Tool coating wires and method thereof

 

(57) Abstract:

The application describes a means of covering wires containing polyester resin or polyetherimide resin or incorporating hydroxyl group of the polyol together with the isocyanate component, free isocyanate groups which is completely blocked. The proposed tool coatings are produced by the esterification of polyhydric alcohols naphthalenemethanol(s) acid (s) and/or its (their) tarifitsiruemye derivatives optionally in a mixture with other dicarboxylic acids and/or their derivatives with the addition of catalysts, organic solvents and additives, as well as optional using contains kidnie group or forming kidnie group starting substances, which improves its resistance to thermal shock, stability during storage and cut-through. 2 S. and 9 C.p. f-crystals, 4 PL.

The present invention relates to a tool for coating wires containing polyester resin or polyetherimide resin or incorporating hydroxyl group of the polyol with the isocyanate component, free isocyanate groups which is completely blocked.

Used the different binders, such as polyesters, polyetherimide and contain hydroxyl groups of the polyesters with blocked isocyanates in solvents, optionally in combination with a commercially available hydrocarbon diluents.

Funds to cover the wires on the basis of polyester resins are known, for example, from the following publications: US 3342780, US 3249578, EP-B 144281 and PCT/EP 92/02776. As the hydroxyl component in these publications use of Tris(2-hydroxyethyl)isocyanurate (THEIC). Wire, covered by polyester resins are distinguished by the fact that the lacquer film has good bond strength with copper wires. In addition, having such a coating wires have a high cut-through, if used polyester resin modified THEIR.

From application PCT/EP 92/02776 it is known further that due to the adulteration of bismaleimide resins can significantly increase the level of efficiency polyester funds coating, modified THEIS, especially resistance to thermal shock and cut-through.

The lack of funds to cover the wires on the basis of polyester resins is that is covered with polyester lacquer wires have diskotechnyj coatings, applied in such a way that these coatings of polyester resins form a primer (primer lacquer), which is then applied polyamidimide lacquer as a top coat.

Polyetherimide resins are known, for example, made up of applications of Germany DE-OS 1445263 and 1495100, as well as from international application WO 91/07469 (PCT/EP 90/01911). These resins due to their good mechanical, thermal and chemical properties are widely used in mechanical engineering. Their thermal and chemical properties polyetherimide significantly inferior to the two-layer coatings using polyamideimide as a finishing varnish.

Insulating means coatings based on polyurethanes are described, for example, in applications Germany DE 144749 and DE 1957157. Insulating means covering this type when they are applied to cover the wires differ primarily high insulating properties. Along with this they have the advantage of being able to undergo maintenance. When immersing the past such processing service insulated wires heated to elevated temperatures tub soldering insulation layer is destroyed and due to this frees up the metal of the conductor, and this factor is maximally reduced time necessary to remove the insulating lacquer coating. However, the requirement for high thermal requirements in terms of soldering is not consistent with high heat resistance, which is an indispensable condition for the application of the coated wires in electrical nodes. This requirement for enhancing the heat resistance brazed wires with lacquer in principle contrary to a short service time required for fast processing of wires.

Based on the foregoing, the invention was based on the task to provide means for coating wires containing polyester resin or polyetherimide resin or incorporating hydroxyl group of the polyol with the isocyanate component, free isocyanate groups which completely blocked, which would eliminate the above disadvantages of the currently known resources of the coating and thereby significantly improve their properties. Funds to cover the wires according to the invention must first of all have storage stability, good grip force primarily with copper wires, high cut-through, and high resistance to Teplova while simultaneously optimal for processing viscosity. When using polyurethane funds cover had to be simultaneously reduced maintenance time.

This task is solved in an unexpected way due to the fact that the proposed remedy for the coating of wires includes in its composition polyhydric alcohols, esterified naphthaleneboronic acid and/or its tarifitsiruemye derivatives, optionally in a mixture with other dicarboxylic acids and/or derivatives of these acids, further catalysts, organic solvents and additives, and optionally containing, respectively, forming aminogroup educt.

Thus according to the invention in contrast to the above prior art as carbonisation components used naphthalenesulphonate acids or their derivatives. Sudden and unexpected factor is the possibility of getting through modification naphthalenemethanamine acids, their derivatives, respectively coatings for cables with very good adhesive strength to electrical conductors, first and foremost to the copper wires, and providing their extremely high technological properties. The want to make and resistance to thermal shock, as well as good storage stability and a high solids content while simultaneously optimal for processing viscosity.

