DE2011808A1 - Molding and coating compounds - Google Patents

Description

Patent attorneys Dipl. Ing. F. Weickmann ,. ---—-

■ Dipl. ! ng. H-Wsickmaiiii, Dip !. Phys. Dr. K. Fincke

Dipl. Ing. F. Λ. Weickmsn », Dipl. Ciiem. B. Huber

8 Munich 27, ftliihlstr. 22nd

Sch / Gl ₌ . . IHPAiJgIlTO - 808646

AMBRICAlT MACHINE AND POUlTDRY COMPANY, New York, K. Y. / USA

Molding and coating compound

The "invention relates to new porra and coating compositions den & n high quality items with improved physical and chemical properties can be produced. Furthermore, a method for the production falls within the scope of the invention. development of such masses.

also.The new © rflndungsgeraässen Porm- and 0f "can be used to share ,, a variety of products hßVfMB, they are turned back preferably Mr Hersteilung vo" Bowlißg-KegeXiieisgesetst. The E3 "resourceful" is yy

BAD OFHGWAt

_ ρ -

not limited to this application.

The use of plastics and products coated with plastics for the manufacture of. Objects that have previously been made from metal, wood and various other naturally occurring materials have been increasing steadily for several years. For some time now, there have been developments in the field of plastics and new plastic compounds. However, many of the plastics currently available do not yet meet the demands placed on them, even though they are in many ways better than metals, wood and naturally occurring substances when used in the manufacture of variously shaped objects , the manufacture being made by casting , Molding or compression molding can be done. These disadvantages occur particularly in the manufacture of bowling pins. For a number of years, plastic covered bowling pins have replaced the wooden pins. For example, polyurethane coated bowling pins have been used extensively. Nevertheless, there is a need for cones of this type which, in contrast to the cones used hitherto, have better physical and chemical properties.

The present invention now addresses this need Fulfills. The invention provides coating and molding compounds provided with improved physical and chemical properties. These masses consist of an im essential moisture-free polyurethane polymers and a smaller amount, i.e. about 1.0 - 5 »0 Gewiohta- #, an epoxy hair and a hardening agent,

Under the term "essentially Jfeuohtigkeiteir ·!" «Oll

BATH ORIGINAL

003 * 40/1364

should be understood to be 0.5 wt% or less based on on the weight of the mass, moisture or water. The essentially complete lack of moisture as well as the presence of the epoxy resin in the mass contribute in unexpected way to the favorable properties. Are for example inventive masses for the production of with Polyurethane-coated bowling pins are used, then products are obtained which have an increased service life, whereby also the deformation resistance and the crack resistance of the polyurethane coating are improved. In contrast The polyurethane covers of bowling pins in which the humidity is above 0.5% by weight deform Coatings also do not contain epoxy resin, in excess Manner, creating bubbles which, with continued and repeated blows, develop cracks which lead to the coating can only be used for a limited period of time. In addition, when cones are used, which have such defects in automatic cone setting devices Disturbances on. .

These disadvantages of moisture-containing polyurethane coatings without epoxy content occur with those coated according to the invention No more bowling. Particular attention should also be given to the formation of grooves, which occurs in the case of the known coatings provided cones occurs. This groove formation is also no longer detected according to the invention. The grooving depends on the resilience of the coating at the points where the ball hits the cone. These places should have constant and uniform elastic properties with regard to the service life of the cones.

Vary the components which may have been used for the production of the inventive pGlyurethannassen ₉ significantly.

In general, these components consist of the polyurethane compositions however, made of elastomeric materials that differ from organic. Derive isocyanates, i.e. it is diisocyanate and Triisocyanate measures with alcohols and ethers, i.e. polyols and / or polyether glycols, also called polyether polyols are known, have been implemented.

Examples of polyether polyols, which together with the organic Isocyanates can be used are polyalkylene ether glycols of the general formula

HO-On H _2n 4 O-C _n H _2n * _χ 0-H

where η is an integer from 2-8 and χ is a 2 number, which symbolizes a molecular weight of less than about 8C00 and at least about 400, namely at Molecular weight of the polyurethane prepolymer used in. the Reaction of the polyether polyol with an organic isocyanate accrues.

