pot life (ca.
0 minutes). If carried out, the reaction components are kept separate and brought together only immediately before application. This requires duplicate pumping equipment and accurate metering equipment, increasing the cost and complexity of the system. Single component deposition therefore offers significant advantages.

Therefore, it is an object of the present invention to provide a method for coating an FRP molded article in a mold with a -component coating composition while avoiding the problems described in 1 above.

Another object of the present invention is to provide a one-component composition suitable for coating inside a mold of an FRP molded product.

Yet another object of the present invention is to provide a cured molded FR having an adhesive coating in-mold with a component in-mold coating composition.
To provide molded products or parts.

These and other objects of the invention will become apparent to those skilled in the art from the following detailed description and examples.

FRP Cedar products are coated in-mold using a one-component free radical peroxide initiation composition consisting of the following ingredients: (a
) (1) polyurethane-based oligomers with at least two acrylate groups, (2) epoxy-based oligomers with at least two acrylate groups, and (3)
) a polymerizable oligomer selected from the group consisting of polyester-based oligomers having a plurality of internal ethylenically unsaturated groups and mixtures thereof; (b) a copolymerizable ethylenically unsaturated monomer; (c) at least 10 carbon atoms; (d) a promoter for peroxide initiators;
and (,1) polyvinyl acetate. Optionally and desirably, the composition may also include (f) -00- groups and -NH2, -
Monounsaturated compounds with NH- and/or -OH groups, (
g) copolymerizable liquid compounds with 2 to 4 vinyl groups, free of urethane, type aliphatic and aromatic groups, and up to about 1500 molecular weight; (h) at least 10 carbon atoms; Contains a fatty acid calcium salt with atoms, and a filler.

This composition has good flow properties and is stable for about a week even when containing peroxide. You can mold this in a short time. The resulting thermoset coating exhibits good adhesion to different FRP substrates and accepts many paint finishes, reducing the need for brimers.

The polymerizable or crosslinkable diacrylate-terminated polyurethane oligomer can be polyester urethane diacrylate, polyether urethane diacrylate or polyester ether urethane diacrylate or other polyurethane oligomers having two or more acrylate groups. To make these materials, polyether diols (
e.g. polypropylene ether diol), polyester diol (e.g. polyethylene adipate diol)
and/or a polyether ester diol (e.g. polypropylene ether adipate diol) or a triol, etc., with a diisocyanate such as trilene diisocyanate), 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, etc. to form an isocyanate-terminated polyurethane prepolymer. Reacting with enough nails and then reacting this prepolymer with hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. will result in diacrylate-terminated polyurethane oligomers or polymers. − occurs. These acrylate end points 1] Urethane oligo?
- can be used. As used herein, the term “
"Acrylate" is intended to include methacrylate, methacrylate as well as acrylate. Of these materials, it is preferred to use diacrylate polyester urethane oligomers. Acrylate-terminated polyurethane oligomers are well known to be curable, for example by light, ultraviolet light, lightning, and/or infrared radiation, and are sometimes referred to as irradiation or radiation curable materials.

Epoxy-based oligomers with at least two acrylate (or methacrylate or fly ethacrylate) groups include acrylic σ2, methacrylic acid, or botacrylic acid, etc., such as bisphenol A epoxy, Tetrabu IJ Mobisphenol A epoxy, Phenono L [novolac epoxy, It is made by reacting with epoxy-based oligomers or resins such as tetraphenyloethane epoxy, dicycloaliphatic epoxy, and the like. Mixtures of these epoxy-based oligomers can be used. Of these materials, it is preferred to use diacrylate-terminated bisphenol A epoxy oligomers.

Such materials are well known. Furthermore, regarding these errors, +t'P L/
aunikj, ti, s), Teahni, cako B
u],]θf;in XSC: 116-76, Shell Chemical Company, June 1976, and Shell Chemical Company, Te
Chnical Bulletin So: 16
See 76 and SO:60-78.

The polyester-based oligomers used with a number of internal coylene unsaturations include maleic anhydride, ethylene oxide, butylene oxide, isobutylene oxide, etc., and mixtures thereof.
It is produced by copolymerizing carbon molecules with alkylene oxide. Propylene oxide and mixtures of propylene oxide and ethylene oxide are preferred. Alkylene oxide can be used in a larger molar ratio than maleic anhydride to obtain essentially or entirely OH-terminated polyesters, such as polyester diols. About 50 mole percent of the maleic anhydride can be replaced with saturated anhydrides such as phthalic anhydride, its functional anhydrides, and mixtures thereof. Telogens such as 7-marl can also be used. Preference is given to using maleic anhydride. These unsaturated polyesters can be made in benzene, styrene, or other low solvents using a double metal cyanide (cyanide containing multiple metals) catalyst as shown in the 'Cyber+4 Patent No. 3,538,043. can. As shown in that patent, an isomerization catalyst such as piperidine is used to isomerize the maleate double bonds of the polyester to fumarate double bonds. Morpholine can also be used as an isomerization catalyst, as shown in US Pat. No. 3,576,909.

These polyesters have a molecular weight of about 800 to 2,500, preferably about 1,000 to 15,000.

Maleic anhydride, maleic acid, fumar L-shun, itacon t# or citraconic acid with a small amount of phthalic acid, phthalic anhydride 1-e-41H→--4・Nanako-di→→Kijuji se Propylene glycol and dipropylene glycol polyester can be used. Substantially aliphatic polyesters, such as the fumarate polyesters made using the double metal cyanide catalysts described above, are preferred for use. For more information on the history of unsaturated polyester production, see Encyclopedia of Polymer Science and Technology, Interscience Publishers.
See John Wiley and Sons Department of Ceremonies, New York, Vol. 11, 1969, pp. 129-168.

Organic free radicals or free radical generating initiators, such as peroxides, are used to catalyze the copolymerization or crosslinking of ethylenically unsaturated oligomers with other ethylenically unsaturated materials. Examples of 7-radical initiators are tert-butyl per-octoate in diaryl heptatarate, diacetyl peroxide in dimethyl heptatarate, dibenzoyl peroxide, dibutyl phthalate, The past
Dredged di(p-chlorobenzoyl), di(2,4-dichlorobenzoyl) peroxide with diptyl 7-talate, dilauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide in dibutyl 7-talate, 3°5 -dihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethylhexanoate), buryl peroxide, 2,5-dimethyl-2,5
-di(benzoylperoxy)hexane, 1-hydroxycyclohexylhydroperoxide-1, t-butylperoxy(2-ethylbutyrate), 2,5-dimethyl-2゜5-bis(1-butylperoxy) Hexane, cumyl hydroperoxide, diacetyl peroxide, t-butyl hydroperoxide, di-tert-butyl peroxide, 3I5-dihydroxy-3,5-dimethyl-1,
Includes 2-okinacyclopentane, 1,1-bis(1-butylperoxy)-3,3,5-)limethylcyclohexane, and mixtures thereof. It is sometimes desirable to use initiator mixtures and take advantage of different decomposition rates and times at different times. The preferred initiator for use is tert-butyl perbenzoate. Sufficient amount should be used to overcome the effects of the iAV+ rθ action initiator inhibitor and to cause crosslinking or curing of the ethylenically unsaturated) material. Generally, peroxide initiators can be used at about 5% by weight, preferably up to about 2% by weight, based on the weight of the ethylenically unsaturated material used in the mold coating composition.

Accelerators are used for oxidation initiators and desiccant agents, such as cobalt octoate.

Other materials that can be used are zinc naphthenic acid, naphthenic acid, cobalt naphthenate, and manganese heptathenate. Soluble On, Mn of riruonic acid.

pb can also be used. Accelerators only need to be used in small amounts.

In general, about 0.00% per 100 polymerizable oligomers.
A total of 0.05 to 2 thick parts of accelerator is used.

A mold deposit of a diluted zinc salt having at least 10 carbon atoms is also used in the mold coating composition and is believed to function as a mold release agent and a secondary accelerator of curing. fat! '1
1? It is well known. “Organic Chemistry 1 Feaser &
Fleser (Fko θSer and Fleser)
, D. O., Heath & Company, Boston;
1944, 88'i! , 381-390.39
8 and 401, and Huck Chemistry Dictionary - 1, Grant, McGraw-Hill Publishers, New York, 1969, p. 261. Mixtures of zinc salts of fatty acids can be used. Examples are valmitin (zinc chloride, zinc stearate, zinc resinolate), etc. It is preferable to use a curved lead salt of a fatty acid such as lead stearate. ``Lightington Plastic Dictionary''Lightington (Whl, ttillgton),
See also: Mink Publishing, Schunford, Conn., 1968, 35.102.261. About 0.2 to 75 parts of zinc salt per 100 aiJ of polymerizable oligomer are generally used.

Preferably, a small amount of a fatty acid calcium salt having at least 10 carbon atoms, such as about 0.2 to 5 parts by weight of calcium salt per 100 parts by weight of polymerizable oligomer, is separated. It is used in mold coating compositions as a molding agent and to control hardening speed. Fat r? is well known, see above. Use a mixture of fatty acid calcium salts.

Some examples of calcium jp include d1, calcium stearate, calcium palmitate, calcium oleate, etc. Preferably, calcium salts of saturated fatty acids are used, such as calcium stearate.

Polyvinyl acetate is used as a low shrinkage or low profile additive in the in-mold composition. Also, this is
Improve the adhesion of paint to the inside of the mold. The polyvinyl acetate is used in small amounts compared to the total density of the ethylenically unsaturated material in the internal coating composition, but in sufficient amounts for paint adhesion. Generally, polyvinyl acetate is used at about 40 to 80 parts per 100 parts of polymerizable oligomer.
,ru.

The R-merizable ethylenically unsaturated mono-yellow compound is used at a concentration sufficient to copolymerize and crosslink with at least 1 F-merizable oligomer, such as styrene (preferred), alpha methylstyrene,
Includes vinyltoluene styrene, chlorostyrene, methyl methacrylate, diallyl phthalate (with styrene or i7Tt methyl methacrylate, etc.), triallyl cyanurate, triallyl isocyanurate, divinylbenzene, methyl acrylate, etc., and mixtures of straws. Generally, one unsaturated mass is used at about 80 to 150 parts by weight per 100 parts by weight of polymerizable oligomer.

