DE1779748A1 - Use of thermoplastic polyarylene polyethers with at least one layer of a fiber material for molding tools and processes for producing these tools - Google Patents

Description

Use of thermoplastic polyarylene polyethers with at least a layer of a fiber material for molding tools and methods of manufacture these tools.

The invention relates to the use of thermoplastic Polyarylene polyethers with at least one layer of a fiber material for molding tools for the molding of polymeric materials molding tools, in particular printing plates, which are made from consist of a fibrous carrier and a thermosetting synthetic resin binder, are described in U.S. Patents 2,278,291 and 2,509,499; In the preparation of however, various difficulties have arisen from molded articles with these molds There was such a problem, for example, in poor reproduction in particular if there are fine halftone dots te with 1 120 Grid lines every 2.5 cm or more where it is difficult to flatten enough depth into the shadow This is due to the non-homogeneous nature of the printing plates in general and in particular attributable to fiber shear during the manufacture of a die. Another one The problem is dimensional instability due to moisture in the panels. The moisture also causes a plate (foil) in different directions inconsistently shrinks during the manufacture of a die, resulting in a poor one Reproduction of the original leads. Furthermore, the shrinkage of the plate varies to plate, making color overlay between plates of a set difficult power.

The use of a thermosetting binder for the fiber-containing Trager requires undesirably long curing processes.

Insufficient curing of the thermosetting resin causes a Gluing the die surface, which shortens the useful life of the die. Since the thermosetting binder is hardened in an unsmeltable state, the die cannot be reused to produce other dies.

Thermoplastic materials produced by conventional methods are usually not suitable for use as a molding tool, as they usually do during the deformation occurring elevated temperatures a poor thermal and have dimensional stability. It was found that the maximum temperature for the actual use of a thermoplastic material as Formé tool under normal deformation conditions about 22 - 28 ° below the Glass transition temperature of a polymer is. In the case of high-quality polymers, like a polycarbonate resin with a glass transition temperature of 150 °, the maximum use temperature about 121. Deteriorated at temperatures above 1210 The tensile modulus and tensile strength of the polycarbonate rapidly, which this resin unsuitable for use as a molding tool at deformation temperatures above about 121 ° power.

The object of the invention is therefore to create molds for Forming of polymeric materials, o ie in particular for the production of printing plates and records made of polymeric material are suitable and the above-mentioned disadvantages the previously known molds do not have for this purpose. According to the invention The forming tools used should be an excellent reproduction of an original, including fine halftone halftone dots. the molding tools used have a satisfactory dimensional stability, i.e. problems arising from inconsistent shrinkage and throwing avoided will. Furthermore, there are long curing processes and sticking of the mold surface avoided.

The invention relates to the use of thermoplastic Polyarylene polyethers with at least one layer of a fiber material, vorzugsw @ ise made of glass fibers, as molding tools for Forms of polymeric substances, the thickness of the thermoplastic polyarylene polyether on the surfaces of the composite foil is thicker than the deepest, while making one Forming tool indentation. The molding tool according to the invention shows a uniform deformation shrinkage in all directions of 0.5% and less thermally stable and dimensionally stable at deformation temperatures of up to 177 ° and re-deformable. The deformation shrinkage is, as indicated above, a special one Problem with thermosetting fiber reinforced plastic sheets.

; In the case of matrices made from these plastic sheets, there is deformation shrinkage insoluble in different directions, and this insolvency varies biun to a Lewis La # from die to die. Some deformation shrinkage, i.e. the size reduction of an iiatrize compared to the original template, after the die has been made from it, it can be in the order of magnitude up to 0.5 %% are tolerated; However, it is essential and extremely useful that the deformation shrinkage of Die to die is uniform and uniform for each die in all directions is.

The matrix according to the invention has this property. She delivers a true reproduction of the original template with a tolerable, uniform Reduction in size which is the same from male to female. Well-known matrices do not even come close to showing this uniformity.