If -G Hp - stands for -Cp H, -, then the polyol can be regarded as a derivative of ethylene oxide or ethylene glycol. If -C _n H _{? P} ~ stands for -C ^ H ₆ -, (ie for (CH ₃ -GII ₂ -CII ₂ -). Then the polyol can be regarded as a derivative of prepylene oxide or propylene glycol. If -C Hp - for -C.Hp-, then know the polyurethanes as derivatives of 1,4-butanediol, 1104OH ₂ ? .OH or Tetraliy drof uran

Ho-CG-II ₉
H ₉ -C CH ₀

² V -

> P ■

BATH ORIGINAL

Are polyether polyols of the general formula HO-G.Hg- (O-G.Hg) OH in various dimensions with tolylene diisocyanate (TDl) reacted in excess, then products with changing molecular weights are obtained. 3 polyurethanes, i.e. polytetramethylene ether glycol adducts of tolylene diisocyanate, with excellent properties which fall under the general formula can be characterized by the following data:

Weight of free NCO Approximate molecular weight

4 - 3000

6 1500

9 850

According to the invention the preferred is polyalkylene ether glycol the addition product of tetramethylene glycol and ethylene oxide with a molecular weight of at least 500. It is a simple product made up of relatively few molecules is formed. However, the polyol can also be the intermediate reaction product of many molecules. Becomes propylene oxide is used, then a branched chain, for example, is obtained.

The basic polyol unit does not need to be a simple glycol with adjacent hydroxyl groups; it can also be a diol in which the hydroxyl groups are not adjacent, as is the case, for example, with the following compound: HO- (GHp) .OII. The simplest polyether on this Basifj is as follows: HO (GH _2).-0- (CH ₂₎ .011.

There can also be more than 4 methylene groups Polyether polyol can also be a more complex type, for example

BäO OfiiÖlNAL

wise a condensation product of 2 or more different Polyols (or polyols and ethylene oxide-like compounds). Examples are hexanetriol and propylene oxide or hexanetriol, Pentanediol and propylene oxide. Many isomers as well as mixtures can be included in your product. Suitable polyols are described, for example, in U.S. Patents 2,901,467 and 2,917 described.

The isocyanates used to synthesize the polyurethanes can be aliphatic or aromatic. A suitable common aliphatic diisocyanate is 1, e-Hxaineth.ylentl.iiSG-cyanat. The most commonly used aromatic diisocyanate is lolylene diisocyanate. which is known in the usual way as toluene diisocyanate (I ¹ DI). This designation also includes the isomers and mixtures of isomers of tolylene diisocyanate. The most frequently used diisocyanate material is the _{00/20 mixture of 2, / t} - ^r üolylene diisocyanate and 2,6-tolylene diisocyanate. Each 3-TGO residue in these compounds can react in one of several ways. As a result of: .-: possible reactions, the large molecules formed have multiple cross-links or chain branches. In general, the more numerous these are, the stiffer and harder the finished polymer. The fewer the crosslinks and chain branches, the softer and more pliable the polymer will be. The reaction to form a lakroir.olokül creates a thermosetting polymer. In general, this can be post-deformed by the action of heat and pressure, so that the materials are actually thermoplastic, thermosetting materials. During the deformer, the partially cured preform continues to cure, but not necessarily to completion. The product can then actually be released by heating in a tunnel or by leaving it to stand at room temperature for a period of time

D098ÄQM3S4 bad original

Period of a few weeks: to be post-cured. Usual Storage periods prior to shipment are sufficient to allow hardening to end.

Because the reactions practically "run to completion," it should nevertheless be pointed out that they are reversible, so that new equilibria are established can result in changes to the properties. An example of this is the extreme sensitivity to moisture of some polyurethane polymers. Further there are examples of sensitivity to oxidative reactions. In general, however, is the chemical Resistance and resistance to solvents Well.