Optionally and preferably for further copolymerization and crosslinking,
and -co- groups and -NH, -NH- and/or - in order to improve the hardness of the resulting coating.
〇 Monoethylenically unsaturated compounds with H groups can be used.

Examples of such monomeric compounds are hydroxylpropyl methacrylate (preferred), hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl crotonate, hydroxypropyl acrylate, hydroxypolyoxypropylene acrylate, hydroxypolyoxypropylene methacrylate, hydroxypolyoxy These include ethylene methacrylate, acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and mixtures thereof. These arsenals can generally be used in amounts of about 0 to 120 parts by weight per 100 parts by weight of polymerizable oligomer.

Optionally, and preferably, as a partial alternative to polymerizable oligomers, having 2 to 4 vinyl groups, free of urethane, cycloaliphatic IJh groups, and aromatic groups, about 1
Liquid acrylate compounds that can be polymerized or crosslinked with an average molecular weight of up to 500 111 can be used. Examples of such compounds are trimethylonopropane trimethacrylate, 1, and trimethylolpropane.

Vantriacrylate, pentaerythritol tetraacrylate, triethylene glyfur diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol diacrylate moiety substitute 3-butylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glyfur diacrylate, polyethylene glycol Dimethacrylate or poly(dexaethylene glycol dimethacrylate) (preferred), pentaerythritol triacrylate, 1,6-hexanediol diacrylate, polypropylene glycol dimethacrylate, polyethylene propylene glycol diacrylate, etc. and the like.

Includes mixtures. These reactive polyfunctionals? Some of the Il1 isomers are produced by reacting unsaturated acids with alcohols, so they contain some 01-1 and/or 0OO
Contains H group. The reactive polyfunctional monomer is generally used in an amount of about 0 to 120 parts by weight per 100 parts by weight of polymerizable oligomer.

The unsaturated material is thus used in an amount sufficient to provide a thermosetting composition upon curing (eg, polymerization, copolymerization, and/or crosslinking).

-NH2, -NH- and/or -OH with -oo- group
monoethylenically unsaturated compounds with groups (such as hydroxypropyl methacrylate) or with 2 to 4 vinyl groups and no urethane, cycloaliphatic and aromatic groups (such as polyethylene glycol dimethacrylate). )
Liquid copolymerizable acrylates, or their solid compounds, should be used in mold coating compositions when applied with water-based threads after curing.

To prevent premature gelation of the ethylenically unsaturated material and provide improved f♀ shelf life or shelf life, the desired amount of inhibitor is added to the composition or provided in the raw material prior to use. Examples of inhibitors are hydroquinone, benzoquinone, p-t
-butylcatechol, etc., and mixtures thereof.

Optionally, the entire in-mold composition is filled or compounded to provide the composition with the desired viscosity and fluidity for molding, and to impart desired physical properties to the resulting thermoset coating. can. Fillers may also improve adhesion. Examples of such filler or powder ingredients are clay, talc, MgO1Mg(OH)2.0aOO
3 and fillers such as silica, other mold release agents, red iron oxide, TlO2, carbon black including conductive carbon black, pigments, anti-mold agents, UV absorbers, calcium silicate, paraffin wax, hollow glass or resin microspheres,
These include thickeners and other low-shrinkage additives. One preferred filler is talc, and the polymerizable oligomer 100 is
It is used at about 50 to 150 parts per part. The use of an electrically conductive filler, such as electrically conductive carbon black, allows the coating to be applied using conventional static painting techniques.

Such conductive carbon black is about 5 to 100% per 100 polymerizable oligomers! Can be used in total of 5 heavy cavalry. These fillers and powder ingredients should be used with enough song to give satisfactory results. However, it is important to be careful when handling products with high filler content. This is because it results in high viscosity and makes flow and handling difficult. Materials such as carboxylated butadiene-styrene block copolymers and aliphatic alfur phosphates are difficult to use in the in-mold composition of the present invention.

For convenience, materials such as polyvinyl acetate can be dissolved in an anti-uniaxial solid mass such as styrene.

The viscosity of the olicomer can be reduced by diluting it with styrene or the like. The components of all in-mold compositions can be easily mixed, combined, and handled at ambient or room temperature or at flow rates below the polymerization temperature so that the composition can be easily pumped into the mold. It should be done as follows.

Warm the ingredients before or during mixing, but you may heat them.

It can also be mixed in stages to facilitate complete lubrication, dispersion, and dissolution of the composition.

When with a peroxide initiator or f411:IJM, the entire in-mold composition exhibits a shelf life of approximately 1 week at room temperature (approximately 25°C), and without initiator a shelf life of several 1'' at room temperature. Indicates lifespan. The initiator is added to the composition immediately before molding, and it is preferred that all components of the in-mold coating composition be completely combined to obtain a manageable result and to prevent porosity formation. , it should be kept dry, with minimal moisture, or the moisture layer should be adjusted.

Mixing of the ingredients of all in-mold compositions should be thorough.

1), compression molding, transfer molding, or combination molding equipment or machines can be used for the internal coating.

The coloring device f (and method are described in U.S. Pat. No. 4,07TJ,
780 Lee-1 No. 4,076.788, No. 4,081,
No. 578, No. 4,082,486, No. 4,189,5
No. 17, No. 4, No. 222, No. 929, No. 4,245,
No. 006, No. 4,239,796-1 and No. 4,23
It can be found in No. 9,808. Also, “Strong Plastic 7”
/ Re-alpha product! (1 [Report of the 32nd Annual Meeting of the Institute JSP Engineering, Washington, February 1977 1Griffi
7h), etc., 2-0, pages 1-3, and l'-1978 Reinforced Plastics/Composite Products Research Institute, Plastics Industry Association 33rd Annual Technical Meeting Report, SP Engineering, Ongena
See also, na), 14 B top, pages 1-7. The in-mold coating composition is heated to a temperature of about 290-310°C (143°C).
, 3°C to 154.4°C), pressure approximately 1000 psi (
30,3~) for about 0.5 to 3 minutes,
Can be hardened.

The method and product of the present invention can be used to manufacture automobile parts such as grills; headlamp assemblies, deck hoods, fenders, door panels, and roofs, as well as food trays, appliances, electrical parts, furniture, machine covers and preservation products; Can be used to manufacture bathroom fixtures, structural panels, etc. Those intending to apply the whole in-mold composition to glass fiber reinforced thermosetting plastics (FRP) such as polyester resin or vinyl ester resin and glass fiber composition substrates are sheet molded and bulk molded (SM(!)). Molding compound (BM
O) Can be other thermosetting FRP materials as well as high strength molded mound (HMO) or thick molded mound. The FRP substrate can have about 10 to 75% glass fiber by weight. SMO compounds are usually around 25-3
It contains 0% glass fibers, while HMO powder contains about 55-60% glass fibers by weight. Fiberglass reinforced thermoset (FRP) substrates can be rigid or semi-rigid (softening moieties such as adipate groups can be included in the polyester). The substrate may also contain other softening polymers, such as styrene-butadiene block copolymers, and elastomers and plastomers. Unsaturated polyester glass fiber thermosetting resins are described in [Modern Plastics Encyclopedia] 1975~
1976, October 1975, Vol. 52, No. 10A, McGraw-Hill Publishing, New York, 61.62, and 105
-107 pages: [Modern Plastics Encyclopedia J 1979-1980. October 1979,
Volume 56, IOA No. 55.56.58.147 and 1
p. 48; “Modern Plastics Encyclopedia J 1980-81, October 1980,
Volume 57, IOA No. 59.60, and 151-153
pp. McGraw-Hill, New York, N.Y.,
It is very well known. For more information on vinyl ester resins, see the Shell Chemical Company technical report mentioned above.

The compositions of the invention exhibit good pumpability and flow into the mold. These are 7 below 300 (148,9℃)
It hardens rapidly in a short period of 5 to 90 seconds. They also show good adhesion to paints and can be used not only as an in-mold coating to cover defects, but also as a good conductive coating for electrostatic paints.
Also used as a brimer for most paint finishing systems such as soluble acrylic lacquers, acrylic dispersion lacquers, waterborne acrylic enamels, high solids solution acrylic enamels, acrylic non-aqueous dispersions and urethanes. can.

The following examples are provided to illustrate the invention in more detail to those skilled in the art. In these examples, parts are parts by weight unless otherwise indicated.

Example 1 The following ingredients were mixed together.

Ingredients Heavy wrinkles parts r, p
90 150150150150225 Juwisen (
UV engineering THANK) 783 150 1.80 1
80 225 150 Chemlink (OHKMLIN
K) 600 180 90 - -
90 nodloprobile methacrylate) -
90-90180 Styrene 90 1
35 51 90 45 2% benzoquinone in styrene 13.5 15 9 12
15 Next, the following ingredients were mixed.

Zinc stearate 1.62 1.8 1.0
8 1.53 1.89 cobalt octoate)
, 54. 6. 36. 51. (12% as 00 in 63 soy oil) Next, the following ingredients were mixed.

VULOAN carbon black 27
30 18 25.5 31.5 slides
Stone (630) 159 180 10
8 156 192 For each composition, total in-mold assembly 10
1 part by weight of initiator TBPB was added per 0 parts by weight.

The entire in-mold composition exhibited the following properties.

Gel resistance under 230°C (110,0°C) H1, 7,3/
3309.1/3364.5/3167.7/Tsu181
4020 minutes/under peak wetness (165,6℃) (168,
9'c) (157, &C) Q, "B, 9℃) (16
0.0 DEG C.), a conventional polyester-styrene-glass component, heat-cured, in some cases additionally containing a carboxylated butadiene-styrene block female polymer; The overall results obtained for the in-mold coating compositions are shown below.