Suitable for use for the purposes described above naphthalenemethanamine acids are 1,4-, 1,8-, 2,3 - and 2,6 - natalijagolosova acid. Particularly preferred of them 2,6-natalijagolosova acid.

Can also be used esters and halides of these compounds. It is suitable for use, tarifitsiruemym derived primarily include methyl-, ethyl-, propyl-, butyl-, amyl-, hexyl - and octylsalate. Can be used as palefire, dialkyl ethers, and mixtures of these compounds.

Naphthalenesulphonate acid, respectively, their derivatives can be used as the sole acid component or in a mixture with other carboxylic acids. Suitable carboxylic acids for such mixtures with naphthalenemethanamine acids, respectively, their derivatives are, among others, phthalic acid, isophthalic acid, terephthalic acid, and their tarifitsiruemye derivatives, for example methyl, ethyl, propyl, butyl, amyl, hexyl and oktilovom esters. In these above-naphthalate acceptable to the acid halides.

According to the invention can also be used aliphatic dicarboxylic acids, for example oxalic acid, malonic acid, succinea acid, glutaric acid, adipic acid, Emelyanova acid, azelaic acid, sabotinova acid, maleic acid, fumaric acid or sorbic acid. The ratio between naphthalenemethanamine acids and other carboxylic acids from among the above is chosen so that the binder contains from 0 to 100 mol.% naphthaleneboronic acid and from 0 to 99 mol.% other dicarboxylic acids based on 100 mol.% the total number of carboxylic acid.

In more detail below describes the components used to obtain the offer of funds to cover the wires.

Obtaining polyesters carry out the esterification described above naphthalenesulphonic acids or their derivatives, individually or jointly with other dicarboxylic acids, respectively, with their derivatives, which is carried out by interaction with polyhydric alcohols in the presence of appropriate catalysts. Suitable for these purposes alcohols are primarily diols, and thiols. As examples of such queries is Anglican, triethylene glycol, glycerin, trimethylacetyl, trimethylolpropane and THEIR. The last of these triolo for polyester resins are preferred. It provides the most favorable softening temperature funds to cover the wires. Particularly preferred mixture of diols and triolo. In these cases, the preferred primarily of a mixture of ethylene glycol and THEIR.

The number of individual components is chosen so that the ratio between hydroxyl and carboxyl groups in the polyester is from 1.1:1 to 2.0:1, preferably from 1.15:1 to 1.60:1.

The preferred application of the proposed means for coating wires, based on polyester resins are ethylene glycol, THEIR, dimethyl 2,6-naphthaleneboronic acid and terephthalate. The hydroxyl number of the polyester is preferably in the range from 95 to 280 mg KOH/g

According to the invention, the catalysts are used in quantities of from 0.01 to 5 wt.% based on the amount of the mixture, preferably from 0.3 to 3 wt. %. In these cases, we are talking mainly about the usual esterification catalysts, such as, for example, salts of heavy metals, organic titanates, rerieve the wine and zinc acetate. To apply for the above mentioned purposes the titanates include, in particular, Tetra-n-butylsilane, tetraisopalmitate, tetrapropylene, tetraphenylmethane, tetramethylsilane, tetracyanoethylene or triethanolaminato. The example uses an organic acid is p-toluensulfonate.

Acceptable for the proposed coating the wires with organic solvents are crenoline and Nekretnine organic solvents. As examples of such can be called cresol, Xylenol, phenol, phenylglycol, butylglycol, metildigoxin, ethyldiglycol, butyldiglycol. Along with them can also be used glycol containing simple and complex ester group, such as, for example, methylsiliconate, atilglukuronida and butylglycol. This list can be supplemented with cyclic carbonates such as ethylene carbonate resulting and polypropenkarbonat, complex cyclic ethers, such as butyrolactone, and other solvents such as dimethylformamide, N, N-dimethylacetamide, N-organic and benzyl alcohol, which may not necessarily used in combination with the above solvents. Organic solvents can be used partially with the UYa for these purposes, xylene, toluene, ethylbenzene, cumene, Solventnaphta, Solvesso and various types of Shellsol .