Representative examples of typical organic isocyanates which can be used to produce the new coating and molding compounds according to the present invention are m-phenylene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexaraethylene diisocyanate, tetramethylene diisocyanate. 1,4-diisocyanate, cyclohexane-1,4-diisocyanate, l-taphthylene-1,5-diisocyanate, 1-methoxyphenyl-1,2,4-diisocyanate, methylenebis (4-phenylisocyanate), 4,4'-biphenylene diisocyanate, or the like . Mixtures of toluene-2,4- and 2,6-diisocyanate can be used. In general, preference is given to the diisocyanates in which diisocyanate groups are substituted on aromatic rings. Generally about 4.0-11.0 moles of the organic diisocyanate reactant are used. Other polyfunctional isocyanates can also be used, for example the triisocyanates, for example toluene triisocyanates, either alone or in a mixture with one or more bioisocyanates. In this connection, reference is made, for example, to US Pat. No. 2,531,392. " ^r *

BATH ORIGINAL

A variety of epoxy resins can be used in the invention Coating and molding compounds are used. In addition, you can these epoxy resins are aromatic or aliphatic polyetheroxy types and have a molecular weight of about 300 to own about 2000. In general the ones are aromatic Polyatherpolyepoxyde the reaction products of bisphenol Δ and epichlorohydxine and correspond to the general formula

CH -j

JH,

CCTICZ ^ -G ("\ -G ~ 001I _o 0EGeX-ö —Ο ~ ^ΰ —O

OCIi ₉ ClICIL

CHv

CH ₅

woxYi.n η is an integer from 0 to 7 inclusive. The aliphatic Polyätherpclyepoxyde are the reaction products of aliphatic glycols with Epichlorhyörin and correspond to: -! the general formula

C)

I ^{/ N}

ti fiTjnTT _n ι— ^r 'i ^T —Γ "Τ-Τ — Π -—PTT ΡΤ-Τ — Π — ΡT-T —C'V— PIT

έ. C C. <: ί Cd

wherein R is lower alkyl radicals having 1 - 5 is Kohlenstoffatcmen, and η is an integer of 3 to e the chi ie ss J. I is 6.

The production of the polyurethane materials according to the invention is generally carried out in one of a two-stage process, with an excess when carried out in one step. the organic isoeyanate with the polyol odor polyether polyol e j'hit Kt and then ml i: cj.nc!. :: Jia:.; J.Ti, v, ^r (.: Jc] ie; i das J-Ia i.rrial :: ur Er: 'ciigiui, ^; : hoclif es ter r:? I: l .hü: bt ^ ι · ν · .l.it;> i ^; .v-: r ilaiMiün ! ^!. '! .. yaorisj.oj / t and γη rnotiöt, \ -; c ^u c: v-ji' / iu ,. "Wf i:. · Ο A , Ί ^! -! Ίο i'iYlonbi." ■ - (. '-Ch! Ο.ι'? Ί "ι Π.ΐη) οο <τ ΐ ·] οthy. ·. Ο) \ ~

BATH ORIGINAL

dianiline come into question. It should be noted, however, that "any other suitable hardening agent of this type can be used.

The production of the coating and molding compositions according to the invention provides a multitude of procedural steps during Any appropriate care must be exercised to ensure that the masses are kept essentially free of moisture i.e. that the moisture content is less than ■ ^ about 0.5% by weight based on the total weight of the Hate being hired. Generally, the polyurethane prepolymer component is used the masses obtained by known methods from representative precursors such as those given above after its production as a polyurethane with suitable properties (namely both physically and chemically). It is generally a fluid material with a molecular weight weight from about 400 to about 8000.

The polyurethane is fed to a mixing device which is sealed off from the atmosphere and is connected to a drying tube is provided. A curing agent and a suitable epoxy resin as above are added to the polyurethane with stirring has been defined. The mixture is stirred or agitated in any suitable manner until a homogeneous mass has been obtained. Die-made in this way Compound is excellently suited as a coating and molding compound. It can be done in a simple way deform a shaped object according to known methods. They can also be used to form a synthetic resinous Use a coating layer on a preformed core, the core being either a plastic Metal or wood. For making bowling

BADORlQfNAL

Cones generally prefer preformed wooden cores.

In the masses according to the invention, the polyurethane represents the Main component, while the epoxy resin in smaller Amounts from about 1.0 to about 5.0 weight percentages based on the weight of the polyurethane. The hardening agent used should be present in an amount that sufficient to bring about an approximately substantially complete hardening of the mass. Generally about 5.0 to about 25 C-ews · - ^. based on the weight of the mass, a suitable curing agent is used.