A special feature of the atrize according to the invention is theirs Deformability. It takes place by creating a first die, or a film of the thermoplastic Polyarylene polyether with a first template in contact and warmth and Apply pressure, then make a second die, indel the back the first catheter brings into contact with a second original and warm and Applying pressure. In this process, the first die is deleted and formed a smooth back for the second ila-trize. This procedure can be repeated multiple times like @recovered are used to produce two, three, four or more different or identical ones Ilatrices made from the same sheet of thermoplastic polyarylene polyether. The thermoplastic Polyarylene polyethers in film form, which are shaped into the matrices according to the invention are linear thermoplastic reaction products of an alkali metal double salt a dihydric phenol with a dihalobenzoid compound.

The polymer has a basic structure made up of the following recurring Units: -O-E-O-E'-in which E stands for the remainder of the dihydric phenol and E ' for the rest of the benzenoid compound (iryl compound) with an inert electron withdrawing group in at least one of the or p positions to the valence compounds are and both radicals are valent through aromatic carbon atoms to the ether oxygen atoms are bound.

The @est E of the dihydric phenol can z. @. nuclear phenylene group from @ydroquinone and resorcinol, or it can be a two or polynuclear residue be. It can also be used with other, inert nuclear substituents, such as stalogen-, Alkyl, alkoxy, etc., be substituted.

The dihydric phenol is preferably a weakly acidic dinuclear one Phenol, such as the Dioxydiphenylakane or the nuclear halogenated derivatives thereof, commonly known as "bisphenols" - such as 2,2-bis (4-oxyphenyl) propane, 1, 1-bis- (4-oxyphenyl) -2-phenylethane, bis- (4-oxy-piienyl) methane, or the Chlorinated derivatives with one or two chlorine atoms on each aromatic ring. Other suitable, dinuclear dihydric phenols are the bisphenols with a symmetrical one or unbalanced O linking group, such as e.g. B. oxygen (-O-), carbonyl (-C-), Sulphide (-S), sulphone (-SO2-) or a hydrocarbon radical in which the two phenolic nuclei on the same or different carbon atoms of the remainder bound, such as the bisphenol of acetophenone, the bisphenol of benzophenone, the bisphenol of vinylcyclohexene, the bisphenol of α-pinene and similar bisphenols, in which the uxyphenyl groups are attached to the same or different carbon atoms an orange, linking group.

Such dinuclear phenols have the following structure in which Ar stands for an aromatic group, preferably a phenylene group, e and Y 'can be identical or different inert substituent groups, such as alkyl groups with 1 to 4 carbon atoms, halogen atoms, e.g. fluorine, chlorine, bromine or iodine, or alkoxy groups with 1- 4 carbon atoms; r and z are integers with a value from 0 to 4, and R stands for a bond between aromatic carbon atoms, as in Dioxydi @ i @ nyl, or for a divalent radical including all inorganic radicals, how -SO2- uni divalent organic hydrocarbon radicals, such as alkylene-alkylidene, cycloaliphatic radicals or the halogen, alkyl. aryl-substituted alkylene, alkylidene and cycloaliphatic radicals and also alkalicyclic, alkarylene and aromatic radicals and a ring fused to both Ar groups. special divalent polynuclear phenols include: the bis (oxyphenyl) alkanes, such as 2,2-bis (4-oxyphenyl) propane, 2,4'-dioxydiphenylmethane, bis (2-oxyphenyl) methane, sis- (4-oxyphenyl) methane, bis (4-oxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,1-bis (4-oxyphenyl) ethane, 1,2-bis (4 oxyphenyl) ethane, 1,1-bis (4-oxy-2-chlorophenyl) ethane, 1 1 1-bis (3-methyl-4-pxyphenyl) propane, 1,3-bis (3 -methyl-4-oxyphenyl) -propane, 2,2-bis- (3-phenyl-4-oxyphenyl) -propane, 2,2-bis- (3-isopropyl-4-oxyphenyl) -propane, 2,2- Bis- (2-isopropyl-4-oxyphenyl) -propane, 2,2-bis- (4-oxynaphthyl) -propane, 2,2-3-is- (4-oxyphenyl) -pentane, 3,3-bis- (4-oxyphenyl) pentane, 2 2,2-bis- (4-oxyphenyl) -heptane, bis- (4-oxyphenyl) phenylmethane, 2,2-bis- (4-oxyphenyl) -1-phenylpropane, 2, 2-bis (4.-oxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc .; Di- (oxyphenyl) -sulfones such as bis- (4-oxyphenyl) -sulfone, 2,4'-dioxydiphenylsulfone, 5'-chloro-2, 4'-dioxydiphenylsulfone, 5'-chloro-4,4'-dioxydiphenylsulfone, etc. .; Di (oxyphenyl) ethers, such as bis (4-oxyphenyl) ethers, the 4,3 ', 4,2', 2,2 ', 2,3'-dioxydiphenyl ethers, 4,4'-dioxy-2 , 6-dimethyldiphenyl ether, bis (4-oxy-3-isobutylphenyl) ether, iBis (4-oxy-3-isopropylphenyl) ether, bis (4-oxy-3-chlorophenyl) ether, bis ( 4-oxy-3-fluorophenyl) ether, bis (4-oxy-3-bromophenyl) ether, bis (4-oxynaphthyl) ether, bis (4-oxy-3-chloronaphthyl) ether, 4 , 4'-dioxy-3, 6-dimethoxydiphenyl ether, 4,4'-dioxy-2, 5-diethoxydiphenyl ether, etc.