The proposed means of coating the wires on the basis of polyester resins contain mostly 0.5 to 5.0 wt.%, preferably up to 4.0 wt.% phenolic resin, calculated on the total weight of coverage tools, including the proportion of phenolic resin.

Used phenolic resins are condensation products of phenol, substituted phenols or bisphenol A with formaldehyde. The properties of these phenol-formaldehyde resins depend on the type of phenol and aldehyde components from the set in the process of obtaining the pH value and the quantitative ratio of both cocomponent. According to the present invention, the phenolic resin can be modified by introduction of other compounds when conducting polycondensation or subsequent modification of phenolic resins and different technology for the realisation of the reaction process. Needless to say, that along with the products of polycondensation with formaldehyde may also be used with any other aldehydes.

Thus, coatings with particularly good properties have the following composition: 30-55 wt. % of polyester resin, 0.5 to 2.5 wt.% catalyst, preferably 0.5 to 1.5 mA is for the mixture of solvents based on the total weight of the coating, 100 wt.%. In addition, coating of the wires according to the invention can contain also conventional auxiliary substances and additives. Their amount is preferably up to 1 wt.% in terms of the total weight of the components. As auxiliary substances for funds coating according to the invention can be used, for example, improves the spreading of the melamine resin to improve the spreading of the substance based on polyacrylates.

The usual way to obtain polyester resins according to the invention is that the alcohols condensed with carbonnanotube components in an organic solvent, preferably a cresol, and mixed with a catalyst, and optional phenolic resin, other auxiliary substances and additives. The individual components used in the above proportions. The funds cover the wires according to the invention can contain the above-described polyester resin in an amount of from 15 to 65 wt.%, preferably from 25 to 55 wt.% and especially from 30 to 55 wt.% in terms of the total weight of tool coatings. Most preferably the amount of from 40 to 50 wt.%.

The processing means of the coating of the wires by Yves each case, the thickness of the lacquer films produced by its application in a number of techniques, moreover, before applying the next layer of each of the previous deposited layer utverjdayut without swellings. Typical temperature curing are in the range of 300-550oC.

Obtained according to the described technology tools covering wires unexpectedly have good stability during storage and high solids content while simultaneously optimal for processing viscosity, although entered into their composition natalijagolosova acid has a significant molecular weight and rigid structure. Therefore, the effect of surprise to a person skilled in the art is that the polyester resin is not vysokomaslichnoy and thereby partially soluble.

Coverage of the means according to the invention after application of hot and drying have unexpectedly high adhesive strength to elektroprovodnyi primarily to the copper wires. Unexpectedly, it was found that the coatings produced from the means according to the invention, is distinguished by its exceptional range of excellent properties. First of all, it was unpredictable that wire with the proposed coverage, have not only extremely high cut-through, but also deposits of level property with polyester varnish for wires, modified not by the above-described technology, so far without success.

Getting used according to the invention polyetherimide resins is carried out by esterification described above naphthalenesulphonic acids, respectively, their derivatives, or their mixtures with other carboxylic acids, their derivatives, respectively, ongoing interaction with polyhydric alcohols, optionally with the addition of hydroxycarboxylic acids and using a forming aminogroup the original substances. Instead of the free acids and alcohols can also be applied to their reactive derivatives.

As polyhydric alcohols are acceptable, as and when received polyester resins, as diols, and trioli. Examples thereof are ethylene glycol, 1,2 - and 1,3-propylene glycol, 1,2-, 1,3 - and 1,4-butanediol, 1,5-pentanediol and neopentylglycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane and THEIR. Called last triol especially preferred. Its application leads to an increase in the softening temperature obtained funds for the lacquer coating.

Forming aminogroup the original substance can be obtained, for example, vzaimodei, and at least another functional group, while the other has in its composition than the primary amino group at least one functional group. In the role of other functional groups are primarily carboxyl or hydroxyl group. You can also use other primary amino group or groups, anhydrides of carboxylic acids.

