DE2339490A1 - THERMAL MOLDING COMPOUNDS AND THEIR USE FOR THE MANUFACTURE OF MOLDED BODIES - Google Patents

Description

Dlpl.-lng. P. WIRTH ■ Dr. V. SCHMIED-KOWARZIK Dipl.-Ing. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 β FRANKFURT AM MAIN

TELEPHONE COeil)

287014 GR. ESCHENHEIMER STRASSE 3Θ

Gases C-9I33-

UNION CMSIDE C
270 Park Avenue
New York, ii.a. '. 1001 ?, USA

Thermosetting molding compounds and their use for production

of molded bodies

The invention relates to new thermosetting molding compositions and methods for their manufacture, their use for the manufacture of moldings and new resins for use in the Molding compounds; in particular it relates to thermosetting molding materials containing resins which are used in "one stage", i. without the addition of hardening or crosslinking agents, heat-cured and which have a combination of advantageous properties due to which they are highly are advantageous for use in injection molding, compression molding and compression molding processes.

the field of deformation of synthetic resins has been nan since have long been searching for a thermosetting resin that cures in "one step", a molding material or a

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Molding compound can be admixed, which (which) has the following properties and / or receives:

(1) a light initial color and the ability to pastel, tones to be pigmented;

(2) good color stability even when heated and exposed to ultraviolet light;

(3) excellent deformation properties such as:

(a) the ability, during the stay: .n Y.'arm pouring channels * at about 120 ⁰ C,

devices are used to sufficiently maintain their plasticity and flow properties;

(b) the ability to cure quickly in heat when they are brought to a certain deformation temperature, and

(c) A suitable flowability (fluidity) in the mold so that it fills the mold to the exclusion of formation of cavities and the production of complex moldings allowed;

(4) minimal shrinkage during curing in the mold and after aging at ambient room temperature (for example 20 to 25 ^° C.);

(5) the molded body produced from it should be very stiff and retain its shape at elevated temperatures, so that it can be removed from the mold while it is still hot. This becomes the time consuming stage the cooling of the mold before removing the molded body is avoided; this property is technically called a "Heat resistance or Yiarm stiffness" or as a high modulus referred to at elevated temperatures;

(6) the molded body produced therefrom should be used at high temperatures, for example at more than 200 G, have a low degree of deformation;

(7) as those made from the mixed thermosetting resins Moldings are believed to be heat-resistant, they should also have the ability to absorb moisture

* (warm runners)

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and to withstand stresses caused by temperature differences in the walls of the moldings. This can can be defined as high resistance to water vapor cracking (water vapor cracking resistance) and moldings, that have this property can be used for such purposes as would be expected is that they are exposed to poor and water vapor, such as with stretcher irons;

(8) since thermosetting resins are widely used in the manufacture of molded articles such as those used for electrical and electronic applications are used excellent electrical properties highly desirable.

A variety of thermosetting resins are available to the moulder that can be used to make useful Molding compounds can be used, and the resulting Frare is whether one of these, when properly compounded, yields a molding compound (a molding material), possibly all of them Desired criteria given above are met.

First and foremost are the "1-step" phenol-formaldehyde resin Mentioning molding compositions containing. You do not meet a number of the criteria given above, e.g.

(1) they have a dark initial color and cannot be pigmented into pastel shades;

(2) They are poor in staining stability when heated and / or exposed to UV light;

(3) They are viscosity sensitive at high temperatures and viscosity increases too quickly when in Y / arm runners, as used in injection molding, are kept and when the viscosity or the flowability is adjusted by reformulating the molding compound or the molding material a loss of heat strength in those made therefrom Molded body on;

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(4) they shrink to an undesirable extent, although they are better than most in this regard thermosetting resins, and

(5) the water vapor cracking resistance of a phenolic molding compound with a good molding period (margin) is not sufficient.

Therefore, molding compounds or molding materials which contain 1-stage phenol-formaldehyde resins, although they are beneficial in many ways, very important Fox-m-criteria and product requirements do not.

Next are the "1-stage" melamine or urea-formaldehyde resins to mention · These molding compounds are known to have good light color properties because the resins are not disadvantageous in this regard. However, these molding compounds have the following disadvantages:

(1) the molding compounds have a high degree of shrinkage the shape and the shrinkage continues as we age continued at room temperature;

(2) a melamine or urea molding compound that has a good DeformuiigsZeitraum (margin) has, has poor V / arm strength properties; and

(3) They have poor steam crack resistance.

Polyester resins are known thermosetting resins, but they are not "1-stage" resins and if they are Molding compound are incorporated, the molding compound shrinks considerably in shape and when exposed to high temperatures is exposed. To keep this disadvantage to a minimum, the moulder must add a low profile additive to the molding compound, which causes the resin surface to expand expands on the mold surface to thereby form a molded body to produce that is closer to the capacity \ .ind configuration of the form annai.'t.

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The present invention relates to a molding compound which contains at least one inert filler which is superior to any of the desired properties mentioned above 1 to 8 can meet.