Furthermore, various other ingredients can optionally be added, for example mold release agents and pigments, for example titanium dioxide. The addition to the masses takes place in smaller amounts of about 0.1 to about 2.0-3.0% by weight, based on the weight of the masses. As previously mentioned, the polyurethane, epoxy compound and curing agent are simply mixed together at ambient temperature, taking care to avoid the addition of moisture. Then it is agitated or stirred until a homogeneous mass has been obtained. In those cases in which it is necessary, heat can be applied during processing and stirring in order to achieve a homogeneous mass. When heat is allowed to act, then the temperatures between room temperature are (about 21 ⁰ G) and (300 ⁰ F) to avoid about 149 ° G to excessive polymerization of the prepolymer. However, it is generally preferred to prepare the prepolymer blend at room temperature, with serge worn to prevent moisture from being introduced. In addition, the molding and coating compounds should be used within a relatively short period of time after manufacture. In general, the YorpolyiüGreri life is

0 §% A Xy / * % I & BAD ORIGINAL

at room temperature no more than 120 minutes before use to form a molded article. However, the pre-polyning mass can also be under for longer periods of time Can be stored cool, either before or after deformation into the preform.

According to a preferred embodiment of the production of the prepolymer molding and coating compositions according to the present invention and the subsequent use for the production of plastic-coated bowling pins, the following process steps are carried out: Sin container I for the polyurethane prepolymer is provided with a drying tube, to prevent the dragging in of moisture. The polyurethane is introduced by gravity into a heated mixing vessel in which it is to a temperature of about 49 - is brought - (125 ⁰ F 120) 52 ° 0th A 50 volume mixture of Freon (halogenated hydrocarbon) and a mold release agent is slowly added to the heated polyurethane with stirring in an amount sufficient to add 0.1% by weight of the mold release agent, based on the total weight of the prepolymer molding compound to provide for grouting "Pas freon is removed by evaporation and degassing in a Entgaßungseinheit, wherein the mixture in the unit of g at a temperature of about 77 - 85 ⁰ C (170 - 185 ° F) and under a vacuum of less than 5 mm Hg is maintained. This removes all volatile materials. The Mischui "g of 'polyurethane and mold release agent of a mixing apparatus is then supplied wroraüf a pigment mixture containing 60 ° / o of titanium dioxide and 40 ^c /> epoxy resin includes, a mixing vessel is fed. The mixture does not contain more al? 0.6 weight ^ Moisture. The mixing and stirring is carried out until a homogeneous mass has been obtained. This mixture is then used as one of the two "starting streams used".

008840/1304

BAD OBiGJNAt

The curing agent is used as an additional output stream in an amount of 25 parts per 100 parts of the formation of polyurethane, mold release agent, pigment and spoxy compound to form the finished Yorfiolyneren porcelain mass.

The HiJrtunjrünittel is heated during a hand, breakdown of about X hours before use to all drive moisture from ζυ, v / ith 4, ^4! -Methylene bis (2-chloraniiine), a pesticide, is used, then this compound is first melted and heated to 121 ⁰ C (250 ⁰ F).

The use of this mass aur manufacture of bowling cones carried anseMiessenu after given below of operation: Sine suitable amount, preferably 85 - 113 g (3 - A ounces), the molding composition / ird in a Aluminiumvorforir given v wherein the cavity of the Porm in roughly corresponds to the shape of a bowling pin from head to floor. The life of the VorfoxTj-m.i3ch.ilng should not exceed 120 minutes at 22 ° C (? 2 ° F). In production, this rope line between the treatment in the pre-cut training device is kept essentially constant on a core until after the test is carried out, unless storage is carried out in a non-Tex-cooling manner, as mentioned above.