Adhesion to substrate Pass Pass Good time rate Pass Pencil hardness Fail Pass Pass Pass Pass ASTM D3363-74 B
HB 2H2HHB Actual/fni Example 2 The method of this example was similar to that of Example 1 above, except for the following changes. The results obtained with the mold inner jacket yt-J- were satisfactory.

The following ingredients were mixed together.

G LP90 75 100 Juwisen
783 100 75 Chemlink 600 - 25 Hydroxypropylene methacrylate 30 20 Styrene 3010 2% Benzoquinone in Styrene 55 The following ingredients were then incorporated.

Zinc stearate, 675. 675 Calcium stearate, 675. 675 Next, the following ingredients were mixed.

Palkan Carbon Black 1111 Slime
70 70 To each composition was added 1 part by weight of initiator TEPB per 14 parts by weight of total in-mold composition.

The whole intramold compositions F and G are L's actual Mi Example 1', 1
Passed all of the exams shown in Metrics A-K.

Actual ', 'HQi Example 3 In this example, the mold inner coating g was
A preferred method of making the composition is shown. - Mixed ingredients in order as in Toy 1.

T, IP 90 100.0
Lightning side Chemlink 600 25.0
“Hydroxypropyl methacrylate-1□ 20
．． Ott 2% benzoquinone in styrene 5
0 〃1. These materials are fed into the reactor and blended.

Styrene 50 tons Stearin can 11F ship 0. (i75 rt calcium stearate 0.675
2. Preliminarily mix the 10 ingredients and charge them into the reactor. Add the above ingredients and heat to 44℃ (110”F) while mixing.
Heat to.

TJVTTHANE 783 (4
At 9°C, add 75.0 parts of 1 part 3 of Juwisen 783 to the reactor and mix until the material is homogeneous. Cool to 38°C (below 100°C).

Palkan carbon black 1t, o +J
i it s (4, add carbon black to the reactor,
Knead for 30 minutes. Maintain temperature at 38°C (below 100°C).

Talc (beaver whey) 200) 70.0
Part 5 by weight, add talc to the reactor and adjust the temperature to 38°C (10
Mix for 1 hour while maintaining the temperature (below 0). Remove sample.

6. Check the gel time. If less than 8 minutes, add 1 part by weight of 2% benzoquinone in styrene and mix for 30 minutes. Check gel time again. Repeat the above steps until the gel time is between 8-10 minutes.

7. Subtract the number of stacked parts of 2% benzoquinone in styrene from 5 and add the difference as styrene.

Mix for 30 minutes, degas for 15 minutes, and filter through a 6o mesh sieve. Save iii/Z below 45.

Brookfield viscosity, below 86 (30,01?:) #
7 spindles, 100 rpm 13,000-15
, 000 gel time, under 230 (110,0°C) 8-H
a*) 1,Q parts by weight of TBPB per 100 parts by weight of the total composition.

When replenishing materials to check gel time, total composition 1
Add 1.00 g of TBPB and thoroughly mix before performing the gel test.

Example 4 The method of this example was similar to the above example.

H engineering JK LP90 100 100 100
100k Bokril Q+; pooRyL) 370
75 Chemball (aHmMpoL) 4825
75 Yuvi v- (UVIMER)
580 757 Ware Tank (ALTAC) 382Rj
75
Chemlink 600 25
25 25 25 Hydroxyprivi methacrylate 20 20
20 20 styrene 1
．． 0 10 10 10 2% Benshanone in styrene 5 5 5
5 Stearinated zinc 0.675 0.
675 0.675 0.675 'Calcium stearate 0.675 0.67
5 0.675 0.675 Palkan Carbon Black 11 11 11 1
1 Beaver White 200, Talc 70
70 70 70 For each composition,
@ Covering composition 100 iii Saliva part initiator TBPB
1 part by weight was added.

ψHaiji, 230 below (110,0℃) 5.79114
8.3/324 15. M (228,77323100
rpm In-mold coating properties on molded thermoset glass fiber-polyester-styrene substrate.

Hot strength Good Marginal Good Further separation None None None
-Doukan Kyousei (Lancebeke 1 [no n intervention) 165
16α-465165 - Example 5 The method of this example was similar to the above example.

LP -90100100100100 Juwisen 8
93 75 polyester
75 Yuvmaa 530
75 Nubor (NU
POL) 46-8012
75℃M N O Chemlink 600 25
25 25 25 Hydroxyptamermethacrylate) 20 20
20 20 styrene
10-10-2% Benzoquinone in Styrene 5 5 5 5 Zinc Stearate 0.675 0.675 0.
675 0.675 Calcium stearate 0.675
0.675 0.675 0.675 Cobalt octoate 0.225 0.225 0.2
25 0.225 (12% as CO in mineral oil) Palkan Carbon Black II 11
11 11 Beaver White 200, Talc 70 70 70 70
To each composition was added 1 part by weight of initiator TEPB per 100 needles of total mold coating composition.

Gel time fil, below 230°C (100°C)
14.9/308 6. L/322 7.5/3
34 25.3/248 In-mold coating properties on molded thermosetting glass fiber-polyester-styrene substrate.

Hot strength Good Marginal Good Poor layer
Separation No Yes Excessive
- Among Examples 4 and 5, actual tiH% I, L is the best one.

Notes for examples: TJp-90-Baker f) T, P-90-Styrene solid vinegar clam vinyl 40% by weight, viscosity 1,800 at 25°C
Centipoise (model LVT Brookfield viscosity puller #4 spindle, 60 rpm), specific gravity 20/20°C (
HO-1) 1.008, coagulation degree 5°C, union carbide fuboration.

Yu'j Isen (UVITANE) 783-Polymerization 6
A functional urethane material or oligomer, diacrylate-terminated polyester urethane polymer. 49℃
It has a viscosity of 600 to 2000 poise at 82°C and 50 to 110 poise at 82°C, and a degree of unsaturation (equivalent per 100 q) of 0.
17 Coal Corporation.

Chemlink 600 or C1,600-polyoxyethylene glycol 600 dimethacrylate. Molecular weight approximately 770
oC36H66017゜Ware Chemical Corporation.

Parcan (VUIIOAN) -XO-72B, N
472° conductive furnace carbon platter. Cabot Corp.

Talc - Hydrous magnesium silicate.

TBPB - tert-butyl perbenzoate.

Evocryl 370 - non-volatile diacrylate ester of liquid bisphenol A epoxy resin. Viscosity 25℃ (10
0% resin) 9,000, acidity equivalent per 100g 00
07, equivalent weight per 100 g of epoxide 002, Gardner color 4, weight/volume (lbs/US gallon) 999, flash point > 204°C, Gardner viscosity, 25°C (80 ERW% resin in xylene) v-yo Shell Chemical Company.

Chemball 4825 - (19-4825) tn Solvent-free epoxy acrylate-1 resin containing active acrylic unsaturation on the conjugate molecule. Acid value 3-10, color 1-
4. Viscosity 4000~6 at 140'F (60,0℃)
000 centipoise, 1 at 160°F (71,,1°C)
400-1800 centipoise. Weight per gallon: 98~
100 true.

Contains up to 2% free acrylic acid. Freeman Chemical Corporation.

UV MrcR 580 - A polyethylene unsaturated monomer IJ with high reactivity in free radical polymerization. A crystalline amber liquid with a mild caustic odor. Viscosity (Gardner color)) Z6 ~ Z7 (
200-500 poise), color (Gardner-Holt) max. 3, weight 96±01 lbs per US gallon, flash point (closed cup) approximately 210"F (98,9C).

Polychrome Corporation.

ATLAO381-Bisphenol A-polyester resin. IC e America Inc.

893 - Polymerizable urethane oligomer and viscous liquid. APHA color up to 110, mild odor, weight 10 bonds per gallon at 77 below (25,0°C), viscosity 9 at 120°F (48,9°C)
00 to 2200 poise, 80 at below 160 (71,1℃)
30 to 80 poise at ~180 and 180 °C (822°C), 0.150 to 0.175 per 100 g of unsaturation, and isocyanate content max. 0.2%. Thiokol Corporation.

Polyester - A polyester made by the copolymerization of propylene oxide, ethylene oxide, maleic anhydride, fumaric acid, and phthalic anhydride using a double metal cyanide axis. It has a molecular weight of about 1,200 and has a molecular weight of about 1,200.

UV Engineering MU () 530 - Polyethylene unsaturated liquid (4C oligomer) with extremely high reactivity in free radical polymerization. Viscosity (Gardner-Holt) z
7-Z8 (375-600 poise), color (Gardner-Holt) up to 5, weight per US gallon 98.060
5 bond, and flash point (closed cup) approximately 210'F.

Polychrome Corporation.

46-8012 - A mixture of 70% acrylate terminated beads, 28% styrene, and 2% hydroxyethyl methacrylate.

Applicant: The General Tire and Rubber Company 1' Agent: Patent Attorney Dantabe Sasai 1 (and 1 other person) - Continued from page 1 ■Int, C1, 3 Identification code Internal reference number: 0 Inventor: Donald F. 9286 Reichenbach Street 2°0 Inventor: Henry Schatzky.