Mixtures of two or more different, bivalent ones can also be used Phenols are used0 The radical E in the above-mentioned polymer structure can therefore stand for the same or different aromatic radicals.

The term "remainder" used here to define the remainder E of the dihydric phenol "refers to the R £ -'st of the dihydric phenol after Removal of the two aromatic hydroxyl groups. It can therefore be seen that Polyarylene polyether repeating groups of the remainder of the dihydric phenol and the remainder of the benzene compound contained by bonds of aromatic Ether atoms are connected to each other.

The group E 'of the benzene compound can be derived from any dihalobenzoid compound or mixture of dihalobenzoid compounds stam @ en that have two halogen atoms bonded to benzene rings, one that withdraws electrons Have group in at least one of the o- or p-positions to the halogen group. The dihalobenzoid compound can be mononuclear where the halogen atoms are attached to the same Benzenoid ring are bound, or polynuclear, o they are bound to different benzenoid rings are bound as long as there is an activating, electron leaving group in the o- or p-position of this benzenoid nucleus.

The halogen atoms can have any reactive halogen substituents be on the benzenoid compounds, with fluorine- and chlorine-substituted benzenoid materials preferred.

Any electron withdrawing group can be used as an activator group in the dihalobenzoid compounds0 The strongly activating groups, such as the sulfone group, are preferred which connects two halogen-substituted 3enzenoid nuclei, such as in 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodipnenylsulfone, although other strongly withdrawing groups, as mentioned below, can also be used.

It is also preferred that the ring do not donate electrons Contains groups on the same benzenoid nucleus as the halogen atom, although the presence other groups on the core or in the rest of the compound can be tolerated, Preferably all of the substituents on the benzenoid nuclei are either hydrogen atoms (i.e. that do not withdraw any electrons) or other groups with a positive sigma * value, see J.F.Bunnet in Chem. Rev. 49, 277 (1951) and Quart.Rev. 12, 1 (1958).

The electron withdrawing group of the dihalobenzene compound can either be through the resonance of the aromatic ring as represented by such groups with a high sigma * value, i.e. above about +0.7, or by induction, act like in perfluorocompounds or similar electron traps ("sinks").

The activating group should preferably have a high sigma * value, preferably above -1.0, although sufficient activation is determined even in groups with a sigma * value above 0.7. The activating group can in principle consist of one of the following two Types consist of (a) monovalent groups, such as activating one or more ealogenates on the same ring, such as a nitro group, phenyl sulfone or alkyl sulfone, cyano, trifluoromethyl, nitroso and hetero nitrogen, as in pyridine, (b) divalent groups that have a replacement of halogen atoms activate two different rings, like the sulfone group 0 tr left I1 OO the carbonyl group-C-; the vinyl group -0 = 0 =; the bulE'oxyd- 1 H II group -5-; the azo group -N = I {-; the gods of Iluorohlen- substance groups -CF2CF2-; organic phosphine oxides; and the where R is a hydrocarbon group, ethylidene group in which X represents a hydrogen or halogen atom; or activate the @alogenatoms on the same ring, as for example with difluorobenzoquinone, 1,4-; 1,5- or 1,8-difluoroanthraquinone.