Examples of amines are used primarily dsupervise diamines, such as Ethylenediamine, tetramethylaniline, hexamethylenediamine were, monomethylaniline and other aliphatic dsupervise diamines. Acceptable further aromatic dsupervise diamines, such as diaminodiphenylmethane, diaminodiphenylsulfone, -sulfon, -sulfoxide, -ether, -tiefer, phenylendiamine, toluylenediamine. Finally, suitable for use for the purposes described above cycloaliphatic diamines, such as 4,4'-dicyclohexylmethane. As containing amino compounds with another functional group can be used as aminoalcohols, such as monoethanolamine and monopropylene, then aminocarbonyl acids such as glycine, aminopropionic acid, aminocarbonyl acid or aminobenzene acid.

Polyetherimide injected into a means of covering wires usually in quantities of from 15 to 65 wt.%, preferably from 15 to 60 wt.%, first of all, from 25 to 55 wt. %. The most preferred range is from 30 to 55 wt.%, first of all, from 30 to 50 wt.% in terms of the total weight of coverage tools.

Also used according to the invention lucky for wire-based polyurethanes include in its composition a combination of one or more containing a hydroxyl group of a polyether with OH number, typically from 200 to 900 mg KOH/g, preferably from 250 to 750 mg KOH/g, and one or more adducts of blocked isocyanates.

To obtain containing hydroxyl groups of the polyesters can be used the same components for the build (polycarboxylic acid and polyol) and observed the same conditions reaktivnie for these purposes polycarboxylic acids are described above. Be used can free acids or their derivatives. Naphthalenesulphonate acid, respectively, derivatives thereof used individually or in a mixture with the above-described polycarboxylic acids, respectively, with their derivatives.

It is known that modification containing hydroxyl groups of the polyesters kilograme improves thermal properties formed from polyurethane varnish them for the wires. To implement kidney modifications to fit the same form aminogroup source substances, which are described above upon receipt of polyetherimides.

It is suitable for use in these processes alcohols include, among others, ethylene glycol, 1,2 - and 1,3-propylene glycol, 1,2-, 1,3 - and 1,4-butanediol, 1,5-pentanediol, neopentylglycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane and THEIR. The preferred use are a mixture of diols and triolo.

Suitable for use in the above processes, catalysts and solvents are identical to the above, which is used when obtaining polyesters and polyetherimides. We are talking about conventional esterification catalysts, such as salts of heavy metals, organic titanate, cerium compounds, crenoline and Nekretnine organic solvents.

Adducts of isocyanate is produced by interaction of the diisocyanate with the polyol, and the amount of these compounds is chosen so that the equivalent ratio of NCO: OH is from 1:2 to 9:1. Residual free isocyanate groups of the adduct is subjected to interaction with a blocking agent. Of course, there is also an option when first isocyanates are interacting with a blocking agent, and the residual free isocyanate group is subjected to interaction with diola. Building adduct of isocyanate preferably carried out in an inert towards isocyanate groups, good solvent of the resulting polyurethane solvent in the presence of a catalyst in the temperature range from 30 to 120oC. as examples suitable for these purposes diisocyanates can be called tetramethyldisilane, hexamethylenediisocyanate, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-delete the entry, 1,4-delete the entry, 2,5-toluenediisocyanate, 2,6-toluenediisocyanate, 4,4'-biphenylenediisocyanate, 1,5-naphthylenediisocyanate, 1,4-naphthylenediisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3 .3m-trimethylcyclohexane, bis(4-isocentrically)methane, bis(4-isocyanatophenyl) Menil) methane.

Examples of polyols suitable for the formation of adducts are trimethylolpropane, neopentylglycol, glycerin, hexanetriol, pentaerythritol, ethylene glycol and propylene glycol. Preferred of them trimethylolpropane. The preferred adduct obtained from 1 mole of trimethylolpropane and 3 moles of toluylene diisocyanate and/or bis-4-(isocyanatophenyl)methane.

To block the free isocyanate groups fit all the known blocking agents. As such compounds include, for example, aliphatic, cycloaliphatic or aromatic alcohols, in particular butanol, Isobutanol, 2 - ethylhexanol, cyclohexanol, Cyclopentanol, benzyl alcohol, phenol, cresol. Then you can call hydroxyalkyloxy ether, such as butylglycol, amines, such as di-n-butylamine, di-n-hexylamine, oximes, for example, methylethylketoxime, diethylketone, hydroxylamine and lactams, such as caprolactam, and a number of other compounds containing a hydrogen atom which, thanks to its reactivity provides the interaction of the blocking agent with the isocyanate. As the preferred blocking agents are used phenols and Cresols. The amount of hydroxyl-containing polyesters and predpochtitelno from 25 to 55 wt.%. Especially preferred quantity range 18-40 wt.%, first of all, 25-35 wt.% in terms of the total weight of tool coatings. The number of blocked isocyanate adducts is from 150 to 500 wt. parts per 100 wt. parts containing hydroxyl groups of the polyesters.

