The method of manufacturing of plastic parts, in particular fittings polyurethane

 

(57) Abstract:

The invention relates to the manufacture of plastic parts using a form, the inner surface of which is wholly or partly made of steel. A method of manufacturing polyurethane products in the forms, the inner surface made of tool steel, containing components in the following ratio, wt.%: at least one element from the group comprising tungsten, molybdenum and vanadium content of tungsten, from 0 to 40 wt.%, molybdenum from 0 to 12 wt.% and vanadium from 0 to 5 weight. %; at least one element from the group including chromium and aluminum with a chromium content of from 1 to 6 wt.% and aluminum from 0 to 15 wt.%, iron rest. If necessary, the steel contains carbon from 0.1 to 1.5 wt.%, cobalt from 0.1 to 10 wt.% and nitrogen in the nitrided layer from 0 to 10 wt.%. The technical result of the invention is the separation of the product from the mold without the use of internal lubricants. 2 C.p. f-crystals.

The invention relates to an improved method of manufacture of plastic parts, in particular molding of polyurethane, and use the device for the manufacture of shaped parts made of polyurethane, vnutrenestey, in particular, products from polyurethane, according to the prior art known to the application of grease to separate the product from the mold. As lubricants use polishes, silicone or soap, soluble/dispergirovaniya in water and/or organic solvents. For a long time the aim of the development was the reduction in the use or complete elimination of lubrication. For this there are a number of reasons, well-known specialist:

the cost of lubricants

time and the lengthening of the cycle due to the separation

precautions when using a lubricant (aerosol)

the cost of subsequent removal of grease by way of "washing jet under pressure" or sandblasted and so on.

Many proposed so far solutions aimed at application of the so-called internal lubricants, which (pre -) is injected into the plastic mixture prior to its injection into the mold and which should provide improved dispersion effect. Using the selected artificial materials made of polyurethane have made some improvements. Known application of internal lubricants (Oertel (publisher), Kunststoffhandbuch I. VII. Polyurethanes, published by Hanser). Here also it is often necessary to maintain vnutrennego, for example, a varnish coating. Internal lubrication under certain circumstances can also be identified and reduced, thus, the useful properties over time. On the other hand, there are cases when you cannot use the internal lubrication, for example, when the metal tabs, which should provide strong adhesion, for example foamed metal rails of the wheel.

The prior art known to use devices for processing pressure nitrogen tool steel with the following ratio of components (in wt.%):

Nitrogen - 0.4

Vanadium - 1,6-15

at least one element selected from the group including

Tungsten - 0-20

Molybdenum - 0-10

Chrome - 0-15

Cobalt - 0-15 assuming 0,2+0,2 V+N0,5+0,2 V

Iron - Rest

If necessary, the steel may contain 0-3% Nickel (see patent GB 1583878, With 22 38/12, published 04.02.1981).

Also known proposals for improvement of material forms. From the works of according K. Menges and others, among which (Kunststofftechnik 13 (1974), No. 9/10, pp. 181 FF) it is known that aluminum has a significantly improved performance branch, i.e. less adhesion with respect to the polyurethane, than the form of steel. But the it Department has also been proposed ceramic forms, in addition siliconized, galvanized, Nickel, chrome, coated with polytetrafluoroethylene, and so forth. In case of damage forms with coatings, repair them if it is possible at all, is extremely expensive. None of these modifications steel surfaces not to say that they could find application in the industry.

The closest analogue is the application of tool steels for moulds to produce polymeric materials (see Y. A. Geller, "Tool steels", M, metallurgy, 1968).

Currently there is a great need for the production of polyurethane mouldings without lubricants or at least with a small amount of residue. This takes into account economic, environmental causes, and working conditions.

The objective of the invention is to develop a method of manufacturing polyurethane products in the forms, the inner surface made of tool steel, which ensures the separation of the product from the mold without the use of internal lubricants.

The problem is solved in the method of manufacturing polyurethane products in the Ah, the inner surface made of tool steel, containing components in the following ratio, wt. %: at least one element from the group comprising tungsten, molybdenum, vanadium content: tungsten, from 0 to 40 wt.%, preferably from 2 to 30 wt.%, particularly preferably from 3 to 10 wt.%, molybdenum from 0 to 12 wt.%, preferably from 0.1 to 5 wt.%, particularly preferably from 0.5 to 2 wt.%, vanadium from 0 to 5 wt.%, preferably from 0.5 to 4 weight. %, particularly preferably from 1 to 3 wt.%; at least one element from the group including chromium, aluminium containing: chromium: from 1 to 6 wt.%, aluminum from 0 to 15 wt.%; if necessary, the carbon content of from 0.1 to 1.5 wt.%, preferably from 0.15 to 1.0 weight. %; in case of need, the cobalt content of from 0.1 to 10 wt.%, preferably from 2 to 8 wt.%, especially preferably 4 to 6 wt.%; if necessary, the nitrogen in the nitrided layer with a content of from 0 to 10 weight. %; and iron rest.