2388 Banbury Road, Akron, Ohio 44313 4゜5゜6゜7゜8゜Procedural Amendment Commissioner of the Patent Office Mr. Kazuo Wakasugi (Mr. Patent Office Chief Examiner) (Mr. Patent Office Examiner) Display of Case 1982 Patent Application No. 189383 Title of Invention Type Cover
Relationship with the person filing the reversal/amendment case Patent applicant name The General Tire and Rubber Company Address of agent 2-8 Shinjuku, Shinjuku-ku, Tokyo 160 Japan
No. 1 Shinjuku Seven Building Room 608 (a6ooi famous patent attorney Yatabe Sasai)
(No. 354-1285 - 6) Date of amendment order Number of inventions increased due to voluntary supplementary amendment No increase Description (171) 1. Title of invention゛ In-mold coating 2. Claims 1. (a) 100 parts by weight of at least one polymerizable epoxy-based oligomer having at least two acrylate groups and a weight average molecular weight of about 500 to 1500; (b) at least one copolymerizable ethylene; about 80 to 160 parts by weight of sexually unsaturated, (c) -00- group and -NH2, -NH-1jjf;4d-OH group 2+
-4-=-at least one copolymerizable monoethylenically unsaturated compound having about 10 to 120
parts by weight, (d) about 20 to 90 parts by weight of polyvinyl acetate, (,
a) about 0.2 to 5 parts of a zinc salt of at least one fatty acid having at least 10 carbon atoms; (f) about 0.01 to 1 part of at least one promoter for the peroxide initiator;
．． Between type 0, (g) conductor? about 5 to 30 parts by weight of Jf carbon black, (h) about 50 to 155 parts by weight of filler, and (1) about 2
having a weight average molecular weight of 50 to 5000, (■) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (■) at least one polyurethane having two acrylate groups; 1. A composition useful as a thermosetting coating composition comprising a diacrylate compound based on an oligomer and about 5 to 120 parts by weight of a diacrylate compound.

2. The patent wherein the composition additionally contains at least one organic free radical peroxide initiator up to about 5% by weight of 7-B based on the weight of the polymerizable ethylenically unsaturated material. Composition according to claim 1.

3. (The composition of claim 1 Jn, wherein hl comprises talc.

4. The composition additionally contains at least one organic free radical peroxygen initiator in an amount up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated material. Composition according to item 3.

5 additionally (+) a calcium salt of at least one fatty acid having at least 10 carbon atoms from about 0.2 to
The composition of claim 1 containing in an amount of 5 parts by weight.

6. The claimed composition additionally contains up to about 5% by weight, based on the weight of the polymerizable ethylenically unsaturated additive, of at least one organic free radical peroxide initiator. Composition according to Scope No. 5.

7. Additionally (j) at least IM with at least 10 carbon atoms! Calcium salt of fatty acid of about 0.
A composition according to claim 1, wherein h) comprises talc in an amount of 2 to 5 parts by weight.

8. The composition additionally contains at least one organic free radical peroxide initiator in an amount up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated material. Composition by around 7.

9. (a) is diacrylate ester of liquid bisphenol A1 epoxy resin (b) is styrene, (C) is hydroxypropyl methacrylate (θ) is zinc stearate, (f) is fluorine 9, octoate (-l) L2
The composition of claim 1, wherein (h) is talc and (1) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770.

3. Detailed Description of the Invention The present invention provides a polyester resin or vinyl nysder resin (FRP) that does not require combining two or more components immediately before use.
) Thermosetting mold coating compositions useful for coating molded glass fiber reinforced thermoset plastics, such as molded articles or parts.

Compression molded thermosetting glass fiber reinforced polyester #(
Major drawbacks of molded products (PRP) are surface defects such as dents, porosity, surface cracks, corrugations, and sink marks. The in-mold coating method of US Pat. No. 4,081,578 overcomes these deficiencies by generally molding a low viscosity thermoset onto the FRP surface in a second molding operation. The compositions described in U.S. Pat. No. 4,081,578 contain free hydroxyl as well as incyanate groups that co-react at room temperature, resulting in a limited pot life (approximately 30
minutes). If carried out, the reaction components are kept separate and brought together only immediately before application. This requires dual pumping equipment and sophisticated metering equipment, increasing the cost and complexity of the system. Single component coatings therefore offer significant advantages.

Moreover, conductive carbon black cannot be formulated well in in-seal auto-based in-mold coating compositions and is difficult to obtain even coatings after in-mold coating and subsequent electrostatic coating.

It is therefore an object of the present invention to provide a method for in-mold coating of IPRP molded articles with a -component coating composition, while avoiding the difficulties mentioned above.

Another object of the present invention is to provide a composition suitable for coating inside a mold of an FRP molded product.

Yet another object of the present invention is to provide an adhesive coating coated in a mold with a component mold coating composition.
To provide Rp molded products or parts.

These and other objects of the invention will become apparent to those skilled in the art from the following detailed description and examples.

In accordance with the present invention (a) at least two acrylate groups and from about 500 to
100 parts by weight of at least one polymerizable epoxy-based oligomer having a weight average molecular weight of 1500; (b) about 80 to 160 parts by weight of at least one copolymerizable ethylenically unsaturated polymer; (c) -00- group, -NH2-, -NH- and 〆1
At least one copolymerizable monoethylenically unsaturated compound having 10 to 120 parts by weight and 11F parts, (CL) polyvinyl acetate about 20 to 90 tons M parts, (θ) about 0.2 to 5 parts of at least one zinc salt of fatty CD having at least 10 carbon atoms, (f) about 0.00 parts of at least one accelerator for harsh chemical initiators;
1 to 1.0 heavy needle part, (g) ? lU %l-carbon black approx. 5-3
0 parts by weight, (h) about 50 to 155 parts by weight of filler, and (h) about 50 to 155 parts by weight of filler;
1) It has a ti average molecular weight of about 250 to 5000, and (■
) at least one polyoquine alkylene glycol-based oligomer having two acrylate groups; and (■) at least one oligomer having two acrylate groups:
1+1 polyurethane-based oligomers, 1 (1) and (II) O mixtures, and about 5 to 120 weight co-composable or diacrylate compounds selected from the group consisting of: The initial heat ω, based on the free needle of the components, consists of M, parts, ! FR using a chemical coating composition
P molded products can be coated within the mold.

Optionally and desirably, at least one calcium salt of a fatty acid having at least 10 carbon atoms can be added to the composition in an amount of about 0.2 to 5 parts by weight.

The organic free radical peroxide initiator contains about 5% by weight based on the weight of polymerizable ethylenically unsaturated material in the composition.
, preferably at 2% by weight.

This composition has good flow properties and is stable for about a week even when containing peroxide. You can mold this in a short time. The resulting thermoset +JI coating exhibits good adhesion to different 'FRP substrates and accepts many paint finishes to alleviate the need for brimer.

The carbon black also distributes well throughout the composition and, when cured, provides an in-mold coating that can be electrostatically sprayed to provide a consistent paint or film. The coatings of the present invention also generally eliminate the need for a subsequent step of priming the in-mold cover with a conductive brimer prior to electrostatic painting.

Polymerizable epoxy-based oligomers with at least two acrylate (or methacrylate or ethacrylate) groups include acrylic acid, methacrylic acid, or ethacrylic acid, etc. , tetraphenyloethane eboxy, dicyclo
Fats H1j Its are made by reacting with epoxy-based oligomers such as epoxies or mint fat. Mixtures of these epoxy-based oligomers can be used. Of these materials, it is preferred to use diacrylate-terminated bisphenol A epoxy oligomers. These have a weight average molecular weight of about 500-1500. Such materials are well known. For more information about these materials, see [Heat-Resistant Hinyl Ester Resin J.M.B.

B, Launl, kitis), Technic
al Bulletin, So: 116-76,
Shell Chemical Company, June 1976 and Shell Chemical Company, Techn: Lcal Bulletin So:
16-76 and sa: see 60-78.

Copolymerizable ethylenically unsaturated monomers used to copolymerize and crosslink with polymerizable oligomers include styrene (preferred), alpha methylstyrene, vinyltoluene, 1;
-butylstyrene, chlorostyrene, methyl methacrylate, diallyl phthalate (with styrene or methyl methacrylate-1, etc.), triallyl, annulate, triallyl isocyanurate, divinylbenzene, methyl acrylate, etc., and mixtures thereof. Generally, the unsaturated monomer is used in an amount of about 80 to 160 parts by weight per 100 parts by weight of polymerizable epoxy-based olibore.

Monoethylenically unsaturated compounds with 100- groups and -NH2, -NH- and/or -0H groups are used. Examples of such monomeric compounds are hydroxylpropyl methacrylate (preferred), hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl crotonate, hydroxybrobyl acrylate, hydroxypolyoxypropylene acrylate, hydroxypolyoxypropylene methacrylate, hydroxy These include polyoxyethylene methacrylate, polyacrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and mixtures thereof. The Kowara compound is generally polymerizable eboxyno, (about 10 to 12 parts by weight per 100 parts by weight of disc oligomer).
It can be used in an amount of 0 parts by weight.

Polyvinyl acid salts are used in in-mold compositions to improve paint adhesion of in-mold coatings to substrates.

The polyvinyl acetate is used in a small amount compared to the total weight of ethylenically unsaturated material in the mold coating composition, but sufficient for paint adhesion. In general, polyacids and vinyls are used at a concentration of about 2 per 100 mold parts of polymerizable epoxy-based oligomers.
0 to 90 parts by weight are used.

Zinc salts of fatty acids having at least 10 carbon atoms may also be used in the mold coating composition to function as mold release agents and secondary accelerators of curing.

Greasy! /i Drunkenness is well known. ``Organic science'' Fiessr and Fiessr
eser) XIF.

C. Heath & Company, Boston, 1944
2010, 88 pages, 381-390.
, McGraw Building Publishing, New York, 1000, 2.
See page 61. A mixture of zinc salts of fatty acids can be used.

Some examples of zinc salts are zinc valmitate, zinc stearate, zinc resinoleate, and the like. Preference is given to using zinc salts of saturated fatty acids such as zinc stearate. [Wittington Plastic Dictionary] Wittington (Whj
Tttington), Technomic Publishing, Stamford, CT, 1968, 35.102.
See also page 261. Polymerizable epoxy-based oligomer 1
An amount of about 0.2 to 5 parts by weight of zinc salt per 0.00 parts by weight is generally used.

Accelerators are used for peroxidation initiators and desiccants, such as materials such as cobalt octoate. Other materials that can be used are zinc naphthenate, lead naphthenate, cobalt naphthenate, and manganese naphthenate. Rill-in soluble Co, Mn, and Pb can also be used. Mixtures of accelerators can also be used. (Traditionally, about 0.01 to 1 part of accelerator is used per 100 parts by weight of polymerizable epoxy-based oligomer.) During the in-mold coating composition, conductive carbon black is polymerizable. It can be used in an amount of about 5 to 30 parts by weight per 100 parts by weight of the base oligomer.