Along with the above-described components of the product coatings based on polyurethanes contain more and conventional auxiliary substances and additives, preferably in a quantity from 0 to 1 wt.% in recalculation on weight of a binder, respectively, calculated on the weight of binder and hardener. As auxiliary substances introduced into the funds of the coating according to the invention can be used, for example, improves the spreading of the phenolic or melamine resins or other common substances of this type, for example, based on the polyacrylate.

The funds cover the wires on the basis of polyurethanes contain, as a rule, also the catalysts. As such, can be considered metal salts such as zinc acetate, or amines, which are used usually in amounts of from 0.5 to 2.0 wt. % based on the total weight containing hydroxyl groups of the polyesters and blocked isocyanate adducts.

Below the invention is explained in more examples.

Used in the proposed means of coating wire binder (polyesters, polyetherimide containing hydroxyl group of the polyol together with blocked isocyanate adducts) can be obtained by the method of condensation in the melt or condensation in solution in an appropriate solvent such as cresol, Xylenol, N-organic, metalliville, ethyldiglycol or ethylene glycol.

Examples

Receipt containing 2,6-naphthaleneboronic acid THEIC-polyester varnishes for cables

Example 1oC get polyester resin with a hydroxyl number of from 140 to 260 mg KOH/g THEIC-modified polyester resin softens at 150-180oC 298,15 g of cresol and 108,38 g Xylenol. After cooling to room temperature, add 104,27 g solvent-naphtha, 19,48 g butylmalonate and 40,69 g of commercially available phenolic resins.

Viscosity (23oC): 540 mPas.

Solid (1 g, 1 h, 180oC):39%.

Example 2

From 49,14 g of ethylene glycol, 26,76 g of cresol, 230,68 g of dimethyl ester of 2,6-naphthaleneboronic acid, 108,54 g of Tris - 2-hydroxyethylmethacrylate and 0.27 g of butylmalonate by heating to 200oC get polyester resin with a hydroxyl number of from 140 to 260 mg KOH/g THEIC-modified polyester resin razmagchaut at 150-180oC 300,66 g of cresol and 98,97 g Xylenol. After cooling to room temperature, add 130,04 g solvent-naphtha, 17,79 g butylmalonate and 37,15 g of commercially available phenolic resins.

Viscosity (23oC): 550 mPas.

Solid (1 g, 1 h, 180oC):35.1 per cent.

Example 3

From 21,48 g of ethylene glycol, 21,44 g of cresol, 191,25 g of dimethyl ester of 2,6-naphthalenemethanol KIS is the first number from 140 to 260 mg KOH/g THEIC-modified polyester resin softens at 150-180oC 388,79 g of cresol. After cooling to room temperature, add 160,00 g solvent-naphtha, 14,75 g butylmalonate and 30,79 g of commercially available phenolic resins.

Viscosity (23oC):820 mPas.

Solid (1 g, 1 h, 180oC):40,6%.

Example 4 (comparative)

Getting THEIC-modified polyester lacquer

From 55,24 g of ethylene glycol, 30,08 g of cresol, 206,20 g of dimethyl terephthalate, 122,03 g THEIS and 0.32 g of butylmalonate by heating to 200oC get polyester resin with a hydroxyl number of from 140 to 260 mg KOH/g THEIC-modified polyester resin softens at 150-180oC 306,07 g of cresol and 111,26 g Xylenol. After cooling to room temperature, add 107,03 g solvent-naphtha, 20,00 g butylmalonate and 41,77 g of commercially available phenolic resins.

Viscosity (23oC): 530 mPas.

Solid (1 g, 1 h, 180oC):39,0%.

Obtained in examples 1-4 varnish was coated wire using a standard apparatus for coating materials. When this was applied as a single layer and two-layer coatings. In two-layer coatings of polyester varnishes used is available polyamidimide nail wires, preferably Allotherm 602 L-35 (firm Dr.Beck, BASF L+F). This method is known and represents the level of technology.