The molding compound (molding material) of the invention is characterized by being about 20 to about 70 Gev /.-% one light-colored resin, which is produced by reacting bisphenol A (hereinafter abbreviated to bis-A, known under the chemical Description 2,2-bis- (4-hydroxyphenyl) propane) with formaldehyde has been made, and about 30 to about 80 wt.> £, each based on the weight of the molding compound, contains a reinforcing filler for the resin. The resin acts it is the product of the reaction of formaldehyde with bis-A in a molar ratio of et? / a 2 bia about 3j75 in the presence an alkali metal or barium hydroxide condensation catalyst to form a 1-stage thermosetting resin. It has a pH of about 3 to about 8. The reinforcement filler it can be a particulate, for example pulverulent or fibrous, solid, that after mixing with the resin and after curing the resin to the solid state, at least one of the following Resin properties improved: tensile strength, tensile modulus, notched Izod impact strength, flexural strength and flexural modulus.

The first, by Dr. Leo H. Baekeland 1910 produced phenolic molding compounds or molding compounds were under Use of a device originally designed for ver-r Forming of rubber was intended to be deformed under pressure. When deforming under pressure (compression molding), usually with a cavity and a force from above or a A cold powder or preheated preforms are used. That Compression molding continues to be a main process for the production of thermoset molded articles or parts.

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Transfer molding or plunger molding was later developed. In this process, the preheated molding compound inserted into a separate plunger or shaft and then transferred (or injected) into the mold. The process is ideal for molding around inserts and for molding intricate parts or for molding with small tolerances.

Injection molding with reciprocating screw presses is the most recent advance in the field of molding of thermosetting materials, an advance that Interest in the 60th year old phenolic molding compounds and other thermosetting molding materials revived Has. The reciprocating auger device has heretofore been used for thermoplastics and has only recently been used modified for the processing of thermosetting materials. In principle, with the device, the molding compound is in Form of a powder from the funnel into the screw flights (screw flights) transported, whereby the material is heated, is melted and plasticized, and then with the help of the screw, which acts as a piston, the material is directly in injected the mold. The advantages of injection molding with reciprocating screw devices include high degree of automation and control, the elimination of preheated preforms, very fast curing cycles and the vertical removal of the molded body or molded part, the molds and the device correspond with respect to The cost and complexity of construction are those used for transfer molding.

The recently developed ability to produce thermosetting molding compounds Subjecting to injection deformation has reevaluated those used in many areas of injection deformation Materials led. The curing cycles for phenolic, thermosetting molding compounds are often shorter than the cooling cycles for engineering thermoplastics, especially thick ones

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or large moldings · Most thermosetting materials become stiff when cured and can while they are still hot, must be removed from the mold while the thermoplastics in the mold have to be cooled. The costs for the production of moldings from thermosetting molding compositions are now much cheaper than when they are used of the competing materials. Take, for example, the properties of molded phenolic resin parts (especially their 'heat resistance and dimensional stability) are favorable to the properties of Parts made from injection-molded metals (die-cast metals). Of course, the heat resistance and dimensional stability of thermosetting resins have always been those superior to so-called technical or sophisticated (engineered) thermoplastics.

Simultaneously with the development of the injection molding process progressed the development of improved thermosetting molding materials, e.g. phenolic molding compounds, which are more suitable for the respective requirements of injection molding. Examples of properties that improve are as follows: the density and the granulation, which are a steady supply both in the machine hopper as well as in the screw flights allow the sliding ability of the material for better control of the frictional heat in the drum and for better mold release and the melting and flow properties that allow the materials for most critical applications can be used. New resin developments make it possible that molding compounds in the heated drum of the Spraying machine can be kept for longer periods of time with a lower loss of flowability. In addition, once inserted into the mold, the material delivers because of its high heat resistance (V / arm stiff he it) in combination with the use of hotter molds (within the range of about 175 "to 2üO G) better distortion-free parts with extremely short ones

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Forming cycles.

It is expected that the "warm runner" method of processing thermosetting resins will become very popular in the next few years, particularly in the form of molds that currently use multi-cavity molds and deposition "sprue and runner" systems. which are 20 to 50 % of the total shot size. The "warm runner" deformation is sometimes referred to as "cold runner", "hot manifold" or "runnerless" deformation.

In the standard form for injection molding thermosetting materials, the material is in the "sprue and runner" system together with the parts (moldings) hardened and smashed when the entire moldings are removed from the mold will. In a "warm runner" form, the material is in the pouring sprue and a larger section of the "runner" system kept at a temperature at which it flows but does not harden by using the "sprue and runner" system in a separate isolated section of the mold. If now the hardened parts are removed from the mold the material in the sprue and runner becomes part of the next deformation, rather than being thrown away to become.

The accompanying drawing shows a cross-sectional view with self-understandable lettering of a typical "warm runner" shape. It can be seen that the tapping spout (runner), the pouring funnel (sprue) and the nozzles of the hot portion of the mold separated by a transition piece and are surrounded by water channels which hold the pipeline and nozzle temperatures at about 90 to 110 ⁰ C. . With effective temperature control in these sections, the molding material will actually remain flowable, only 0.952 cm (3/8 inch) or less from another section in the mold where the parts will cure at mold temperatures up to 205 ° C.

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From the above discussion it can be seen that the most obvious advantage of using the "warm runner" deformation method is that molding material can be saved, that is not thrown away but used effectively. According to the invention, however, additional Benefits can be achieved, for example better dimensional control, improved cycles and higher Degree of automation.

The properties of the used in the "v / arm runner" form Molding material (molding compound) are critical. The connection must have an exceptionally long service life (durability), i.e. it must only lose its fluidity very slowly if it is kept at the elevated pipe temperature. At the same time, once the material has entered the mold, which is at a considerably higher temperature, it must cure asap. .