Optionally, the polymers with Tiischungen of two or more dihalobenzoid compounds, each of which has this structure and which are different, Electron withdrawing groups can be made. so can the rest E 'of the benzenoid compounds in the polymer structure are identical or different be.

From what has been said above, it is apparent that linear thermoplastic polyarylene polyethers are preferred in which E is the residue of a dinuclear dihydric phenol and E 'is the residue of a dinuclear benzene compound. These preferred polymers contain the following repeating units: in which R stands for a bond between aromatic carbon atoms or a divalent connecting radical and R 'stands for a sulfone, carbonyl, vinyl, sulfoxide, hydrogen, saturated fluorocarbon, organic phosphine oxide and ethylidene group; Y and Y 'stand for inert substituent groups such as halogen atoms, alkyl groups with 1-4 carbon atoms and alkoxy groups with 1-4 carbon atoms, and r and z are integers with a value of 0 to 40. Particularly preferred are the thermoplastic polyarylene polyethers of the above formula, in which r and z are ITull, R for a divalent connecting remainder where R "represents a hydrogen atom, a lower alkyl group, a lower aryl group, and the halogen-substituted groups thereof; and R 'is a sulfone group.

The thermoplastic polyarylene polyethers intended for the use of molding tools are characterized by high molecular weights, which is indicated by a reduced viscosity in specified solvents. According to the invention, it is preferred that the thermoplastic polyarylene polyethers have a reduced viscosity above about 0.35, in particular above about 0.4. The method for determining the reduced viscosity is described below. Films of thermoplastic polyarylene polyether used for Verse are suitable in the slatrize according to the invention can be produced by the methods known for the production of thermoplastic materials, extrusion, compression molding, injection molding, casting from the solution, etc. The thickness of the foils used is not critical, but is primarily determined by practical considerations such as cost and ease of manufacture. In general, suitable thicknesses for thermoplastic polyarylene polyether films are between about 0.75 mm to about 6 mm, although thicknesses between about 2-3 mm are preferred.

As indicated above, the die according to the invention is composed of a composite Film material made of a fiber-reinforced thermoplastic polyarylene polyether with the proviso that the thickness of the thermoplastic polyarylene polyether on the surfaces of the composite film is thicker than the deepest indentation, which takes place during the production of a die. Any fiber reinforcing material can be used for this purpose Material to be used. Sole reinforcements are z. B. woven and non-woven fibrous fabrics, fiber mats, nonwovens, continuous fibrous threads and Strands, etc. Also fiberglass, especially in the form of a thin mat or one woven fabric has been found to be suitable. The use of a fiber reinforcement increases the strength of a die and thus extends and reduces its service life the uniform deformation shrinkage to an order of magnitude of only 0.1%.

Optionally, one or more layers of the same or one different fiber reinforcements can be used. that the fiber reinforcement used is sufficiently porous or open to a complete Impregnation of the same by the thermoplastic polyarylene polyether during the Allow production of the foil and die.

A composite solid, through one or more layers of fiber reinforcement bonded between layers of a thermoplastic material can be conveniently made by adding an intermediate layer of fiber reinforcement between two sheets of thermoplastic polyarylene polyether places and heat and Pressure applies to the layers into a single composite, fiber-reinforced Bring slide. A composite sheet with two or more layers of fiber reinforcement can be made by making a film or a thin in a similar manner Laying film of thermoplastic polyarylene polyether between fiber layers, then the so produced to "sandwich" structure between two layers of the thermoplastic Polyarylene polyether brings and applies heat and pressure to the layers into one single, composite, fiber-reinforced film. Others can too Processes are used such as extrusion and joining of two foils of the, thermoplastic polyarylene polyether, whereby one prior to the joining of the films interposing a layer of fiber reinforcement O Other methods of manufacture a composite film to ensure that'the thickness of the thermoplastic Polyarylene polyethers are thicker on the surfaces of the composite film as the deepest indentations made during the manufacture of a die are that Known to those skilled in the art. Suitable thicknesses for the composite film are the same Range as specified for a film of the polyarylene polyether.