Conditions coating:

Single-layer coating

drying oven: MAG AW/1A

temperature: 520oC

application equipment: nozzle

the diameter of wires: 0.71 mm

the unwinding speed: 32 m/min

the number of broaches: 10

magnification: 2L

Double-layer coating

drying oven: MAG AW/1A

temperature of 520oC

application equipment: nozzle

the diameter of wires: 0.71 mm

the unwinding speed: 30 m/min

the number of broaches:

priming lacquer 8

top coat varnish 2

magnification: 2L

Covered wire was tested according to IEC 851. The results obtained are presented in table 1.

Put on wire single-layer coating of THEIC-modified polyester varnish (example 4) has a very good adhesive strength when the winding wire lxd preliminary stretching of 25% and a high softening temperature equal to 400oC. the Disadvantage of this coating is a low resistance to thermal shock lxd 155oC and low temperature, a sharp increase in tan 150oC. Kompensirovannogo and cover it polyamideimide varnish. These so-called wire with two-layer coating belong to the prior art. Created this by isolating primer lacquer along with good adhesive strength also provides a high softening temperature, while the top coat varnish provides high resistance to thermal shock.

Obtained in examples 1-3, we offer lucky for wires with high strength adhesion to copper wires in accordance with existing regulatory requirements and have a high surface quality. Having a single-layer coating of the wire in terms of its resistance to thermal shock and thermoplasticity noticeably superior wire, covered with traditional THEIC-polyesters. Wire coated with lacquers according to the invention are resistant to thermal shock, lxd, 200oC preliminary stretching from 0 to 10% and cut-through 420-450oC. Temperature, a sharp increase in tan . is within 165-179oC. the Level of quality of these wires meets the requirements according to IEC 317-8 to have polyetherimide floor wire, class 180. Wire thermal class 180, covered only with polyester varnishes without coating of lacquer to nastiashurigina its resistance to thermal shock and thermoplasticity wire with two-layer coating, where as a primer varnish use traditional THEIC-polyesters. Wire with two-layer coating lacquer according to the invention are resistant to thermal shock, lxd, 300oC preliminary stretching from 0 to 25% and cut-through 420-450oC. Temperature, a sharp increase in tan is within 164-190oC.

Example 5

Receipt containing 2,6-naphthaleneboronic acid iminodiethylamine polyester 1

From 59,76 g of ethylene glycol, 59,79 g of glycerol, of 23.11 g of xylene, 87,30 g of dimethyl terephthalate, 109,79 g of dimethyl ester of 2,6 - naphthaleneboronic acid and 0.36 g of butylmalonate by heating to 200oC get polyester resin. You get 65,82 g of distillate. If 200oC add immediately 354,79 g of cresol, and after cooling to 90oC enter 76,26 g diaminodiphenylmethane and 148,13 g of anhydride trimellitic acid. Re-heated to 200oC get iminodiethylamine polyester. In addition get more 30,79 g of distillate. Then cooled to 140oC and add 40,42 g of cresol and 40,29 g solvent-naphtha.

Viscosity, 23oC:Pas 55.

The solids content (2 g, 1 h, 200oC):51%.

Example 6

P is ikola, 58,60 g glycerol 22,47 g of xylene, 215,30 g of the ether of 2,6-naphthaleneboronic acid and 0.17 g of lead oxide (II) by heating to 200oC get polyester resin. You get 63,73 g of distillate. If 200oC add immediately 347,48 g of cresol, and after cooling to 90oC enter 74,79 g diaminodiphenylmethane and 145,27 g of anhydride trimellitic acid. Re-heated to 200oC get iminodiethylamine polyester. In addition get more 26,77 g of distillate. Then cooled to 140oC and add amounted to 38.66 g of cresol and amounted to 38.66 g solvent-naphtha.

Viscosity, 23oC: 60 Pas.

The solids content (2 g, 1 h, 200oC):52%.

Example 7 (comparative)

Getting iminodiethylamine polyester

From 61,21 g of ethylene glycol, 61,21 g glycerol 23,47 g of xylene, 178,76 g of dimethyl terephthalate and 0.18 g of lead oxide (II) by heating to 200oC get polyester resin. You get 70,13 g of distillate. If 200oC add immediately 362,85 g of cresol, and after cooling to 90oC enter 78,10 g of 4,4'- diaminodiphenylmethane and 151,70 g of anhydride trimellitic acid. Re-heated to 200oC get iminodiethylamine polyester. In addition recip>/P>Viscosity, 23oC: 25 Pas.