Fillers are included in the in-mold coating composition in an amount of 50 to 155 parts by weight per 100 parts by weight of polymerizable epoxy-based oligomer. Examples of such fillers are clay, MgOSMg
(oH)2, ChOOs, silica, calcium silicate, mica, °γluminium hydroxide, barium sulfate, talc,
Hydrated silica, magnesium carbonate, and mixtures thereof. The filler should be finely ground.

Among these fillers, talc is preferably used. The filler helps provide the desired viscosity, provides fluidity to the embedded acid for molding, and imparts desirable physical properties to the resulting thermoset inner coating. Fillers also improve adhesion. However, a high filler content can lead to high viscosity and flow and handling difficulties, so 2E, u should be paid.

Furthermore, in the in-mold coating composition, the city 1A average part P is about 250 to 50
Evogishi LU disc oligomer 10 which can be polymerized with a copolymerizable or cocurable diacrylate compound having 00
Approximately 5 to 120 parts per 0 parts by weight and 71゛? 1 Used in Konoha, diacrylate compound! ll! (I) an oligomer based on at least 1 fn polyoxyalkylene glycol having 2 acrylate groups; and (■) an oligomer based on at least one polyurethane having 2 acrylate groups; ) and (U
) is selected from the group consisting of a mixture of

Example of the above diacrylate compound v/J(I)
Polyethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate-1, polyethylene glycol diacrylate, polypropylene glycol diacrylate,
Polyethylene glyfur dimethacrylate, or polyoxyethylene glycol dimethacrylate (preferred), polypropylene glyfur dimethacrylate, polyethylene propylene glycol diacrylate, etc., and mixtures of dough. Kohachi's acrylate is made by reacting polyoxydialkylene gelicols such as polypropylene ether glycol with 1 g of acrylic, methacrylic acid, etc. Because some of these reactive bifunctional materials are made by reacting unsaturated acids with alcohols, they contain some OH and/or 0OOH groups.

Examples of the above diacrylate compounds (II) for use in mold implosion 4 compositions Contains polyurethane oligomers. To make these materials, polyether diols (e.g. polypropylene ether diol), polyester diols (e.g. polyethylene adipate diol) are used.
7l) V and/or polyether ester diol (e.g. polypropylene ether adipate diol)
etc., Tori Rangeison-j'nate, 4,4'
-diphenylmethane diisocyanate, hexamethylene diisocyanate, etc. 6-diisonoane-1 is reacted with -r nonanate end 'nff yj-, fl to produce a urethane brebolymer, and then this prepolymer is reacted with bitroxypropyl acrylate. , pydrogyethyl acrylate, pydrogyethyl methacrylate, etc., yields diacrylate-terminated polyurethane gums or polymers. Mixtures of acrylate-terminated polyurethane oligomers can be used. Yojima's "acrylate" used in this specification includes methacrylate-1, ethacrylate-1, and acrylate 1.
-7. There is an intention.

Among the stiff materials, it is preferred to use diacrylate polynitride urethane oligomers. Acrylate-terminated polyurethane cut sesame can be used, for example, by light, ultraviolet light, lightning,
Materials that can be cured by radiation and/or infrared rays are well known, and are sometimes referred to as irradiation or radiation-curable materials.

The above diacrylate compound (1) and/or Fi(TI)
appears to improve the hardness and reduce brittleness of the in-mold coating.

Optionally, and desirably, aliphatic lucium salts having at least 10 carbon atoms are added in an amount of about 0.2 to 5 parts by weight per 100 parts by weight of the polymerizable epoxy-based oligomer as a mold release agent and to control the rate of cure. used in mold in-mold coating compositions.

Fatty acids are well known, see above. Mixtures of fatty acid calcium salts can be used. Some calci8. Examples of lamb salts are calcium stearate, calcium palmitate, calcium oleate, and the like. Preferably, calcium salts of saturated fatty acids are used, such as calcium stearate.

Organic free radicals or free radical generating initiators (catalysts) such as peroxides are used to catalyze the polymerization, copolymerization or crosslinking of ethylenically unsaturated oligomers and other ethylenically unsaturated materials.

Examples of free radical initiators are tert-butyl perbenzoate,
tertiary-butyl peroctoate in diallyl phthalate, cyano7tyl peroxide in dimethyl phthalate, dibenzoyl peroxide, diCp-chlorobenzoyl peroxide in dibutyl heptathalate), peroxide with dibutyl phthalate Di(2,4
-dichlorobenzoyl), AM dilauroyl, methyl ethyl ketone peroxide, i-diglutinated cyclohexanone in dibutyl 7-talate, 3I5-dihydroxy-3,4-dimethyl-1,2-dioxacyclopencune, t-butylperoxy( 2-ethylhexanony)), ioxidizing power pyryl, 2,5-dimethousand-2,5-di(benzoylperoxy)hexane, ■-hydroxycyclohexylhydroperoxide-1, di-butylperoxy( 2
-ethyl butyrate), 2,5-dimethyl-2,5-
Bis(+,-butylperoxy)hexane, cumyl hydroperoxide, diacetyl peroxide, t-butyl hydroperoxide, di-butyl peroxide, 3.
Includes 5-dihydroxy-3,5-dimethyl-1,2-oxacyclopentane, 1,1-bis(t-butylperoxy)-3,3,5=trimethylcyclohexane, and mixtures thereof. It is sometimes desirable to use a mixture of initiators 2 and to take advantage of different decomposition rates M and times at different temperatures. The preferred initiator for use is tertiary butyl chloride. The peroxide initiator should be used in an amount sufficient to overcome the effects of the inhibitor and cause hardening of the ethylenically unsaturated material. In general, peroxide initiators can be used at up to about 2% by weight of F75'', preferably up to about 2% by weight, based on the weight of the ethylenically unsaturated material used in the gold μ74J inner coating composition.

The unsaturated materials described above are thus used in amounts sufficient to provide a thermosetting composition by hardening (eg, polymerization, copolymerization, and/or crosslinking).

To prevent premature gelation of the ethylenically unsaturated material and provide improved shelf life or shelf life, the desired amount of inhibitor is added to the composition or provided in the raw material prior to use. Hydroquinone, benzoquinone, p-t-
butylcatechol, etc., and mixtures thereof.

The in-mold composition may additionally optionally contain other mold release agents, anti-disintegration agents,
It can be pounded with UV absorbers, paraffin wax, solid glass or resin microspheres, thickeners, and other low-shrinkage additives. These ingredients should be used in amounts sufficient to give satisfactory results. It is undesirable to use materials such as butadiene-styrene block copolymers or aliphatic alcohol phosphates in the in-mold compositions of the present invention.

For convenience in handling, materials such as polyvinyl acetate can be dissolved in reactive monomers such as styrene.

Oligomer viscosity can be reduced by dilution, such as with styrene. The ingredients of all in-mold compositions should be easily mixed and handled at ambient or room temperature or humidity below the polymerization temperature so that the composition can be easily pumped and injected into the mold. be.

The ingredients may be warmed or heated before or during mixing.

The mixture can be mixed in stages to facilitate thorough mixing, dispersion, and dissolution of the composition. It is also possible to thoroughly mix most of the components, mix the remainder, including the catalyst, separately and then pump both into a mixing bed, mix, and then pour into the mold.

With a peroxide initiator or catalyst, the entire in-mold composition exhibits a shelf life of about one week at room temperature (about 25° C.), and without an initiator a shelf life of several months at room temperature. Preferably, the initiator is added to the composition immediately before molding and mixed thoroughly.

All components of the in-mold coating composition should be kept dry, have minimal moisture, or have controlled moisture content to obtain reproducible results and to prevent porosity formation.

Mixing of the ingredients of all in-mold compositions should be thorough.

Injection, compression, transfer molding, or other molding equipment or machinery can be used for the mold coating.

Molding apparatus and methods are described in U.S. Pat.
No. 8, No. 4.082.486 can be issued. Also, ``Report of the 32nd Annual Meeting of the Reinforced Plastics/Composite Products Research Institute, JSP Engineering, Washington, February 1977, Qriffi
th) et al., 2-a JH pages 11-3, and r 19
1978 Research Institute for Reinforced Plastics/Composite Products, Report of the 33rd Annual Technical Meeting of the Plastics Industry Association, SP Engineering, Ongena (
See also Section 14B, pages 1-7. The temperature of the powder coating composition in the mold is about 290 to 310°.
F (143,3℃~1544℃), pressure about 1000p
sj, (30,3~) can be applied to the substrate for about 0.5 to 3 minutes and cured.

The method and product of the present invention are suitable for manufacturing automotive parts such as grills; headlamp assemblies, deck hoods, fenders, door panels, and roofs, as well as food trays, appliances, electrical components, furniture, machine covers and protective equipment, bathrooms. Can be used to manufacture fixtures, structural panels, etc. Sheet Molding Hound Bound (sMa) Yabulk Molding Hun Pound is suitable for applications where the entire in-mold composition is intended to be applied to glass fiber reinforced thermosetting plastics (FRP) such as polyester resin or vinyl ester resin and glass fiber composition substrates. (BMO)
Other thermoset FRP materials can be used as well as high strength molded composite (HMO) or thick molded composite. The FRP substrate can have about 10 to 75% glass fiber by weight. SMO flour pounds typically have about 25-30% glass by weight, while HMO flour pounds contain about 25-30% glass fibers by weight. Fiberglass reinforced thermosets (FRP) can be rigid or semi-open (flexible moieties such as adipate groups can be included in the polyester). The substrate may also contain other softening polymers, such as styrene-butadiene block copolymers, and elastomers and plastomers. Unsaturated polyester glass fiber thermosetting resins are described in "Modern Plastics, Encyclopedia" 1975~
1976, October 1975, Vol. 52, No. 10A, McGraw-Hill Publishing, New York, 61.62, and 105
~107LT; rModern Plastic Encyclopedia J 1979-1980. October 1979, Volume 56, IOA Issue, Pages 55.56.58.147 and 148: and [Modern Plastic Encyclopedia J 1980-81. October 1980, Volume 57, IOA So, 59.60, and 151-153 Sada, McGraw-Hill, New York, N.Y., T.
It is well known. About vinyl ester resin A
'! Or read the above Shell Chemical Company technical report #I! 1
．． (0) Composition No. 1 of the present invention exhibits good pumpability and flowability into the mold. They also exhibit good adhesion to paints and are used not only as a defect-covering in-mold coating, but also as a good conductive coating for electrostatic coatings, as well as for soluble acrylic lacquers, acrylics, etc. It can also be used as a primer for most paint-borne systems such as polydispersion lacquers, waterborne acrylic enamels, high solids solution acrylic enamels, acrylic non-aqueous dispersions and urethanes.