The preferred form of the invention is that the molded product is produced by reacting A) polyisocyanates and compounds with at least two relatively reactive isocyanates atoms in which the funds of stitching pore-formers, as well as auxiliaries and additives.

With held in case of need nitriding the surface of the steel can be reduced or eliminated interaction between the surface atoms of the metal and the reactive groups of the used resins and reactive resins. Nitriding leads to further increase the hardness of the surface.

Such superior became known experts in particular varieties of nitrided steel according to DIN 17 007. If necessary, they are well-known method of surface modification, namely the nitriding in the form of nitriding in the salt bath, gas or plasma nitriding and ion nitriding.

A suitable source of steel and how their modifications are described, for example, in the textbook for self-DAG-College, Essen 1982, science, volume 4, page 34, tutorial for self-DAG-College, Essen 1982, science, volume 2, pages 25 and further, Fachkunde Metall, Europa-Verlag, 48 ed., 1987, Tabellenbuch Metall, Europa-Verlag, 38 ed., page 106, Verkstoffkunde für Praktiker Europa-Verlag, 2nd ed., 1985, page 60.

They may also be subjected, if necessary, other mechanical surface treatment, polishing and so on.

Particularly unexpected is that can be processed foamed polyurethane with a low density without the use of lubricants.

Particularly unexpected is the fact that much can be reduced the temperature of the mold. Due to this, reduce the temperature of the mold increases and also the shrinkage process that facilitates the extraction of the product.

Is unexpected, that is known in itself the specialist steel according to the invention has such an effect, while attempts, including the applicant to obtain improved separation using chrome or Nickel plated form, failed (regardless of the problem of repair of such metal surfaces).

The solution according to the invention leads to inexpensive fabrication of plastic parts, as can be fully or largely abolished the processes of separation and further processing.

Suitable raw materials for the manufacture of shaped articles in the form of these steels are all plastic. About the example, separation is due to the chemical nature of these plastics) is the bonding chemical interaction between the plastic and the metal surface. Such plastics are, in particular, reactive plastics, such as styrene and methylstyrene (SMC), epoxides and polyurethanes/polycarbamide, in particular polyurethanes/polycarbamide and other chemical preaddukta isocyanates.

For the implementation of the method of manufacturing shaped elements from polyurethane according to the invention is used, the polyisocyanates A):

1. As initial components aliphatic, cycloaliphatic, analiticheskie, aromatic and heterocyclic polyisocyanate (described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie 562, pages 75 -136) with the formula:

Q(NCO)n,

where n=2-4, preferably 2, and

Q - aliphatic residue with 2-18 carbon atoms, preferably 6-10 carbon atoms, cycloaliphatic residue with 4 to 15 carbon atoms, preferably 5-10 carbon atoms, an aromatic residue with 6 to 15 carbon atoms, preferably 6 to 13 carbon atoms, or analiticheskii residue with 8 to 15 carbon atoms, preferably 8-13 carbon atoms, for example 1,4-tetramethyldisilane, 1,6-exam the NY mixtures of these isomers, 1-isocyanate-3,3,5-trimethyl-5 isocyanatomethyl-cyclohexane (German application DE 1202785, U.S. patent 3401190), 2,4 - and 2,6-hexahydrotriazine, as well as any mixtures of these isomers, hexahydro-1,3 - and/or 1,4-delete the entry, perhydro-2-4'- and/or 4,4'-diphenyl-methane-diisocyanate, 1,3 - and 1,4-delete the entry, 2,4 - and 2,6-teletransmission, as well as any mixtures of these isomers, the difenilmetana-2,4'- and/or 4,4'-diisocyanate, naftilan-1,5-diisocyanate.