The template according to the invention is usually produced by a composite film of the thermoplastic polyarylene polyether described herein brings it into contact with an original plate or template, applies heat and pressure, The die and the original are separated and the die is allowed to cool. This makes an excellent one Reproduction of the original preserved in the die, against the real copies of the original can be deformed in the manner described below.

The temperature at which a die can be produced is not very crucial. Obviously the lowest temperature is the one at which the polymer can be deformed under pressure, and the highest temperature lies below the decomposition temperature of the polymer or the softening point of the original. Temperatures between 213 - 2880, preferably between 218 - 2460, correspond to these practical considerations for the thermoplastic polyarylene polyether. Matrices can be made from unframed copper originals at temperatures of 213 - 2880, made of zinc and magnesium originals at temperatures of 218 - 2460 and made of type metal, like a "Linotype" metal that softens under pressure at 2270 at temperatures from 218-2240.

The deformation pressure can vary within wide limits. Suitable prints are between 14 to 70 kp / cm2, preferably between 217.5 to 35 kp / cm2.

Specific examples of suitable manufacturing processes for one according to the invention Die are in the examples. specified.

As indicated above, the die according to the invention is uniform Deformation shrinkage in all directions and due to thermal and dimensional stability marked at deformation temperatures up to 1770. In general it has been found that the foils of thermoplastic polyarylene polyether described here are deformed shrink into a die on the order of about 0.1-0.5%. This The range is within the limits of a shrinkage of 0.5 ffi for dies used to produce duplicate printing plate parts will. It is noted that a unique feature of the die according to the invention lies in that the amount of shrinkage for any die made from sheets of a thermoplastic Polyarylene polyethers with the same properties, e.g. the same reduced viscosity, is the same, d. H. it eats consistently and consistently in from slide to slide all directions within each slide. This feature makes it for a die maker possible to rely on a uniformly recurring degree of shrinkage for a given Leave polymer formulation and so constant, superior overall results to achieve.

The die according to the invention thus offers the versatility of thermoplastics Materials and still holds the harsh conditions when deforming a die without the usual with thermosetting plastics occurring problems appear.

The polymeric material used to make printing plates, etc. against the die according to the invention can be deformed, a thermoplastic thermosetting, be natural or synthetic polymeric material. In general, anyone can normally solid polymeric material that is raised by the application of pressure and heat can be deformed or cured to about 1770, against the inventive Die are deformed.

Suitable thermoplastic materials include natural and synthetic Rubbers, polyolefins such as polyethylene and polypropylene, polyvinylidene chloride, Polyvinyls, polystyrene, polyethers, polyacrylates, polymethacrylates, polyamides, polycarbonates, Polyoxyethers, polyoxymethylenes, copolymers and mixtures thereof, etc.

Suitable thermosetting resins include phenol-aldehyde polymers, Urea-aldehyde polymers, melamine-aldehyde polymers, epoxy resins, polyester, Copolymers and mixtures thereof, etc.

The polymeric materials to be deformed with the die according to the invention the known additives, such as fillers, dyes, pigments, crosslinking agents, Curing agents, stabilizers, plasticizers, preservatives, lubricants, Anti-oxidation agents, etc., are included. You should use a solvent or Jedoc * contain other materials that are thermoplastic Polyarylene polyether matrix attack. This class includes aromatic and chlorinated solvents. In general Any polymeric material that is inert to the idatricity can be deformed.

The die according to the invention usually separates without aids to detach from the form of an original or the object to be molded. Possibly however, such tools can be used to detach them from the mold for easier separation can be used by the die and the original or the object to be manufactured. The usage Such release agents have proven to be useful in crosslinked molded articles polymeric materials such as epoxy resins and rubbers. Suitable tools for Detaching from the form are graphite, molybdenum disulfide, silicone oils, etc. The use of solvents or auxiliaries that attack the matrix material be avoided.

The following examples illustrate the present invention, without restricting them.