If wooden cores are used for the production of bowling pins, the preformed core has two deforms which are located opposite one another. A spacer made of the same resin compound is not indicated around the upper part of the lurn jerum in order to avoid it; Head of the cone ti n-3 in a Fo to zen sized. ^ in a striking section of wood ρ-- ;. "a / iojjtrierungsb] ock centers the lower part of the cone ;." iJor on diene '/ eiso horgoss romped Kcnni v / ird ajisciilios- ncni i :, g;: "jg ^ - ^ igncte, from, ^ ■.; ·, ". ·.;. Gtücvc]) best ^ hoj; de MeIaIl-

0 0984 Q /; IS 4 BADORiGlNAL

form accommodated in an automatic press and at a temperature between about 93 and about 113 ° C (200-235 ⁰ P), and preferably about 110-113 ° 0 (230-235 ⁰ F) under a pressure of about 7.03 to 70 , 3 kg / cm ² (100-1000 psi) and preferably 28.1-42.2 kg / cm. (400-600 psi) deformed for a period of 6-10 minutes or for such a period of time sufficient to allow hardening to such an extent that removal from the mold is possible.

Test the deformation of the cone is taken and machined surface-ä, whereupon markings, insignia and other decorative tapes, or information applied in the usual manner. Finally, a polyurethane coating is applied, if necessary, prior to inspection and packaging.

In general, in the manufacture of plastic-coated wooden bowling pins in accordance with the present invention, the thickness of the plastic coating can be within relatively wide limits of about 0.25 to about 12.5 mm (10-500 mils), and preferably about 0 , 67 and 6.7 mm (25-250 mils). In practice, thicknesses of 1.37 to 1.87 mm (55-75 mils) _{have been found to be satisfactory for making bowling pins} which have the desired qualities, ^

Any suitable compression molding device can be used to apply the coating to the cone cores.

A device for molding the preform mass onto the cone core consists for example of a mold, the mold halves which are provided with heating elements in a suitable manner

CONSTRUCTION ORIGINAL

Form can optionally be placed between heated plates, Un A centering block is used to keep the core centered in the mold. To be more accurate and faster To ensure centering of the core in the mold, one can use a ring or ribbon that comes with it after up! sen extending emphasis is provided, wherein the highlights have a thickness sufficient to fix the copying end of the core. Furthermore, one can separate Use spacer ^ with a suitable thickness, v / elche serve the same purpose. These are applied at intervals to the cone head before the core with the vestibules is introduced into the mold in the form of a unit. Preferably the sand or spacers consist of one Mass, which corresponds to the pre-forming mass or this is similar to what the protective surface layer is made of is formed, so that when deforming and hardening a mixture takes place with the formation of an integral rope. It can , Depending on the shape used and its position as well as the rigidity of the core device, the Tape or spacers to form a mass that is fully compatible with the polyurethane preforms, but at a higher temperature than the polyurethane preforms melts. i'er? ier may be the same composition trade with buckets of different degrees of hardness.

The following examples illustrate the invention. All percentages included; unless otherwise indicated, refer to the C-nwiolvt, Unless otherwise indicated,]} two preforms vurweiiairU ^ a- ""'areτο;.; a. "v ::. 'ö;'; so, soft such l.'i-.Z; that <.-... '■ <)?:. Lvug ι ~, Λ- : -iir ··. : ·.: · Γ \ ν.Ι: ο of about I ₁ ^ mr Si n · ::.:. · ■:: " ^ /.:.■■-■-."■ ■.:, 0: 01: lit ·· ...

BATH ORIGINAL example 1

A substantially moisture-free polyurethane mas.se, which contains a smaller amount of an epoxy resin, a pigment, contains a mold release agent and a hardening agent, is produced according to the following procedure:

A drum made of a polyurethane prepolymer is fitted with a drying tube to prevent ingress of moisture to prevent. The polyurethane used is made from polytetramethylene ether glycol and tolylene diisocyanate. It has a molecular weight of approximately 850 and has about 9 weight ^ of free NGO groups.

The polyurethane is introduced by gravity into a closed mixing vessel, and vop to a temperature 49 to 52 ° G (120-125 ⁰ P) is heated. The heated polyurethane prepolymer is slowly added a sufficient amount of a mixture of 50 and 50 fo Preon i> a Pormtrennmittels (zinc stearate) with stirring. In this way, $ 0.1 of the mold release agent is made available in the finished mass. A pigment mixture is then added to the mixture which contains 60 $> titanium dioxide and 40 $ of an epoxy resin with an epoxy equivalent weight of 180-195, the moisture content not being more than 0.6 $. The pigment mixture is added in an amount sufficient to provide a finished preparation containing 10 % of the epoxy compound and 2.0-3.0 ^c / o of the titanium dioxide. It is heated approximately 1 hour before mixing with the mixture of polyurethane, zinc stearate and Preon. After sufficient stirring to achieve a homogeneous mass, the Preon is removed by evaporation, whereupon the whole mixture is ^{degassed in a degassing unit at a temperature of 85 0} G (185 ⁰ P) under a vacuum of less than 5 mm Hg in order to achieve complete Removal of the

009840 / 13S4

BATH

to protect whole freons as well as other volatile materials. The mixture obtained is then used as one of two output streams for the formulation of a molding compound used.