In addition, according to the invention apply: triphenylmethane-4, 4' 4"-triisocyanate, polyphenyl-polymethylene-polyisocyanates obtained by anyinformation condensation and final vosganian and described, for example, in patents in the UK 874430 and 848671, m - and p-isocyanatophenyl-isocyanates according to U.S. patent 3454606, perchloroethane arylpropionate described, for example, in German accepted the application DE-1157601 (U.S. patent 3277138), polyisocyanates having carbodiimide described in the German patent 1092007 (U.S. patent 3152162), as well as in German laid bids 2504400, 2537685 and 2552350, norbornane-diisocyanates according to U.S. patent 3492301, polyisocyanates having alliantgroup described, for example, in the United Kingdom patent 994890, patent, Belgium 761626 Yves German patent 10227890, 1222067 and 1929034 and 2004048, polyisocyanates having writegroup described, for example, in the patent Belgium 752261 or in U.S. patent 3394164 and 3644457, polyisocyanates having carboidrati according to German patent 1230778, polyisocyanates having acylated birthrape described, for example, in U.S. patents 3124605, 3201372 and 3124605, as well as in the United Kingdom patent 889050, polyisocyanates obtained by the reaction of telomerization described, for example, in U.S. patent 3654106, polyisocyanates having ester groups mentioned in the patents great Britain 965474 and 1072956, in U.S. patent 3567763 and in the German patent 1231688, the transformation products of the aforementioned isocyanates with acetals according to German patent 1072385 and polyisocyanates containing polymeric ester of a fatty acid according to U.S. patent 3455883.

It is also possible to use the distillation residues obtained in the manufacture of technical isocyanate and having isocyanatopropyl dissolved, if necessary, in one or more of the aforementioned polyisocyanates. In addition, you can use any mixtures of the aforementioned polyisocyanates.

The preferred polyisocyanates are:

Particularly preferably primena mixtures of these isomers ("TDI-toluylenediisocyanate"), polyphenyl-polymethyl-polyisocyanates produced by condensation of aniline-formaldehyde and the final postironium ("crude MDI diphenylmethanediisocyanate") and polyisocyanates ("modified polyisocyanates"), having carbodiimide, writegroup, alliantgroup, isocyanurate, carboidrati or birthrape such modified polyisocyanates derived from 2,4 - or 2,6-toluylene diisocyanate or from 4,4'- and/or 2,4'-diphenyl-mechanisation.

Component b)

Under component B1) refers to compounds with reactive groups of isocyanate, with molecular weight ranging from 1,800 to 12,000, preferably 3,000-7,000 or mixture of such compounds, and the component (b) is the reaction of the accession isocyanate (average) functionality of about 2.5, preferably from 2.6 to 3.0, particularly preferably 2.8 to 3.0. Especially suitable compounds as component b) are the corresponding polyether polyols or mixtures of polyether polyols is described in German application DE-AS 2622951, column 6, line 65 to column 7, line 47, and according to the invention preferred are polyether polyols and hydroxyl group which consists of, at least, for example in the German patent application DE-AS 2622951 polyester, polythioether, polyvinyl acetate, polycarbonates or polyetherimide having a hydroxyl group are suitable, in principle, as component b) according to the invention, as they match the above, however, are less preferred than the polyether polyols.

As the source component B1) are also suitable in accordance with the foregoing, aminopolyamide or mixture of aminopolyamide, i.e. polyether groups, realoneplayer to isocyanatopropyl consisting of at least 50 equivalent %, preferably at least 80 equivalent% from primary and/or secondary aromatic or aliphatic, preferably aromaticheski related amino groups, and the rest of the primary and/or secondary alifaticheskii linked hydroxyl groups. Such suitable aminopolyamide are compounds mentioned, for example, in European application EP-IN-0080701, column 4, line 26 to column 5, line 40.

As the source component B1) are also suitable, but are less preferred ethers having an amino group, with the above range of molecular weights.

Needless to say, as component B1) may, if the EPA by aminopolyamide.

Components B2).

As used if necessary together high-molecular alcohols or polyamines talking about any non-aromatic compounds with at least two groups reactive to isocyanatopropyl, with a range of molecular weights 18, 60 to 1799, preferably 60-500, especially 62-400. Can be taken into account, for example, polyvalent (polyatomic) alcohols, is described in European application EP-IN-0081701, column 9, lines 32-50; in particular, as component B2) are preferred are the following alcohols: EG (ethylene glycol), DEG (diethylene glycol, triethylene glycol, polyethylene glycol, diphenylguanidine, triphenylguanidine, butadion, hexadien. In addition, using, for example, also aliphatic polyamine having a group of simple ether, such as polypropylene oxides having an end (terminal) of the primary amino group with the specified range of molecular weights. Are also of high molecular weight alcohols having cycloaliphatic rings, such as 1,4-dihydroxy-cyclohexane or 1,4-bis-hydroxymethyl-cyclohexane and polyamine, such as 1,4-cyclohexane-diamine, ISOPHORONEDIAMINE, bis-(4-aminocyclo-hexyl)-methane, bis-(3-methyl-4-aminocyclohexanol the UNT B3).