In the injection molding process, the granular molding compound is poured directly into the hopper of the injection molding machine. The auger then rotates and moves backwards, drawing material from the hopper and at the same time pulling it plasticized to a putty-like soft mass. When the required weight of material has been plasticized, will the rotating screw stops and then it moves forward, acting as a piston, and pushes the mold joint through the pouring funnel, pouring chutes and slide into the cavities of the mold · After the required hardening time the mold is opened, the finished parts or moldings are removed and the cycle begins again.

Most of the thermoplastic injection molding machines can be converted for the shaping of thermosetting compounds, by installing a new screw and a new drum (a plasticizing unit) specially designed for this Materials are suitable. The length / diameter ratio of the screw for thermosetting compositions is normally

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14: 1 and is less than the 20: 1 to 24: 1 ratio for thermoplastics. The compression ratio (compression volume between the screw flights between the feed end and injection end) is typically 1: 1 for thermosetting materials compared to about 2.5: 1 for thermoplastics. In the case of thermoplastics, the cylinder is heated to around 2GO to around 320 G. The temperature control in the mold is within the range of about 35 to about 95 ° C · In the case of thermosetting compositions, the Tromrielteniperatur is normally within the range of about 60 to about 110 ⁰ C. The deformation temperatures are about 205 to about I50 ° C.

The screw speed in rpm is an essential factor for the correct plasticization of the screw flights passing material. A higher screw speed leads to a shorter one for a given load Plasticizing time. Thermosetting materials are usually produced with a screw speed between 5 ° and 75 rpm, which is less than that of 90 to 220 rpm, normally used for thermoplastics will. The screw back pressure is the pressure that is exerted on the material when the screw moves during the Plasticizing stage backwards against the applied hydraulic Resistance moves. This hydraulic resistance is controlled by the counter-pressure injection cylinder flow valve and normally the plasticizing pressures in the material are within the range of 28 to 211 kg / cm " (400 to 3,000 psi).

The resins according to the invention are prepared by reacting from about 2 to about 3.55 moles of formaldehyde with 1 mole of bis-Δ. Although the reaction of formaldehyde with Bis-A is described in the literature (see, eg, US Patent Nos. 1,225,748 1,614,172, 1,637,512, 1,873,849.

1 933 124, 1 948 469, 1 970 912, 2 017 877, 2 031 557,

2 050 366, 2 059 526, 2 070 148, 2 O79 210, 2 O79 606,

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2 169 361 , 2 279 526, 2 389 078 . 2,464-207, 2,522,569,

2 621 164 , 2 623 891, 2 667 466, 2 854 415, 3 OOP 847 ,

3024285, 3080331, 3159597, 3211652, 3264266,

3 390 128, 3 586 735 and 3 644 269, no resin is described therein, all of the above properties up / down if it is compounded in a suitable manner (mixed) is. Novolak resins (2-stage resins) prepared from these reactants are described in many references. These reaction products have been suggested as tackifiers in adhesives. Resole resins described by others (1-step resins) are mainly recommended for paints · Nowhere is the conversion of these two reactants has been proposed in the manner described in the present application, in which the inventive new resins are created.

It has been found that the reaction between formaldehyde and bisphenol A in the V / _s should be ise carried out by treating them with an alkali metal or Bariumhydroxydoder -oxyd catalyst mixed to obtain an initial mixture with a pH of about 8 to about 11. The resin is then treated with an acid in order to lower the pH of the resin solution to a value below about 8, preferably between about 3 and about 8, in particular between 5 and 8. Acids used with preference are mineral acids such as sulfuric acid, phosphoric acid, phosphorous acid and the like, carboxylic acids such as lactic acid, citric acid, acetic acid, trichloroacetic acid, honochloroacetic acid, oxalic acid and the like. The acids most preferred for neutralization are phosphoric acid, acidic acid, lactic acid and citric acid.

The initial mixture of Bis-A and formaldehyde is a Temperature carried out below the rapid condensation and the mixture is stirred to the condensation temperature brought. As a rule, the reaction temperature is at least 80 ° 0; the reaction is preferred carried out at about 90 to 100.degree. The temperature is

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preferably controlled in such a way that the reaction is carried out under reflux and it can be a reduced Pressure or atmospheric pressure can be applied · The implementation is continued until the desired degree of reaction is achieved, this can be about 30 minutes to 1 hour or longer last · In general, the degree of conversion is determined by the desired polydispersity. if once this degree of realization is reached, the product becomes cooled, neutralized with acid and then subjected to the application of heat and reduced pressure of water and unreacted Materials freed. These process steps are known per se.

In some cases, the stripped resin may contain unreacted formaldehyde. If the amount of unreacted formaldehyde results in an offensive odor during molding of the resin, it may be desirable to add a formaldehyde removal agent to the resin during its manufacture, before or after stripping, or as part of the molding material composition. The remover (cleaning agent) is any compound that can react with formaldehyde, such as amides, amines, and alcohols. Examples of suitable compounds are melamine, urea, n-butanol, sec-butanol, n-hexanol, polyvinyl alcohol, ethylene glycol, glycerol and the like. The amount of cleaning agent used can be within the range from 0 to 25% by weight , based on the weight of the resin, and it depends primarily on the amount of free formaldehyde present. In most cases, however, it is advisable not to use more than about 15% by weight of the aldehyde cleaner or aldehyde remover, based on the weight of the resin.