The second output stream is prepared in such a way that a sufficient amount of 4,4'-methyleneMs- (2-chloroaniline) curing agent is ^{heated to a temperature of 121 °} G (250 ^° I?), Such an amount of this curing agent that is used about 20 wt- ^ in the paver. Mass present. This gown is held for a period of 1 hour at a temperature of 107 ⁰ C (225 ⁰ I?) To V to remove ater /. Then there is a mixing with the extreme output stream.

100 parts of the first output stream and 25 parts of the second Output currents are then taken with each other Stir mixed in a sealed kettle. A molding compound is produced which is less than 0.05% by weight Contains moisture, as on the basis of a gas chromatographic analysis is determined.

A suitable amount, preferably 85-113 g (3-4 ounces) the molding compound produced in this way is poured into two aluminum preforms at room temperature. the Cavities in the molds roughly correspond to the shape of a bowling pin. The two deforms become from the shapes pulled out and opposite to each other on a preformed Haul bowling cone core put on. A spacer of the same resin composition is applied around the top of the core to form the head of the core in a mold center. An outstanding section of wood is used for this

009840/1364

-.17 -

■ uses to center the lower part of the frame in a form.

The core and the two preforms are then "given the shape of a bowling cone. This form is transferred to a -automatic press and there" in a two-part mold with the at a temperature of 112 ⁰ C (235 ⁰ F) currency • rend "" 35 »2 kg / cm (500 psi) pressure for 10 minutes. The shaped cone is then removed from the mold, the surface is cleaned more often and with markings and labels. according to usual 'methods, provided,. ■.

The cone made in this manner has a plastic coating about 1.62 mm (65 mils) thick. Gas chromatographic analyzes of samples of the coating show a moisture content of less than 0.05 %.

Example 2

The procedure described in Example 1 is repeated, except that no precautions are taken to keep moisture away from the cash register. the Gas horroraatographic analysis shows that about $ 0.7 Moisture is present before the compression deformation. The coating obtained is porous, non-homogeneous and shows premature .Cracking both when performing a laboratory impact test and during practical use.

3 example 3

The in Example 1 beschriebene'Arbeitsweise wird'wiederholt, except that a · Pigmentmisclmng is used die'70 "fi titanium dioxide and 30 / ί contains dioctyl phthalate. Gaschrcmatographische shows an analysis is that a

BATH ORIGINAL

Moisture content less than 0.05 ° / ° prior to compression molding. The resulting coating exhibits a high degree of deformation, with the deformed areas cracking prematurely during repeated impacts in use.

3e is pi el 4-

The procedures of Examples 1 and 3 are followed, with 10 bowling pins being produced after each procedure will. The cones are checked using a "stub alley tester" tested, the results obtained reflecting the properties of each cone, compared to a known cone with a plastic coating with a Thickness of approximately 1.37 mm (55 rails). This coating consists of an acrylic latex primer coating with a thickness of 0.025 mm, a nitrocellulose intermediate coating with a Approximately 0.050 mm thick and an outer covering 1.25 mm - 1.30 mm (50 - 52 mils) thick of ethyl cellulose.

The test is performed over 4500 cones. The 3 corresponds to approximately 3000-3500 actual cones, as the test does not include the situations in which one or several cones are hit directly by the ball. The test results are summarized in the table below.