Under the diamines used, if necessary together as other components B3), refers to aromatic diamines of the type mentioned in the example in European application EP-IN-0081701, column 5, line 58 to column 6, line 34, preferably according to the invention are preferably those diamines which are specified as preferred.

As auxiliaries and additives B4) used if necessary in the manufacture of polyisocyanate-priduct, it is, for example, about the internal dividing means, if necessary catalysts for polyisocyanat-preductive reaction, a pore-forming additives, water, surface-active additives, regulators porosity, organic and inorganic pigments, dyes, UV and thermal stabilizers, plasticizers or fungistaticeski or bakteriostaticheski active substances, for example described in European application EP-IN-0081701, column 6, line 40 to column 9, line 31.

To apply if necessary utilities and additives include known fillers and/or reinforcers, such as barium sulphate, kieselguhr, otmochennye mA.

The implementation of the method according to the invention:

The reagents according to the invention is subjected to a reaction between a known single-stage method of curing the prepolymer or the way polyetherimide prepolymer, often using mechanical devices, which are described, for example, in U.S. patent 2764565. Details of processed devices which are also used according to the invention are described in Kunststoff Handbuch, volume VII, released in Viweg and Hoechtlen" publishing house Karl-Hanser, Munich 1966, e.g. on pages 121-205.

The products made according to the invention, are, for example, the following application: gasket furniture, textile inserts, mattresses, seats for vehicles, armrests, spongy metal and building structural elements, seat upholstery and fittings, body parts for vehicles carrying modules, door trim, steering wheel cover types.

Examples:

The following examples use steel grade S 6-5-2 (Dmo5) composition 0,86-0,94 With, 3,80-4,50 Cr, 4,70-5,20 Mo, 1,70-2,00 V, 6,00-6,70 W; impurity 0,45 Si 0,40 Mu, 0,030 P 0,030 S, and iron rest, available in nitrided and easterbunny form.

Example 1: the Experience of the Department with material IMR

2 parts polyricinoleic acid with an acid number of <5
0,7 parts amine catalyst, Air Products

0.1 part of tin catalyst Witco

0,1 siloxane stabilizer Goldschmidt AG.

100 parts of component (recipe above) this recipe polyhydric alcohol is treated 66,2 parts ureterovaginal the difenilmetana-diisocyanate with an NCO content of 24.5 wt.%. The concentration of plate = about 1 l/kg

The result: lack of adhesion on steel for a long time, which is essential for the invention.

Example 2: the Experience at the Department of materials EMR

Bayflex 110 EMR: VP. PW 505 BX/Desmodur Pa 09

Component a polyhydric alcohol:

75,60 parts of a polyether with a hydroxyl number equal to 27 get phased by adding first 87 wt.% of polypropylene oxide and then 13 wt.% of ethylene oxide to trimethylolpropane

21 part of a mixture of 65 parts of 1-methyl-3,5-diethyl-2,4-diaminobenzene and 35 parts of 1-methyl-3,5-diethyl-2,6-diaminobenzene

0,3 parts of amine catalysis is on and ethylene diamine with a hydroxyl number equal to 1600 mg KOH/g

100 parts of component a polyhydric alcohol obrabatyvat 56,7 parts ureterovaginal of diphenylmethanediisocyanate with NCO content equal to 24.5 wt.%. The concentration of plate = about 1 l/kg

The result: no adhesion to steel for a long time, essential for the invention.

Example 3: Experience in the Department of materials EMR

Baydur - integral hard foam

Component of high molecular weight alcohol:

38,10 parts of a polyether with a hydroxyl number equal to 27 get phased by adding first 87 wt.% of propylene oxide and then 13 wt.% of ethylene oxide to trimethylolpropane

33,60 parts of a polyether with a hydroxyl number equal to 865, get phased by adding propylene oxide to trimethylolpropane

22,40 parts of a polyether with a hydroxyl number equal to 1010, get phased by adding propylene oxide to trimethylolpropane

1.6 parts of amine catalyst, Air Products

2,7 part of the stabilizer based on silicon

of 1.6 parts of water.

100 Parts of this recipe polyhydric alcohol is treated 164,4 part of raw diphenylmethanediisocyanate Desmodur 44V20 with NCO content equal to 31.5 wt.%. The oxygen is La inventions.

Example 4: Easterbunny steel

Not detected differences from examples 1-3.