The resin obtained generally has a viscosity of no more than about 30 cSt at 25 ° C., determined by hand a 35 wt .-% solution in ethanol. A viscosity of 7 to 15 cSt at 25 ° C is suitable for most compounding and

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Deformation process is often preferred. These viscosities however, are essential to the practice of the invention not critical.

The resins of the invention are proportionate by one characterized by a narrow molecular weight distribution and a low molecular weight. For example, the "polydispersia" of these resins and is within the range of about 1.5 or slightly below to about 5 or less something about it. The polydispersity is preferably about 1.7 to about 3. The "polydispersity" here is the ratio the weight average molecular weight to the number average molecular weight. The resin is usually a mixture of dimers and primers and tetramers as the predominant components and has a methylol content that condenses during the hardening reaction can.

As is typical of thermoset resins, mixed with reinforcing materials (compounded) _l to improve the above physical strength properties. The filler materials can be in the form of non-fibrous particles and in the form of fibrous particles. They can be inorganic or organic and they can be a wide variety of materials, such as cotton fibers or fabric to glass fibers, from asbestos to wood flour, from a silicon dioxide filler to hydrated aluminum oxide, from sisal to ground nut shells (e.g. walnut shells), from carbon fibers to zirconium or boron fibers, from polypropylene fibers to polyvinyl alcohol fibers and the like. Boron fibers are used, for example, in amounts of up to about 50% by weight of the molding compound (molding compound). They are light in weight and increase strength. Carbon and graphite fibers are used in amounts up to about 50% by weight to achieve a high mechanical strength that is maintained even at high temperatures. In the case of asbestos, e.g. chrysotile, anthophyllite, grocidolite,

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Tremolite or octinolite asbestos, it is one • fibrous filler, · in amounts of. about -5 "to 50 % By weight, based on the weight of the molding compound, is used is used to improve strength and heat resistance. Fibrous alumina and zirconia fillers are used used in amounts up to about 60% by weight to improve physical properties, to achieve high Strength / weight ratio and to improve resistance at elevated temperatures. Are glass fibers particularly advantageously in amounts from about 30 to about 4-5 Wt .- / ■ £ to achieve high strength and durability to water, alcohols and other chemicals · Polyvinyl alcohol fibers are eminently suitable for the molding compositions according to the invention in amounts of about 10 to about 10 to about 1 / a 50% by weight to achieve exceptionally high impact strengths Cotton torn into pieces is beneficial, especially when the molded joint is used for such purposes which do not have notched Izod impact strengths greater than about 0.4-5 ft.-lbs./inch (0.024-5 mkg / cm) is required are.

Particulate fillers of the pigment and non-pigment type (i.e. those that color or not color) are highly desirable and include sand, quartz, triple silicon dioxide, diatomaceous earth, aluminum silicates (e.g. clays), mica, talc (magnesium silicate), modified novaculite, fumed colloidal silicon dioxide, nepheline, syenite, wollasto-. nit (calcium silicate), glass beads, kaolin clay, calcium carbonate, zinc oxide, aluminum oxide, magnesium oxide, titanium dioxide, beryllium oxide, barium sulfate, wood flour, liusc.helmehl, boron carbide, hollow carbon microbeads (microballoons), hollow phenolic resin microbeads (microballoons ^L ). These types of fillers are used in amounts of 2 to about 70% by weight, based on the weight of the molding compound.

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electrical properties in the molded resin, more specific Strength properties, impact resistance properties and the like, mixtures of these fillers are used. Regarding this see "SPE Journal", Vol. 28, No. 6, June 1972, pages 21-36, published by the Society of Plastics Engineers, Inc., 'Greenwich, Connecticut, USA. It also describes a wide variety of other additives, many of which can be used in the present invention, such as antioxidants, colorants, optical Brighteners, lubricants and ultraviolet absorbers. Before formulating into a molding compound, the resin can also Processing and shaping aids such as lubricants (e.g. stearic acid) can be added and / or they can may be added during the compounding (mixing) of the resin to form the molding composition and / or they may can be added both to the resin per se and to the molding composition. A tool that can be used during Oompounding Production of the molding compound can be added is calcium oxide and / or calcium hydroxide. Its job is the heat resistance properties (Heat stiffness properties) to improve the molded connection or the molding compound. Calcium oxide or calcium hydroxide can be used in amounts up to 11, preferably from about 2 to 7 wt .-%, based on the weight of the molding compound, be admitted. The combinations suitable for effective molding compositions according to the invention are innumerable and advantageous molding compositions are given in the examples below.