The following real-world examples will help those skilled in the art to understand the invention in more detail.
・This is a useless example. In these examples, the section is the heavy M section unless otherwise indicated.

Example 1 The following ingredients were mixed together.

LP'to 150 150 150
1.50 225 1y Isen (UVITHANE) 7
83 150 180 180 225 15
0CHEMLINK 6oo 180
90--' 9 (1-noid lobropyremethacryl) -90-90180
Styrene 90 135 51
90 45 2% benzoquinone in styrene 1
3.5 15 9 12 15 Next, the following ingredients were mixed.

Stearic acid subveneer 1. ．． 62 1.8
1.08 1.53 1.89 cobalt octane), 54. 6. 36
．． 51. (12% as 63C Kan 1 Oki co) Next, the following ingredients were mixed.

VULOAN carbon black 27
30 18 25.5 31.5 Slime (630) 159 180 108
1.56 192 Properties of Uncatalyzed Compositions Each composition contains 1 load e per 100 parts by weight of total in-mold composition.
Initiator TBPB was added with d≦.

The assembled paraboloid in the mold exhibited the following properties.

Under 230℃ (110,0℃) 41, 7.3
/3309.1/3364.5/? (167,7/self 1
814 for 20 minutes/under peak temperature (165,6
°C) (168,9 °C) (157,8 odor (158,9
(Blood, 0°C) A substrate of a molded thermoset conventional polyester-styrene-glass fiber composition (approximately 25% glass fibers), in some cases additionally containing a butadiene-styrene block copolymer. On top, add the above composition 1.
000 psi (70,3~), below 300 (148,
The inside of the mold was coated for about 2 minutes at 9°C. The overall results obtained for the cured in-mold coating compositions are shown below.

Pencil hardness Fail Pass Pass Pass
Passed ASTM D3363-74 B Old 2H2H Old V C・1 Example 2 False 1Nμ The method of Example 1 was the same as that of Example 1 of -F except for the following changes. The results obtained on the in-mold coating were satisfactory.

The following ingredients were mixed in one sheath to form an in-mold coating composition.

Ingredients Part by weight F
G T, P2O75100 Juwisen 783 100
75 Chemlink 600 -
25 hydroxyprivate methacrylate
30 20 Styrene 3010 2% benzoquinone in styrene 55 Next, the following ingredients were mixed.

675. 67
5 Calcium stearate, 67
5. 675 Next, the following ingredients were mixed.

Palkan Carbon Black 11 11
Slime 70 70
For each composition, 100 piles of composition in the whole mold & 1. One part of initiator TEPE was added per part.

The resulting in-mold oxides F and G passed all of the tests set forth in Experiments A-E of Example 1 above. However, while the in-mold composition F had considerable hot strength, the in-mold composition G only had poor hot strength.

Example 3 In this practical example, M
a! A convenient method for making 'ill products is shown. The ingredients were mixed in the following order.

LP 90 100.0 parts by weight Chemlink 600 25.0
//Hydroxypropyl methacrylate 20.
0 2% benzoquinone in styrene 5
．． 0.1. Charge these materials into a reactor and mix.

2. Preliminarily mix the above materials and charge them into the reactor. Add the above ingredients and heat to 44°C (below 110°C) while mixing.

! UVITHANE 783 (preheated to 49°C) 75.0 parts by weight 3 parts by weight Add UVITHANE 783 to the reactor and mix until the material is homogeneous. 38℃ (
100℃).

Palkan Carbon Black 11.0 Part 4 Add the carbon black to the reactor and mix for 30 minutes. Maintain temperature at 38°C (below 100°C).

Talc (Beaver White 200) 70.
0 parts by weight 5, add talc to the reactor and adjust the temperature to 38℃
(below 100) and mix for 1 hour. Remove sample. Brookfield viscosity, 86”F (30
,0℃) #7 spindle, 1.00 rpm 13,
000-15,0006, check the gel time. If less than 8 minutes, add 1 part by weight of 2% benzoquinone in styrene and mix for 30 minutes. Check gel time again. Repeat the above steps until the gel time is between 8-10 minutes.

Gel time, 230°C (110,0°C) 8-10 minutes*)
1 part of TBPB per 100 parts of the total composition, 1 part of Q weight. When replenishing materials to check gel time, total composition 10
Weigh out a 0.0 weight portion, add TBPB 1.0 (1) and mix thoroughly before performing the gel test.

7. Weight of 2% benzoquinone in styrene tft iη5
Subtract the number from 5 and add the difference as styrene.

Mix for 30 minutes, degas for 15 minutes, and filter through a 60 mesh sieve. Sow under 45.

Example 4 The method of this example was similar to the above example.

The following in-mold coating compositions were prepared.

LP90 100 100 100
100 epoxyryl (ipoaRyr) 370
75 CHEMPOL 482
5 75 Yuvimer (trv engineering MER)
) 580 75 ATJTAO 382
75 Chemlink 600 25
25 25 25 hydroxyboubire methacrylate 20 20
20 20 ingredients
Heavy styrene 10H
) 10 2% benzoquinone in 10 styrene
5 5 5 5 Stearin butyzinc 0.675 0.675 0
．． 675 0.675 Stearic Caltum
0.67! 'i 0. fi75 0.67
5 0.675 Palkan Carbon Black
11 11 11 11 Beaver White 200, Talc 70 70
70 70100 rpm To each composition was added 1 part initiator TBPE for every 100 parts total mold coat N composition.

Kuraray I5'i#l, 230'F (110,0℃
) 5.7 yen: ti4 8.3/324
15.9/322 8.7/323 Properties of coating inside mold with cedar finished thermosetting glass fiber-polyester-styrene substrate.

Hot and strong! J′, Excellent Fairly Good Good Even better
None None None -'EX i-formula'l(
y inspur ri p l' reading) 165
160-165 165 Example 5 The method for this practical Mti example was similar to the example above, and the following in-mold coating compositions were prepared.

King, P-! 'io 100 H)U
100 100 Juwisen 893
75 Ho” Riester
75 Yuvmaa 530
75 Nubor (NUPOL) 4.6-8012
75 Chemlink 600 25 25 2
5 25 hydroxybuvir methacrylate
20 20 20 20
Styrene 1.0-10 - 2% Benz A-tun in styrene 5 5
5 5 Stearin lead 0
．． 675 (1,6750,6750,675 stearin calcium 0.675 0.675
0.675 0.675 fuvaltooctoate
0.225 0.225 0.225 0.
225 (12% as CO in mineral oil) Palkan Carbon Blank 11
11. 11 11 Beaver White 200, Talc 70 7 (+
70 To each composition was added 1 part of initiator TBPB per 10011 g of total mold coating composition.

1 hour, %0 below (110℃) 14. 'l
/308 6. M322 7shiu34 25.3/”2
48 In-mold coating properties on molded thermosetting glass fiber-polyester-styrene substrate.

Strong hearing (9) Good Fairly good 6
Good Poor segment No SEIF
Yes i6% degree - 165 165 -
--Actual %i Among Examples 4 and 5, Experiments H, I, and L were the best. It also had the best combination of experimental hot strength, adhesion, mold release and electrical conductivity. Moreover, experiment H and experiment A
M B% 0% D, K, F and G (Examples 1 and 2)
It has superior hot strength compared to other materials.

Example 6 The method of this example was similar to the previous example and the following in-mold coating compositions were prepared.

Ingredient weight 114
Department LP 90 100.0100. O100,
0100,0 Chemlink 600
62.5 25.0 33.0 -
Hydroxyboubishi methacrylate 60.0
7.5 30.0 30.0 Styrene
-2,5-40,0 2% penchanone in styrene 5.0 5. (J
5.0 5.0 Mix the above ingredients well and then add the following? 1-IJII+Eru.

Zinc stearate (1,9(1,9(
'19 0.9 Cobalt Octoe)
0.12 0.12 0,12 0.
12 (12% as 00 in mineral oil) Mix the above well and then add the following.

Evocryl 370 62.5 Wa 5
．． 0 (i7.o 75.0 Mix the above ingredients well and then add the following ingredients.

Palkan car phone black 11.0
11.0 11.0 11.0 MISTRON RO880,080,080,080,0 - N-combine the above items well.

Properties of the resulting composition PQ, R8 Hot strength Poor Good Fairly good
Excellent hardness (ben/nru) F
F F R1 戊
minute heavy lid
TU'V LP 90
)30.0 500 750 Chemlink 60
0-15.0
15.0 Hydroxy/propyl methacrylate
:300 300 300 sti
N 320 4
00 350 Sunalene 2-functional benzoquinone
5.0 5.0 1° Zinc stearate, mixed well with 5.0 and then mixed with the following ingredients:
090909 Mix the above ingredients well and then add the following to Epocryl 3'70
75. ○ 75.0 B5.0 The above ingredients were mixed well and then the following ingredients were added.

Palkan Carbon Black 11.0
11,0 1j.

Mystron RC” 800
800 800 The above ingredients were mixed well.