Example 5: Comparative experience: normal tool steel.

The material of example 1 of about 30-40 upload from the form, the materials in examples 2-3 2-10 parts, then it must be each time to separate.

Example 6: Comparative experience: aluminium alloy Bondur

The material of example 1 of about 60-100 upload from the form, the materials in examples 2-3 from 5 to 30 parts, then it must be each time to separate.

1. A method of manufacturing polyurethane products in the forms, the inner surface of which is made of steel, characterized in that the manufacture is carried out in the forms, the inner surface made of tool steel, containing components in the following ratio, wt. %: at least one element from the group comprising tungsten, molybdenum, vanadium content: tungsten, from 0 to 40 weight. %, preferably from 2 to 30 weight. %, particularly preferably from 3 to 10 weight. %, molybdenum from 0 to 12 weight. %, preferably from 0.1 to 5 weight. %, particularly preferably from 0.5 to 2 weight. %, vanadium from 0 to 5 weight. %, preferably from 0.5 to 4 weight. %, particularly preferably from 1 to 3 weight. %; at least Lucae necessary, the carbon content of from 0.1 to 1.5 weight. %, preferably from 0.15 to 1.0 weight. %; if necessary, the cobalt content of from 0.1 to 10 weight. %, preferably from 2 to 8 weight. %, particularly preferably from 4 to 6 weight. %; if necessary, the nitrogen in the nitrided layer with a content of from 0 to 10 weight. %; and iron rest.

2. The method according to p. 1, characterized in that use form, the internal surface of which contains, if necessary, the Nickel content of > 0.3 weight. % nitrided layer with a nitrogen content in the nitrided layer from 8 to 10 weight. %.

3. The method according to one of paragraphs. 1 and 2, characterized in that the molded product is produced by reacting A) polyisocyanates and compounds with at least two reactive relative to the isocyanate hydrogen atoms and a molecular weight of from 60 to 2000, if necessary, in the presence of chain-extending and/or crosslinking, pore-formers, as well as auxiliaries and additives.

Priority points and features:

12.03.1996 on PP. 1-3 - the method is characterized by the fact that the inner surface forms made of tool steel containing carbon;

27.11.1996 on PP. 1-3 - the method is characterized

 

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FIELD: technological processes.

SUBSTANCE: first part of matrix is made according to template, on which the first layer is coated made of glass tissue, which is soaked with thermal resistant epoxide resin. Then several layers of glass tissue are coated, which are soked with regular epoxide resin, after these layers are dried out, in prepared part of matrix thru openings are drilled on the whole surface in the amount necessary for subsequent vacuum molding. Internal form of second part of matrix is manufactured on the basis of internal side of first part of matrix. On the first part, after it has been treated with lubricant, strips of elastic material connected between each other that have previously been treated with lubricant are laid and fixed above vacuum openings. They form vacuum channels in the second internal part of matrix, and in the point of their crossing - vacuum outlet for connection to vacuum system, through which vacuum forming is done. Afterwards on internal first surface of matrix with strips laid on it with vacuum outlet, several layers of glass tissue are applied, which are soaked with regular epoxide resin. After its hardening on the second part of matrix it is separated from the first, used elastic material is removed, both sides of matrix are degreased and adhered to each other with the help of epoxide resin.

EFFECT: provision of technological and economical method of manufacturing matrix for molding of items of any configuration from polymer materials with method of vacuum moldings and manual molding with application of epoxide resins and glass tissues.

FIELD: metallurgy.

SUBSTANCE: steel contains components at a following ratio, wt %: carbon (C) 0.02-0.09, nitrogen (N) 0.025-0.12, silicon (Si) ≤ 0.25, aluminium (Al) ≤ 0.080, manganese (Mn) 0.55-1.8, chrome (Cr) 11.5-16, copper (Cu) up to 0.48, overall molybdenum (Mo) and half of tungsten (W/2) up to 0.90, nickel (Ni) up to 0.90, vanadium (V) up to 0.090, niobium (Nb) up to 0.090, titanium (Ti) up to 0.025, sulphur (S) up to 0.25, iron and formed during melting admixtures are the rest. Compound of steel satisfies the conditions 0.05≤C+N≤0.17, Si+23Al≥0.20, Si+0.6Al≤0.25, 0.00025≤Al×N≤0.0020, 6.5 ≤ F = (Cr+Mo) + 2(Si+V+Nb) - 27(C+N) -(Ni+Mn/2+Cu/3) ≤13.

EFFECT: increased steel machinability, weldability, corrosion resistance and thermal conductivity.

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