The compounding or mixing is carried out in the usual manner, but taking certain factors into account Need to become. If the production of a light-colored (light-colored) shaped body is desired, then should the reinforcement components should be light or faintly colored and they should not be any during the curing of the molding compound cause unwanted additional coloring. If the molding material is to be used for injection molding, then the viscosity of the resin for the molding process should

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- Ib-

If the molding material is to be used in transfer molding or injection molding, it is desirable that the compound have flow values of at least 38.1 cm (15 inches), and preferably no more than 114- cm (4- 5 inches), which are determined by the following method: the deformation behavior of the thermosetting resin composite is characterized by a flow test similar to that described by KE Hoffmann and EE Fiala in "Paper ZZIV-2 from the Annual Technical Conference of the Society of Plastics Engineers ", Volume 12, 1966, entitled" A Simple Earn Following Apparatus Applied to Spiral Flow of Plastic Holding Compounds ", but with the following modifications: (a) The cross-section of the flow channel is deceptive 0.518 cm x 0.952 cm (0.125 inches 0.375 inches); (b) the molding material is introduced in the form of a pre-heated to 121 ⁰ C preform into the device; (c) a mold temperature of 168 ° C is used; and (d) the compression pressure on the piston is 619 kg / cm (8800 psi). For the purposes of the present invention, the "deformability" of a thermosetting compound is characterized by the number of centimeters (inches) that the material can flow within the molding channel before it hardens (sets) under the test conditions. It has been empirically found that a test flow value of ^. 61.0 cm (24 inches) is required and that a test flow value of "> 4-517 cm φ18 inches is required in this test for good injection compression. Materials with spiral test flow values below 38.1 cm (15 inches) are generally only suitable for compression molding methods with less stringent requirements.

An advantageous property of the mold materials according to the invention or Fornn - ^. Ssen is that that ei? at flow temperatures of about 90 to about 125 ° 0 over a longer period of time x ^v \ ν_: ·. ^η . hinv / eg, at; :: -. iolsv / oise 1 hour or

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BATH ORIGINAL

more, can be held in the molding drum and in the casting channels without hardening, but when they are brought to the hardening temperature of, for example, about 175 ° ^C , they harden quickly to a hard or rigid product which is virtually free of deformation and mold shrinkage, which is at least 30% faster than a comparable 'M-stage' phenol-formaldehyde resin molding material which has been compounded in a similar manner.

Compounding or mixing can take place in the most varied of Devices, for example in a Banbury mixer, an extruder, a kneading device, a two or Three-roller mill and d ^ jl., To be carried out. It is for In practicing the invention, it is important that the components of the molding compound are intimately and thoroughly dispersed so that each part of them practically the has the same composition as any other part thereof.

One aspect of the resin of the present invention appears to have an anomaly in excellent heat resistance properties to be the moldings produced from the molding materials according to the invention. The resin of the present invention provides a Molding material that is fully cured after removal from the mold in rapid molding cycles, a high Has a heat distortion temperature of about "IJO C and the resin molded article made therefrom has electrical properties equivalent to those of can be obtained with most phenolic molding compositions, but when the molding is post-cured it is superior electrical properties. This suggests that the apparently cured molding that so many has excellent properties, not yet implemented Has Hethylolgruppen, which has the potential to achieve the optimal electrical properties adversely

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rivers. It is assumed that these "residual" groups condense as a result of the post-curing and that this has the effect that the electrical properties of the molded body are improved in such a significant manner. Post-curing can take place at temperatures which exceed the reaction temperature of the methylol groups. It is generally at least about 35 », preferably at least 9O ⁰ C. After the post cure, the molded body of the corapoundierten resin of the invention exceptionally good electrical properties, the best properties, with a shaped phenol-formaldehyde resin in a comparable manner compounded, are achievable, are at least equal.

The following examples are intended to explain the invention in more detail. but without limiting it to that. In the following examples, the composition of the molding compound is given in each case the process used to make the resin is given.

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example 1

composition Parts by weight, g Bisphenol Λ 6000 Formaldehyde (40 '/ »ig) 3000 Sodium hydroxide (25%) 72 Phosphoric acid (75%) - 18th water 18th procedure

6000 g (26.4 mol) of bisphenol A and 3000 g (40 mol) of a 40% strength aqueous formaldehyde solution are introduced into a reactor equipped with a condenser, a stirrer and a temperature recording device. The pH of the mixture was adjusted to 9.8 by adding 72 g (4.5 mol) of a 25% by weight aqueous sodium hydroxide solution. The mixture was then heated to 95 ° C. and kept at this temperature for one hour with stirring. The reaction mixture was then cooled to 55 ° C. and its pH was adjusted to 6.0 by adding an aqueous solution prepared by mixing 18 g of a 75% strength phosphoric acid solution with 18 g of water / was then subjected to a vacuum of 7 "I ₁ cm (28 inches) Hg at a temperature between 95 and 100 G and placed on a 150 ° C hotplate for 120 seconds. The resin was then transferred to coolers to immediately stop the condensation reactions. The molding compound obtained with this resin could not be cured.

Example 2

composition 409822/09 9 8 Parts by weight, R. BATH ORIGINAL Bisphenol A. 6OUU Formaldehyde (40 #) 90C0 Sodium hydroxide (25%) 72 Phosphoric acid (75 ') 18 " .. 'as. * 3 he 18th

procedure

In one with a cooler, a stirrer and a temperature recorder provided reactor were 6000 g (26.4 moles) of bisphenol A and 9000 g (120 moles) of one 40% strength by weight aqueous sormaldehyde solution was introduced. The pH of the mixture was determined by adding 72 g (4.5 mol) of a 25% strength by weight aqueous sodium hydroxide solution set to 9.5. The mixture was then at 95 ° heated and stirred for 1 hour at this temperature held door. The reaction mixture was then cooled to 55 ° C. and its pH was adjusted by adding a by mixing 18 g of a 75% phosphoric acid solution adjusted to 6.5 with Π8 g of water prepared aqueous solution. The contents of the reactor were then subjected to a vacuum of 71.1 cm (28 inches) Hg with the application of heat subject. At about 75 ° C. the viscosity of the resin became extremely high, so that the stirrer stopped. When increasing the temperature of 95 ° C turned the stirrer again, but it remained again because of the very high viscosity stand.