Properties of the resulting composition Properties when an FRP substrate is coated in the mold with the composition Adhesion, Scalpel FRP I Substrate Marginal (2) Marginal (2) Dot11 W (2) Beni/Nrui iD
i 19” H positive (
(*Actually, the coating on ++Irin4τf has a very poor adhesion (2jBest adhesion) It had a combination of f.

Example 7 The method of this working example was similar to that of the previous example, and the following in-mold compositions were prepared.

■JP9 (,175,075,075,0 human 1 coxib 5 bire methacrylate 30.0
30.0 30. ij styrene
350: (5, (135+1 2% pentuquinone in suzalene 5.0 5.0
5. OF, mix the ingredients listed above and then add the following:

Ubisen7B2 15,0 3
0.0 -1 Vicen783
-15. Cl Ubisen 893
− − −−The above ingredients were mixed well, and then the following ingredients were added.

AA BB 00 Zinc stearate 0.9 0.9 0.9 Calcium stearate 0.45
0.45 0.45 The above ingredients were mixed well and the following ingredients were added.

Evocryl 370 85.0 7
0.0 85.0 The above ingredients were mixed well and then the following ingredients were added.

Palkan carbon black 11
．． 0 11.0 11.0 Mistron R
cs 80.0 80.0
80.0 The above ingredients were mixed well.

Properties of the resulting composition, Adhesion properties when the FRP substrate is coated with the composition in the mold, Scalpel FRP [1-Pass - FRP ■ -Marginal-
Pencil hardness F F
HLP 90 75, O7
5,075,0 Hydroxybouvil Methacrylate Root
30.0 30.0 30.0 Styrene 35.0 35.0 35
．． 0 2% benzoquinone in styrene 5.
0 5.0 5.0 The above ingredients were mixed well and then the following ingredients were added.

Yubisen 782 - -
-Ubisen 783 30.0
- -Ubisen893-
15.0 30.0 The above ingredients were mixed well and then the following ingredients were added.

Zinc stearate 0.9 0.9
0.9 Calcium stearate
0.45 0.45 0.45 The above ingredients were mixed well and the following ingredients were added.

Evocryl 370 70.0 85
．． 0 70.0 The above ingredients were mixed well and then the following ingredients were added.

)9 Lecan Carbon Black 1
1,0 11.0 ] 1.0''-
Mix the listed ingredients well.

Properties of the resulting composition, properties when the FRP substrate is in-mold coated with the composition, Scalpel FRP I marginal 1-return
Marginal FRP III Pass --FRP 11 Marginal -- Pencil hardness H
Of the HH Fabric Example 7, Run DD had the best combination of hot strength and adhesion.

Example 8 The method of this example was similar to that of the previous example and the following in-mold compositions were prepared.

Evocryl 370 100.0
70.0 70. Or, p90
- 75.0 - Juhisen 783
− − 30.0 θυ
~()G HHI hydroxyboupyremethacl route 50
．． 0 50.0 50.0 Styrene
50.0 5.0 50.0 2% benzoone in styrene 5.0
5.0 5.0 The above ingredients were mixed well and then the following ingredients were added.

Zinc stearate 0.9 0.9
0.9 Calcium stearate
0.45 0.45 0.45 The above ingredients were mixed well and then the following ingredients were added.

Palkan car phone black 11
．． 0 11.0 11.0 Mistron R
OS 80.0 80.0
80.0 The above ingredients were mixed well.

Properties of the resulting compositionProperties when an FRP substrate is in-mold coated with the compositionAdhesion, Scarpel FRP I Failure Marginal Failure FRP Ill Failure
Pass Passed 1 FRP II Failed Critical Critical hardness 2H2H
2H engineering si krill 370 70.
0 70. OLP 90
-Ubisen 783
"""・0 Chemlink 600 30.0
15.0 Hi) o Kishifuyabiremetaku 1 route 50
．． 0 50.0 Styrene
50.0 50.0 2% in styrene
Benzoquinone 5. Q
! 5.0 The above ingredients were mixed well and then the following ingredients were added.

Zinc stearate Q, 9
0.9 Calcium stearate
0.45 0.45 Cobalt octoate 0.12 0.12 (
(12% as CO in mineral oil) The above ingredients were mixed well and then the following ingredients were added.

Palkan Carbon Black 11. ．． 0
11.0 Mystron ROS
80.0 80.0 The above ingredients were mixed well.

Properties of the resulting composition, properties of adhesion when in-mold coating of the FRP substrate with the composition, Scalpel 7” PJ limit failure
Failed FRP I Passed
Passed FRP II
%, j8.711 limit prefecture actual pencil hardness
F2H Example 9 The method of this example was similar to that of the previous example and the following in-mold compositions were prepared.

LP 90 100.0 100.0
100.0 Hydroxyboubire methacrylate
30.0 30.0 30.
0 Styrene 25.0 25.0
25.0 Chemlink 600
- 15.0 15.0 Ubisen 782
30.0 15.
0 2% benzoquinone in styrene 5.0
5.0 Mix the ingredients listed in 5.0 well, then add the following ingredients.

Zinc stearate 0.9 0.
9 0.9 Calcium stearate
0.45 0.45 0.45 The above ingredients were mixed well, and the following ingredients were added.

Evocryl 370 70.0
85.0 70.0 The above ingredients were mixed well and then the following ingredients were added.

Palkan Carbon Black 11.0
11.0 11.0 Mystron ROS
80.0 80.0 80.0Those listed in H were mixed well.

Properties of the resulting composition, FRP substrate Properties when coated in mold with the entire composition Adhesion, Scalpel FRP T Marginal Marginal Marginal % FRP m Pass Pass Pass FRP l
Pass Limit Limit 1 Wa Valley Pencil Hardness
F F F conduction 165+ 1.65
+165+LP90
100.0 75.0 Hydroxylene methacrylate) 35.0
35.0 Styrene 30
．． 0 40.0 Chemlink 600
15.0 15.0 Ubicene 782 15.0150 2 in styrene
%Benzoquinone 5.0
5.0 The above ingredients were mixed well and then the following ingredients were added.

Zinc stearate 0.9
0.9 stearin calcium
0.45 0.45 cobalt octoate) 0.12
0.12 (12% as CO in mineral oil) The above ingredients were mixed well and the following ingredients were added.

Evocryl 370 70.0
70.0-F were mixed well and then the following ingredients were added.

Palkan Carbon Black 11.0
11.0 Mistron RO880,080
,0 4 112j! l'! I cried a lot about it.

properties of the resulting composition; properties of adhesion when the FRP substrate is coated in the mold with the composite;
Scarpel FRP l marginal
Marginal FRP l[I
Pass -FRP ■
Limit drop each grade Limit n% grade Pencil hardness
PF-H Conductivity - Example 1O This example illustrates a preferred method of preparing an in-mold coating composition prior to in-mold coating and curing. The ingredients were mixed in the order shown below.

LP 90 75. Ojlc
N? il<Chemlink 600 15
．． 0 //Hydroxybuhi Jau/Metaku1ru)
3Q, Q //Styrene
25. 2% benzoquinone in Ott styrene 5. o〃1. Place these materials in a reactor and mix.

2. Preliminarily mix the above materials and charge them into the reactor. After adding the above charges, heat to 44° C. (under 110) while mixing using a reflux condenser. Once the object reaches 44°C, set it to remove the heat and apply cooling water.

Evocryl 370 (47℃ preheated) 85.0
Add 3 parts by weight Evocryl 370 to the reactor and mix until the material is homogeneous. Cooling will be required to prevent warming during the addition of Evocryl 370.

Add and mix Bocryl 370 and cool to 38℃ 41
00 below).

Palkan carbon black 110 parts by weight 4
, carbon black to the reactor and mix for 30 minutes.

Maintain flow rate at 38°C (below 100°C).

? Stone 1 (Beaver White 200) 8
Add 5 parts of 0.0 weight M talc to the reactor and mix for 1 hour while maintaining the temperature at 38°C (below 100°C). Exclude sample.

7t, ivy field sticky q (cps)
10 (-1001400086 bottom tl, 7 spindle 100 rpm6, check gel time.8
If less than 30 minutes, add 1 part by weight of 2% benzoquinone in styrene and mix for 30 minutes. Recheck gel time. Repeat the above procedure until the gel time is between 13-14 minutes.

Gel time *230 below 14-16 minutes*TBP
B 1 part by weight/100 parts by weight of total composition When adding materials for gel time check, weigh out 1000 grams of total composition, add 1.00 g of TBPB and mix thoroughly before gel testing.

7. Add one additional portion of 2% benzoquinone in styrene. Subtract the total parts by weight of 2% benzoquinone in styrene made from A5 and add the difference as styrene. Mix for 30 minutes. Degas for 15 minutes and filter through a 60 mesh sieve.

70? Store in.

Notes for the working example: LP -90-Bakelite Lp-=90-Polyvinyl acetate in styrene 40*ffi%, viscosity 1.
8 (10 centipoise (Model LVT Brookfield Viscometer #4 spindle, 6Q rpm), specific gravity 2
0/20°C (H20=1) ■, oo8, and solidification temperature 5°C, Union Carbide Corporation.

783 - Polymerizable urethane-based material or oligomer, diacrylate terminated polyester urethane blebomer. 60 at 49℃
It has a viscosity of 0 to 2000 poise, a viscosity of 50 to 110 poise at 82°C, and a degree of unsaturation (100 L, per liter) of 71).
017-0.205, isocyanate content 0.3%
A viscous liquid with (maximum) K (2/71.3 at 25°C)
). Thiofur/Chemical Division, Thiofur Corporation.

Chemlink 600 or CL 600-polyoxyethylene glycol 600 dimethacrylate. Molecular weight approximately 770
oO3, H6, O,. Ware Chemical Corporation.

Hulcan (VULOAN)-xc-72R1N472o
'41. Electric 7 Arnes sword - Pon black. Capobot Hoop.

Itfite - hydrated magnesium silicate.

TBPB - hyperbenzened, tert-butyl fluoroate.