009840/1364

Regulations

Cone type

Usual cone

Example 3 (dioctyl _: phthalate)
Example 1 (epoxy resin)

1000 cones

common cone 49.6

Example 3 (Dioctyl- 93.5

phthalate)

Example 1 (epoxy resin) 96.6

1500 cones

common cone 109.7

Example 3 (Dioctyl-112.9 phthalate)

Example 1 (epoxy resin) 116.1

Tabel Cracks Coating blow Coating loss separation (cm2) (cm ² ) no none no 26.5 no 'none 2 starting 37.4 no none no 43.9

2000 regulations
usual cone

138.7

Example 3 (dioctyl 125.8 phthalate)

Example 1 (epoxy resin) 122.6 2500 cones
more common. cone

no
no

no

no
no

no

none none

none

none none

none

total (I45.2cnr)

'Example 3 (dioctyl) - "phthalate)

Example 1 (epoxy resin) "none

all cones, beginning with slight and smooth bumps, 50 jS

no all cones

smooth out

40 yo
head
cracks none no no none all cones no none still out-
smooth 100 1o
at the head 40 ° / ö
at the
head no no none all cones no none no

009840/1364

Table (port setting)

3000 regulations
Cone type

3000 regulations
ubli.ch.9r cone

Example 3 (dioctyl) phthalate)

Example 1 (epoxy resin) as a whole

Coating Cracks About2Ugs- at the head blow separation loss (om2) (cm2) gesarat 80 ok 20 io at the 6.45 cm no head in the Ball line 20 io 20 OK _o at the 12.9 cm ^ Bullet- line gesarat no Everyone ) fresamt no no

3500 cones
usual cone

total

Example 3 "(Dioctyl- total phth ^ lat)

Example 1 (epoxy resin) a total of 4000 Kegelun.Ten

Usual cone overall

loo io 100 f> no at the 6.45 - ρ Head u .12.90cui at the at the Bullet head line 40 % ρ 6.45 cm at the Bullet line no none Everyone no none no see above 100 ok no 6.45 - ρ Everyone 12.90 cnT at the head 60 i * ρ 20 <fi 6.45 cm at the Bullet line

easy

009840/1364

Table (continued)

Cone type

4l? OO regulations

usual cone

Coating separation

total

Example 3 (dioctyl "phthalate)

Example 1 (epoxy resin) "

Cracks Coating blow loss (cm2) see above 100 ^ ₂ no 6.45 cm at the head 60 io " 12.90 cnT at the Ku line no no Everyone no ■ none 20 ° / o easy

The values clearly show the superiority of those according to the invention Molding and coating compound as well as the superiority of the bowling pins that have been coated with this compound using the specified methods.

Example 5

The procedure according to Example 1 is repeated - with the Exception that a polyurethane prepolymer with a molecular weight of about 3000 and about 4% by weight of free. N00 groups is used. In addition, methylenedianiline is used ends in such an amount that 9% by weight are present in the finished mass. 10 made of this material cones have properties similar to those in the preceding Properties listed in the table are similar.

Example 6 .

The procedure described in Example 1 is repeated,

009840/1364

BATH

with the exception that a polyurethane-Yorpolymeres with a molecular weight of about 1500 and about 6.0% by weight of free ITCO groups is used. About that In addition, the hardening agent is in an amount of 15% by weight, based on the weight of the mass. There v / earth 10 cones are made which have properties similar to have the cones which have been produced according to Example 1 are. The molecular weights of the materials used are determined according to standard intrinsic viscosity methods,

009840/1364

Claims (1)