Example 3 Composition parts by weight, g

Bisphenol A 6000

Formaldehyde (40%) 5220

Barium hydroxide monohydrate 72

Phosphoric acid (87%) 18

Water 18

procedure

In one with a cooler, a stirrer and a temperature recorder equipped reactor

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6000 g (26.4 mol) of bisphenol A and 5220 g (69.6 mol) of a 40% strength by weight aqueous formaldehyde solution were introduced. The pH of the mixture was adjusted _{to 9 S} 2 by adding 72 g (0.38 mol) of barium hydroxide monohydrate.

The mixture was then heated to 95 ° C and under constant Stirring was held at this temperature for one hour. Thereafter, the reaction mixture was brought to a temperature of Cooled 55 ° C and their pH was by adding a by mixing 18 g of water with 18 g of an 87 wt .-% The aqueous solution prepared with an aqueous phosphoric acid solution was adjusted to 6. The contents of the reactor were taking Apply heat to a vacuum of 68.6 cm (27 inches) Hg. When the resin is heated to 90 to 100 ° C the stirrer remained at 70 ° 0 because of the very high viscosity of the resin. The resin was immediately transferred to coolers and its 150 ° C hot plate gel was 58 seconds.

Example 4

Composition parts by weight, κ bisphenol A 6000

Formaldehyde (40%) 5220

Potassium hydroxide (25%) 72

Phosphoric acid (87%) 18

Water '18

procedure

In one with a cooler, a stirrer and a temperature recorder equipped reactor was 6000 g (26.4 moles) of bisphenol A and 5220 g (69.60 moles) of one 40 wt .-% aqueous formaldehyde solution introduced. The pH of the mixture was adjusted by adding 72 g (0.32 mol) a 25% strength by weight aqueous potassium hydroxide solution to 9t3 set. Then the mixture was heated to 95 ° and with constant stirring for one hour at this temperature

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held. The reaction mixture was then cooled to a temperature of 55 ° C. and its pH was adjusted to 6.0 by adding an aqueous solution prepared by mixing 18 g of water with 18 g of an 87% aqueous phosphoric acid solution. The contents of the reactor were subjected to a vacuum of 68.6 cm (27 inches) Hg at a temperature between 98 and 110 ^{° C.} The resin was placed on a 150 ° C hot plate gel for 110 seconds and then it was transferred to coolers,

Example 5

Composition parts by weight, g bisphenol A 6000

Formalin (40%) 5220

Sodium hydroxide (25%) 72

Phosphoric acid . 18th

Water 18

procedure

In one with a cooler, a stirrer and a temperature drawing equipment equipped reactor 6000 g (26.4 mol) of Ms-A and 5220 g (69.60 mol) of a 40% strength by weight aqueous formaldehyde solution were introduced. The pH the mixture was made by adding 72 g (4.5 mol) a 25% strength by weight aqueous sodium hydroxide solution 9.5 set. The mixture was then heated to 95 ° C and kept at this temperature for one hour with stirring. The reaction mixture was then cooled to 55 ° G and its pH was determined by adding a solution by mixing 18 g of a 75% phosphoric acid solution with 18 g of water aqueous solution adjusted to 6.5.

The contents of the reactor was maintained at a temperature of between ⁰ · 95 and 100 G a vacuum of 71.1 cm (28 inches) Hg subjected, and adjusted to a 150 ° C-Heizplattengel of 190 seconds. The resin was then transferred to cooling devices.

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leads to stop the condensation reactions immediately. Example 6

Composition Wt% Bis-A-formaldehyde resin of Example 5 4-5.75 Zinc stearate 3.50 Behenic acid 0.75 Dibutyl phthalate 1.00 Calcium hydroxide 2.00 Asbestos (chrysotile) 18.50 Cellulosic filler 11.25 Titanium dioxide 10.00 Zinc oxide 7, oo Stearic acid 0.25

The ingredients, a total of 2500 g, were weighed out according to the above composition and mixed in a stone ball mill for 15 minutes. After 15 minutes of mixing, a 500 g-Gharge the starting mixture on a two-roll mill was added · The front roll at 88 to 95 ° O and the rear roller was maintained at 138-144 ⁰ C. The material was then formed into a film (sheet) and further compounded on the mill for 70 seconds. It was then removed from the rollers to cool and became stiff and granulated by grinding to the desired particle size. The granules were then mixed with the remainder of the starting mixture and rolled, cooled and ground in the same manner as described above.

Then the injection deformation period (margin) and the heat resistance (hot stiffness) tested. Shaker beakers made by molding under pressure were more than Subjected to the water vapor crack resistance test for 1 year. To date, the cups do not show any cracks.

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Injection deformation properties

Deformation period high temperature strength

86 minutes

5.4- cm (2 1/8 inches

The physical properties of moldings produced by injection molding are given below. the The deformation temperature was 171 C with a curing time of 90 seconds.