Evocryl 370 - non-volatile diacrylate ester of liquid bisphenol A epoxy resin. Viscosity 25℃ (10
0% resin) 9,000% acidity per 100 g
: 0.007, epoxide 100 f/per it
O,02, Gardner color 4, weight/capacity (bond/
US gallons) 9.99, flash point > 204°C, Gardner viscosity, 25°C (80 wt% resin in xylene) v-y. shell chemical company.

Chemball 4825- (19-4825) A solvent-free epoxy acrylate resin containing active acrylic unsaturation on the polymer molecule. Acid value 3-10. Color 1-4,
Viscosity 4000 to 6000 centipoise under 140 (60,0℃), 14oo to 160”F (71,1℃)
18o.

Centipoise. 9.8 to 10.0 bond weight per gallon.

Contains up to 2% by weight of free acrylic acid. Freeman Chemical Corporation.

580-Polyethylene unsaturated liquid oligomer with high reactivity in free radical polymerization. A lagoonal, amber liquid with a mild characteristic odor. Mucus (Gardner-Holt) Z ~ Z7 (200
~500 poise), color (Gardner-Holt) max. 3, fine slip 9.6 ± 0.1 bond per US gallon, flash point (closed cup) approximately 2101r (98.9°C).

Polychrome Corporation.

ATT, AC382 monobisphenol A-polyester resin. Engineering 0 E America Inc.

Yuvisen (UV Engineering THANK) 893 - Polymerizable urethane oligomer and viscous liquid. APHA color up to 110, mild odor, weight 10 bonds per gallon at 77 below (25,0°C), viscosity 90 at 120 below (489°C)
0 to 2200 Hoaz, 80 at below 160 (71.1℃)
30 to 80 poise at ~180 and 180 °F (82,2 °C), 0.150 to 0.175 equivalents per 100 g of unsaturation
, and isosif*-to including J! Maximum 0.2%. Thiokol Corporation.

Polyester - A polyester made by the copolymerization of propylene oxide, ethylene oxide, maleic anhydride, fumaric acid, and phthalic anhydride using a double metal cyanide catalyst. It is an isomerized product with r)H terminal and has a molecular weight of about 1200.

uVIMKR 530 - A polyethylenically unsaturated liquid oligomer with extremely high reactivity in free radical polymerization. Viscosity (Gardner-Holt) Z, ~Z8
(375-600 poise), color (Gardner-Holt) up to 5, weight per US gallon 9.800, (15 bond), and flash point (closed cup) approximately 210?0 Polychrome Corporation.

Nuvol 46-8012 - a mixture of 70% acrylate terminated polymer, 28% styrene, and 2% hydroxyethyl methacrylate.

Mistron RO3-talc Cyplus Industries Chems.

Ubicene 782 - Acrylated urethane oligomer.

Low melting point congener. APHA Color 5Qmaxot Mild smell. Kf/e of 10.2 (1,2) at 77°C (25°C) o 120'F (
49°C) Teno viscosity 800-(51) 1600 Boise. U 200-3 below 160 (71°C)
50.180 (at 82°C) 85-165° unsaturation equivalents/100, 0.04-0.05° isocyanate content % 0.3 max 0 Thiokol Chemical Division.

Applicant: The General Tire and Rubber Company Representative Patent Attorney: Yatabe Sasai (and 1 other person) (52)

Claims (1)

[Claims] 1. (a) (1) a polyurethane-based oligomer having at least two acrylate groups, (2) an epoxy-based oligomer having at least two acrylate groups, and (3) a plurality of internal ethylenes. (b) copolymerizable ethylenically unsaturated monomers; (c) fatty acids having at least 10 carbon atoms; (d) an accelerator for the peroxide initiator; (θ) a small amount of polyvinyl acetate relative to the polymerizable material but sufficient for paint adhesion; and (f) any other optional components. may contain a copolymerizable monoethylenically unsaturated compound having -ao group and -NH2, -NH- and/or -OH group, (g
) In addition, optionally, as a partial replacement for (a), 2 to 4
(h) Optionally, other The ethylenically unsaturated material may contain a calcium salt of a fatty acid having at least 10 carbon atoms, and (1) may also optionally contain fillers. A composition useful as a thermosetting molding composition, present in sufficient total to provide the composition. 2. (a) (1) a polyurethane-based oligomer with at least two acrylate groups; (2) an epoxy-based oligomer with at least two acrylate groups; and (3) a polyester-based oligomer with a plurality of internal ethylenically unsaturated groups. 100 parts by weight of a polymerizable oligomer selected from the group consisting of oligomers of
(c) about 0.2 to 5 parts by weight of a zinc salt of a fatty acid having at least 10 carbon atoms; (d) about 0.05 to 2 parts by weight of an accelerator for peroxide initiators. , (θ) and about 40 to 80 parts by weight of polyvinyl acetate, (f) optionally containing a -co- group and -NH2, -NH
A copolymerizable monoethylenically unsaturated compound having -1 and/or -OH groups may contain from 0 to 120 monoethylenically unsaturated compounds; (g) Optionally, as a partial replacement for (a), 2
A copolymerizable liquid compound having ~4 vinyl groups, free of urethane, cycloaliphatic and aromatic groups, and having a molecular weight of up to about 1500, containing initial 0 to 120' M fEi parts. and (h) other optionally a calcium salt of a fatty acid having at least 10 carbon atoms.
A composition useful as a thermosetting molding composition according to claim 1, which may contain from 5 parts by weight of (J,) 4F to 5 parts by weight and optionally a filler. 3. A composition according to claim 1, wherein the composition additionally features an organic free radical peroxide initiator of up to about 5% based on the amount of ethylenically unsaturated material. thing. 4. (a) is liquid diacrylate-terminated polyester urethane or diacrylate ester of liquid bisphenol A epoxy resin, (b) is styrene, (c) is stearin-resistant, (,i) is cobalt octoate, ( f) is hydroxypropyl methacrylate, (g) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770, (h) calcium castearate, and (1) is about 5
A composition according to scope 2 of the patent Hl'J, comprising 0 to 150 parts by weight of talc and about 5 to 15 parts by weight of conductive carbon black. 5. Based on the ethylenically unsaturated material Ichikawa, a special compound additionally containing up to about 2% of tert-butyl benzoate
Composition according to Item 4 of 'f# Desired Range 411. 6. A molded thermosetting polyester resin or thermosetting vinyl ester resin glass fiber composition containing about 10 to 75% glass fines is coated in the mold with a thermosetting mold coating composition. In a method comprising in-mold coating under pressure, temperature and time sufficient to cure the coating composition to form an adherent thermoset coating on the molded thermoset glass fiber composition. The in-mold coating composition comprises (a) (+) a polyurethane-based oligomer having at least two acrylate groups, (2) an epoxy-based oligomer having at least two acrylate groups, and (3) a plurality of a polymerizable oligomer selected from the group consisting of polyester oligo V-1 with internal ethylenic unsaturation and mixtures thereof; (b) an ethylenically unsaturated monomer capable of copolymerization; (c) at least 10 (d) accelerator for the peroxide initiator; (θ) polyacetic acid 1'JI vinyl in a small amount compared to the polymerizable material but sufficient for paint adhesion. (f) may optionally contain a copolymerizable monoethylenically unsaturated compound having -〇〇- group and -NH, -NH- and/or -OH group; (g) Optionally, as a partial alternative to (a), a copolymerizable polymer having 2 to 4 vinyl groups, free of urethane, cycloaliphatic and aromatic groups, and having a molecular weight up to about 1500. (h) may also optionally contain a calcium salt of a fatty acid having at least 10 carbon atoms; (1) the G-sweat may optionally contain fillers; Often, the ethylenically unsaturated material is present in an amount sufficient to provide a thermosetting composition upon curing, and the ethylenically unsaturated material is present in an amount of about 5% based on the weight of the ethylenically unsaturated material. 1
．． & A method of having an organic free radical vortex initiator. 7. A molded thermosetting polyester resin or thermosetting vinyl ester resin glass (a) containing about 10 to 75% of glass fibers (a) by a thermosetting mold coating composition ( (In-mold coating under pressure, temperature, and time sufficient to cure the inner coating silk and carve an adhesive thermoset resin onto the molded thermoset resin glass fiber composition.) In a method comprising: (a) () a polyurethane-based oligomer having at least two acrylate groups; (2) an epoxy star disc having at least two acrylate groups; oligomer, and (3) an internal ethylene-free polymerizable oligomer with i, u number of 100 Ichikawa parts, (b) a copolymerizable ethylenically unsaturated fit M-body of about 80 to 150 i [j-placed part, (C) at least 10 1) about 0.2 to 5 parts by weight of a salt of a fatty acid having 1 carbon atoms; e) contains about 40 to 80 polyvinyl esters, (f) and optionally -a o- groups and -NH2, -N
A copolymerizable monoethylenically unsaturated compound having an H-1 and/or -OH group, starting from 0 to 120 parts. (g) Optionally, as a partial replacement for (a), 2.
A copolymerizable liquid compound having ~4 vinyl groups, free of urethane, cycloaliphatic and aromatic groups and having a molecule I of about 15004, containing an initial amount of 0 to 120 parts by weight. (h) may also optionally contain from about 2 to 5 parts of a calcium salt of at least 10 carbon atoms; (j
) and also about 5 weights 11 based on the weight of the ethylenically unsaturated material.
7. A method according to claim 6, characterized in that it contains an organic free radical peroxide initiator in an amount of . 8 (a) is liquid diacrylate-1 terminal polyester urethane or diacrylate ester of liquid bisphenol A epoxy resin, (b) is styrene, (c) is zinc stearate, (d) is cobalt octoate, (f ) is hydroxypropyl methacrylate, (g)
polyoxyethylene glyfur dimethacrylate having a molecular weight of about 770, (h) is calcium stearate, and (1) is about 50
8. A method according to claim 7, comprising from 150 parts by weight of talc to about 5 to 15 parts by weight of conductive carbon black. 9 The initiator is tert-butyl perbenzoate, approximately 2% by weight.
A method according to claim 8, used in trench quantities.