The polyarylene polyether used for the matrices or molding tools has the following basic structure: Example 1 The thermoplastic polyarylene polyethers with a reduced viscosity of 0.49 were extruded into a film 1.8 mm thick. Two sheets measuring 20 × 20 cm were cut from the film and placed on top of one another with a 2.25 mm thick layer of fiberglass in between. This sandwich material was placed in an electrically heated hydraulic press and preheated to 3000 for 5 minutes without pressure with the press platens closed. A pressure of 35 kg / cm 2 was then applied for 2 minutes in order to compress the layers into a sheet material made of a layer of fiberglass between two layers of the thermoplastic polyarylene polyether. The sheet material was removed from the press and allowed to cool; it was 3.8 mm thick and the material on the surfaces consisted entirely of thermoplastic polyarylene polyether.

The composite foil was made with a copper original relief printing plate, which was coated with a silica oil for easier dissolution, brought into contact and placed in an electrically heated hydraulic press with a 10 cm punch. The plate and original were opened for 1.5 minutes without pressure with closed press plates 2430 preheated then the die was by 1 minute long application of 35 kp / cm2 pressure produced. The temperature was reduced to 930 and original and Die removed and cooled to room temperature.

The reproduction was excellent and the shrinkage was 0.4% uniform in all directions. An intimate mixture of a polyoxyether of the following structure: and 5% by weight of a rubber made from 95% butadiene and 5% styrene was molded against the die produced in the described press0 The die and the polymer mixture in contact were preheated to 1490 for 3 minutes without pressure with the press plates closed0 The duplicate printing plates were then heated for 30 seconds at 65, Deformed 45 kgf / cm2 Reproduction was excellent and the die showed no thermal or dimensional deterioration.

Example 2 Four layers of 0.25 mm thick thermoplastic film Polyarylene polyethers with a reduced viscosity of 0.49 were alternated brought together with three layers of non-woven fiberglass mat 2.39 mm thick. The alternating layers were then woven between two layers of one Fiberglass mat of 0.78 mm thickness was placed, and this sandwich material was then between two 20 x 20 x 0.075 cm sheets of a thermoplastic polyarylene polyether laid with a reduced viscosity of 0.49. This composite was then molded into a composite sheet as in Example 1. The sheet obtained was 3.2mm thick and consisted of five layers of fiberglass mat reinforcement between Layers of thermoplastic polyarylene polyether.

The composite foil was sealed against a copper master as in Example 1 deformed by a die. The reproduction was excellent and the shrinkage less than 0.1% uniform in all directions. A duplicate disk was successfully deformed against the Isiatrize as in Example 1 The reproduction was excellent and the die showed no thermal or dimensional change, Example 3 Example 1 was repeated using a layer of non-woven glass fiber mat of 2.39 mm thick as reinforcement and 2.08 mm thick sheets of the thermoplastic Polyarylene polyethers were used. The composite film was 4.1 mm thick; a die made therefrom shrank uniformly by 0.2 in all directions . A duplicate plate was successfully deformed against the die. The results were the same as in Example 1

Claims (4)

Patent claims lo use of thermoplastic polyarylene polyethers with at least one layer made of a fiber material, preferably made of glass fibers, as molding tools for molding polymeric fabrics, the thickness of the thermoplastic Polyarylene polyether on the surfaces of the composite film is thicker than the deepest indentation made during the manufacture of a mold 6 2. Use of polyarylene polyethers according to claim 1, characterized in that that the polyarylene polyether consists of recurring units of the formula (0 - E - 0 - E '-), where E is the residue of a dihydric phenol and E' is the residue of an aryl compound mean, the an inert, electron withdrawing, ending group in at least one of the has o- or p-positions to the bonds, which the two radicals via aromatic Connect carbon atoms with the ether oxygen atoms. 3. Use of polyarylene polyethers according to claim 1, characterized in that the polyarylene polyether consists of recurring units of the formula: where R is a bond between aromatic carbon atoms or a divalent connecting radical, R 'is a sulfone, carbonyi, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphinoxide or ethylidene group, Y and YI are each inert substituents, such as halogen atoms, alkyl group having 1 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms, and r and z are integers each having a value of 0 to 4. 4. Process for the production of at least two molding tools a single film of a thermoplastic polyarylene polyether, characterized in that that the film is brought into contact with a first template and to form one first mold applies heat and pressure, whereupon the back of the first mold brought into contact with a second template and applied heat and pressure, in order to produce a second molding tool.