Notched Izod impact strength in mkg / cm (ft.-pounds / inch) notch (ASTM D 256)

Flexural strength in kg / cm (psi) (ASTM D 790)

Modulus of elasticity in kg / cm (psi) (ASTM D 790)

Bending work to break in mkg / cm ^ (ft.-lbs / inch ^) (ASTM D 790) _ung

maximum deflection / in cm (inches) (ASTM D 790)

Tensile strength in kg / cm (psi) (ASTM D 651)

Compressive strength in kg / cm (psi) (ASTM D 695)

Rockwell hardness E (ASTM D 785)

Heat distortion temperature (AJTLI D 64-8) 203 C "
Water absorption (ASTLI D 570) 0.89 %

0.0174- (0.32) 738 (10,500) 0.067.10 ° (0.95x10 °)

0.00795 (0.37) 0.365 (0.144) 575 (8170) 1850 (26,200)

Example 7

The procedure of Example 6 was repeated, this time producing a molding compound from the following ingredients became:

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composition % Bis-A-formaldehyde resin of Example 5 50.00 melamine 10.00 Calcium hydroxide 4.50 OaIcium Stearate 3.00 asbestos 18.00 Rejected pulp wool (pulp flakes) 6.00 Nigrosine 1.50 volume 7.00

100.00

The resulting molding compound had a flow value of 46.36 cm (18.25 inches), measured at 168 ° 0 using the flow method described above. The molding compound was molded by transfer molding with the formation of ΑΒΐΜ samples, which were cured for ^{2 minutes at a mold temperature of 168 to 171 0 O.} As indicated in the following table, the samples were post-baked for 8 hours post-cured at 177 ⁰ O, respectively, and compared with the first cured samples.

Tabel

ASTM cured in the as-molded post-process condition

Condition (8 hours at '177 ° 0)

Flexural strength in

kg / cm ² (psi) (D 79O) 710 (10100) 850 (12100)

Tensile strength in kg / cm

(psi) (D 651) 502 (7 140) 472 (6710)

Compressive strength in kg / cm

(psi) (D 695) 1890 (26900) 2025 (28800)

Notched Izod Impact Strength

in mkg / cm (ft.-lbs./inch)

Notch (D 256) 18.0 (330) 0.0174 (0.320)

Heat distortion temp. in

⁰ G ( ⁰ F) (I) 648) 232 (450) 254 (490)

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spec. Weight . (D 792) 1.46 1.4-3

• Rockwell hardness E (D 785) 69 80

dielectric strength S / T
in V / mm (mils) (D 149) 15.5 (395) 16.0 (406)

Light arc resistance

in sec. (D 495) 173 184

specific volume _{resistance Λο Λ} ~

stand in Ohmxcm (D 257) 9.3x10 ^ 2.9x10 ^{] d} dielectric constant (D I50)

60 Hz 10.1 5.5

1 EHz 8.1 5.2

1 UHz 5.7 4-, 5

Loss factor (D I50)

60 Hz 0.18 0.04

1 KHz 0.11 0.04

1 MHz 0.07 0.03

The following table shows a comparison between the effects when using short poly (vinyl alcohol) fibers (PV-OH), wood flour, pulp rejects wool and asbestos floating bodies as an impact-resistant agent for the bisphenol A-formaldehyde resin of Example 5 were obtained. The fibers and fillers used are listed below Table given together with the strength properties of the moldings:

Tabel

Moldings

Filler system in% by weight A BG

Wood flour - - 23

Rejected pulp wool ■ 8

Asbestos float -30-

PV-OH fibers (0.01 cm (1/25 inch),

6 denier) - 20

Notched Izod impact strength in mkg / cm

(ft.-lbs./inch). 0.087 0.0191 0.0136

(1.6) (0.35) (0.25)

Ball drop impact strength in cm 102 38.1 35.6

(inches) (40) (I5) (14)

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The molding latitude given above was determined by introducing the molding compound into the barrel of a reciprocating screw injection molding machine while it was in the plasticized state and following a series of "increasing delay times between injection deformations" The maximum delay time in which the screw still reaches the bottom within the liner within a period of 30 seconds (bottoming) is given as the injection deformation period (margin), expressed by the dwell time in the liner. heat stiffness) in the W _e determined ise that produced a test molding and immediately placed horizontally on a vertical rod and the deflection of the thus-arranged portion was measured. the spray deformation temperature strength is expressed as the deflection in cm (inches) of the part relative to the horizontal The water vapor crack resistance ise accuracy was measured in the W _e in that the beaker (diameter 17.8 cm χ 7.6 cm (7 inches produced by pressure deformation χ 3 inches) χ thickness of 0.64 cm (1/4 inches) is formed, wherein 165 to 177 ° C with a curing time of 60 to 120 seconds and 72 hours "conditioned at 22 ° G and 50% relative humidity) was placed over a jet of water vapor, with cool air flowing onto the outer surface so that the water vapor with the inside of the cup came into contact. The water vapor cracking resistance was determined as the time taken for visible cracks to form in the cup.