- 23 claims . 1. Molding and coating composition, characterized in that it consists of an essentially moisture-free polyurethane, a smaller _{amount by weight, based on the weight of 1 of} the polyurethane, an epoxy resin and a curing agent in an amount sufficient for this purpose who hate to harden. ■ 2. Composition according to claim 1, characterized in that the epoxy resin is present in an amount of about 1.0 to about 5.0% by weight, based on the weight of the polyurethane. 3. Composition according to claim 1, characterized in that the polyurethane consists of a polyol with a molecular weight of at least about 400 and an isocyanate were produced that is. 4. Composition according to claim 1, characterized in that the polyurethane has been produced from a polyalkylene ether glycol with a Mole- * kuüargewicht von'wen at least about 400 and a l'sccyanate .. 5. Composition according to claim 1, characterized in that the polyurethane consists of a polytetramethylene ether glycol with a Molecular weight of at least about 400 and tolylene diisocyanate has been made. 6. Composition according to claim 1, characterized in that the Polypropylene glycol polyurethane with a molecular weight of at least about 400 and n-phenylene diisocyanate. 009840/1364 BATH ORIGINAL 7. Composition according to claim 1, characterized in that the Epoxy resin is a polyether polyepoxide with a molecular weight is from about JOO to about 2000. 8. Composition according to claim 1, characterized in that the hardening agent consists of 4,4'-methylei: bis- (2-chloroaniline). 9. Mar-se according to claim 1, characterized in that the Hardener consists of methylenedianiline. Ί0. Cash register according to claim 1, characterized in that it is made of a polyurethane, approximately 1.0 to approximately 5.0 weight #, based on the weight of the polyurethane, of an epoxy resin and a hardening agent, the Mass less than about 0.5% by weight, based on that Total weight of the mass, containing moisture. 11. Shaped: object with a core which is covered with a layer, characterized in that the layer of a substantially deformation-resistant, crack-resistant and moisture-free polyurethane, approximately 1.0 to about 5.0% by weight based on the weight of the polyurethane, an epoxy resin and a hardening agent in an amount sufficient to harden the mass. 12. Bowling pins with a core that cover with a layer is, characterized in that the layer of a substantially deformation-resistant, crack-resistant and moisture-free polyurethane, about 1.0 to about 5.0% by weight based on the weight of the polyurethane, an epoxy resin and a curing agent in such There is an amount sufficient to harden the mass. 009840/1384 ^ _{0 0R1G1NAL} • - 25 - 13. A process for the production of shaped objects with a core which is enveloped by a synthetic resin, characterized in that a partially cured preform made of an essentially moisture-free polyurethane which has a smaller weight reduction based on the weight of the polyurethane contains an epoxy resin and a curing agent in an amount sufficient to cure the epoxy resin enthaitende polyurethane, is molded, at least one preform to the core with centering of the core overall with the partially - * cured preform in a mold having a cavity , which corresponds to the dimensions of the finished object, is applied, pressure is applied to the mold, which surrounds the core and the preform, until the preform flows with the formation of an integral, uniformly adhering enveloping layer on the core and the epoxy resin-containing polyurethane flows is hardened. 14. The method according to claim 13, characterized in that a plurality of preforms on the core prior to insertion of the core is attached to the mold. · 15. The method according to claim 15, characterized in that ™ Centering devices attached to the core v / ground to the core at an equal relative distance from the walls to position the shape and thereby an'even distribution to ensure the polyurethane layer on the core. 16. The method according to claim 13, characterized in that elevated support points are attached to the core at intervals, to "cause the core to center in the mold. 17. The method according to claim 13, characterized in that 009840/1384 bad original the mold is preheated prior to placing the core and preform adhered to the core into the mold. 18., The method according to claim 13, characterized in that the mold is held in a heated state during molding and the polyurethane preform flows over the core is left so that it adheres to this in a substantially uniform layer. 19. The method of claim 13, characterized in that the mold is ^{heated to a temperature between about 93 and about 113 0} G (200 and 235 ⁰ F), the temperature of the mold being within the specified range for a period of about 6 to is maintained for about 10 minutes. 20. Process for the production of an essentially deformation-resistant, Crack-resistant and moisture-free molded article coated with a plastic a core encapsulated in a synthetic resin, characterized in that a substantially moisture-free Polyurethane prepolymer in a minor amount of from about 1 to about 5 weight percent by weight the polyurethane, an epoxy resin and a hardening agent is mixed in an amount sufficient to harden the mass, the mixture is agitated or stirred v / ird and one essentially uniform mass formed from this mixture the mixture is placed in a preform at room temperature is filled and partially polymerized and partially cured in the preform v / ird, the preform obtained a preformed core is applied, the core with the partially hardened preform in a mold with a cavity, BATH ORIGINAL 009340/1364 ■ which corresponds to the measurements of the finished object, is centered, pressure is applied to the mold surrounding the core and the preform is allowed to act until the preform flows and forms an integral, uniform enveloping layer on the core, and to the core-set'schichtete polyurethane is cured.. t 21. The method according to claim 20, characterized in that the constituents which the polyurethane prepolymer ', mixed together and the preform at room temperature • _{% of} temperature are supplied. 22. The method according to claim 20, characterized in that the shaped article to be enveloped is a bowling pin. 009840/1364 BATH ORIGINAL