Claims ι

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Claims (1)

Claims 1. Thermosetting molding compound with an excellent Deformation period or scope, a low degree of mold shrinkage, a high modulus at elevated temperatures, a low degree of deformation at elevated temperatures, an excellent resistance to water vapor cracking and excellent electrical properties characterized in that it consists of about 20 to about 70 wt% of a bisphenol A formaldehyde resin and to about 30 to about 80 wt .- / &, each based on weight the molding compound, of a reinforcing filler for the resin, the resin being the thermosetting 1-stage resin reaction product of formaldehyde and bisphenol A in a molar ratio of about 2 to about 3 »75 in the presence an alkali metal hydroxide or barium hydroxide condensation catalyst having a pH of from about 3 to about 8 and the reinforcing filler around a particulate Solid is that after mixing with the resin and after curing to improve at least one of the the following properties of the molded body produced from it contributes: tensile strength, tensile modulus, notched Izod impact strength, Flexural strength and flexural modulus. 2. Thermosetting 1-step resin reaction product of formaldehyde and bisphenol A, characterized in that it is composed of formaldehyde and bisphenol A in a molar ratio of about afcis about 3i75 in the presence of an alkali metal hydroxide or barium hydroxide catalyst and has a pH adjusted to about 3 to about 8 has been. 3. Process for the production of moldings by injection molding in a screw injection molding device, consisting of an injection molding machine and associated Y / arm injection channels and a form associated with these, in which 409822/0998 the molding compound is introduced into the injection molding machine and kept at an elevated temperature which is sufficient, in order to keep the molding compound in the plastic state, the plastic molding compound is extruded into the V / arm injection channel and is maintained at a temperature below that of the mold, but which is sufficient to make the molding compound flowable and to keep plastic, and the molding compound is transferred from the hot runner into the mold in which the molding compound is used Curing is heated and deformed into a solid shaped body which is removed from the mold, characterized in that that the molding compound used is one which consists of about 20 to about 70% by weight of a bisphenol A-formaldehyde resin and about 30 to about 80 weight percent, each based on the weight of the molding compound, made of a reinforcing filler for the resin, the resin being the thermosetting 1-step resin reaction product of formaldehyde and bisphenol A in a molar ratio of from about 2 to about 3.75 in the presence of an alkali metal hydroxide or barium hydroxide condensation catalyst with a pH of about 3 to about 8 and the reinforcing filler by one particulate solid acts, which after mixing with the resin and after its hardening to improve at least contributes one of the following properties of the molded article produced from it: tensile strength, tensile modulus, notched Izod impact strength, Flexural strength and flexural modulus. 4. Process for the production of moldings by injection molding in a screw injection molding device and a mold connected to the injection molding device, in which the molding compound is introduced into the injection molding machine and held at an elevated temperature which is sufficient, in order to keep the molding compound in the plastic state, the plastic molding compound is extruded into the mold, the molding compound is introduced into the mold, in which it is heated to harden and molded into a solid molded body, the is removed from the mold, characterized in that 409822/0998 the molding compound used is one which consists of about 20% to about 70% by weight of a bisphenol A-formaldehyde resin and to about 30 to about 80% by weight, based in each case on the weight of the molding compound, of a reinforcing filler for the resin, the resin being the thermosetting 1- ^ step resin reaction product of formaldehyde and Bisphenol A in a molar ratio of about 2 to about 3.75 in the presence of an alkali metal hydroxide or barium hydroxide condensation catalyst having a pH of from about 3 to about 8 and the reinforcing filler around a particulate Solid is that after mixing with the resin and after its. Hardening to improve at least one of the following properties of the molded article produced therefrom is: tensile strength, tensile modulus, notched Izod impact strength, Flexural strength and flexural modulus. 5. Molding composition according to claim 1, characterized in that it contains a fibrous filler material. 6. Molding composition according to claim 5, characterized in that it is used as a fibrous filler glass fibers, asbestos fibers, polyvinyl alcohol fibers, Contains cellulose fibers or a mixture thereof. 7. Molding compound according to claim 1, characterized in that it additionally contains calcium hydroxide or calcium oxide. 8. Molding composition according to claim 1, characterized in that it has a pH of about -5 to about 8, which is through Adding an acid to the resin has been adjusted. 9. Molding composition according to claim 8, characterized in that phosphoric acid has been added to it. 10. The method according to claim 3, characterized in that the molded body removed from the mold is post-cured 409822/0998 11. Molding composition according to claim 1, characterized in that it additionally contains a lubricant. 12. Molding composition according to claim 11, characterized in that it is used as a lubricant stearic acid or a metal stearate contains, 1Y. Molding compound according to claim 1, characterized in that that it additionally contains ultraviolet light stabilizers and / or antioxidants. A method of deforming materials containing a thermosetting resin, in which the material is heated and maintained at a temperature which maintains the material in a plastic and flowable state, but which is below the temperature at which the resin is thermally cured thereby characterized in that the material used is a molding compound which consists of about 20 to about 70% by weight of a bisphenol A-formaldehyde resin and about 30 to about 80% by weight, each based on the weight of the molding compound, a reinforcing filler for the resin, the resin being the thermosetting 1-stage resin reaction product of formaldehyde and bisphenol A in a molar ratio of about 2 to about 3.75 in the presence of an alkali metal hydroxide or barium hydroxide condensation catalyst having a pH of about 3 *> is about 8 and the reinforcing filler is a particulate solid which, after mixing with the resin and after it has cured, e.g. To improve at least one of the following properties of the molded body produced therefrom is: tensile strength, tensile modulus, notched Izod impact strength, flexural strength and flexural modulus. Method according to claim 1A, characterized in that that the molded body removed from the mold is post-hardened will. 409822/0998 16. The method according to claim 4, characterized ^ ekennzoicanoi :, dc.ß the out of the form jonoL-uene IPormkürpo;: · n ^ cli ^ c— hart at v; ird. AO 9 82 2/0998 BATH ORIGINAL