The solids content (2 g, 1 h, 200oC):50%.

Example 8

Obtaining polyurethane varnish

At temperatures below 30oC to 21,00 g 1-methoxypropylacetate-2 add 7,19 g of 1,3-butanediol, 9,18 g of trimethylolpropane and 111,83 g of 4,4'-diphenylmethanediisocyanate. The mixture is heated under stirring up to 80-100oC and kept at this temperature until, until the isocyanate content reaches a figure 12-17%. Then cooled to 50-60oC and at this temperature, add 171,71 g of cresol and 57,72 g solvent-naphtha. The mixture is again heated to 80-100oC and kept at this temperature until, until the isocyanate content reaches a rate less than 0.2%. After this is cooled to 40-60oC. Then add 281,66 g iminodiethylamine ester from example 5, 229,82 g of cresol, 107,74 g solvent-naphtha and 2.15 g of octoate zinc and stirred for three hours.

The expiry time, DIN 53211, 4 mm, at 23oC:48 with.

The solids content (1 g, 1 h, 180oC):29,4%.

Example 9

Obtaining polyurethane varnish

At temperatures below 30oC to 22,25 g 1-methoxypropylacetate-2 add a 7.62 g of 1,3-butanediol, 9,73 g trimethylolpropane the th temperature until until the isocyanate content reaches a figure 12-17%. Then cooled to 50-60oC and at this temperature, add 181,96 g of cresol and 61,17 g solvent-naphtha. The mixture is again heated to 80-100oC and kept at this temperature until, until the isocyanate content reaches a rate less than 0.2%. After this is cooled to 40-60oC. Then add 238,78 g iminodiethylamine ester from example 5, 243,53 g of cresol, 114,17 g solvent-naphtha and 2.28 g of octoate zinc and stirred for three hours.

The expiry time, DIN 53211, 4 mm, at 23oC:46 with.

The solids content (1 g, 1 h, 180oC):30,0%.

Example 10

Obtaining polyurethane varnish

At temperatures below 30oC to quintiles these figures were 19.63 g 1-methoxypropylacetate-2 add 6,72 g of 1,3-butanediol, 8,58 g of trimethylolpropane and 104,48 g of 4,4'-diphenylmethanediisocyanate. The mixture is heated under stirring up to 80-100oC and kept at this temperature until, until the isocyanate content reaches a figure 12-17%. Then cooled to 50-60oC and at this temperature, add 160,47 g of cresol and 53,94 g solvent-naphtha. The mixture is again heated to 80-100oC and kept at this temperature as long as the content is modificirovannogo ester from example 6, 308,31 g of cresol, 100,72 g solvent-naphtha and 2,05 g octoate zinc and stirred for three hours.

The expiry time, DIN 53211, 4 mm, at 23oC:59 with.

The solids content (1 g, 1 h, 180oC):29,8%.

Example 11

Obtaining polyurethane varnish

At temperatures below 30oC to 17,22 g 1-methoxypropylacetate-2 add 5,90 g of 1,3-butanediol, 7,52 g of trimethylolpropane and 91,66 g of 4,4'-diphenylmethanediisocyanate. The mixture is heated under stirring up to 80-100oC and kept at this temperature until, until the isocyanate content reaches a figure 12-17%. Then cooled to 50-60oC and at this temperature, add 140,68 g of cresol and 47,28 g solvent-naphtha. The mixture is again heated to 80-100oC and kept at this temperature until, until the isocyanate content reaches a rate less than 0.2%. After this is cooled to 40-60oC. Then add 239,19 g iminodiethylamine ester from example 6, 317,09 g of cresol, 131,63 g solvent-naphtha and 1.83 g of octoate zinc and stirred for three hours.

The expiry time, DIN 53211, 4 mm, at 23oC:50 with.

The solids content (1 g, 1 h, 180oC):27%.

Example 12 Obtaining polyurethane varnish

OPANA and 93,72 g of 4,4'-diphenylmethanediisocyanate. The mixture is heated under stirring up to 80-100oC and kept at this temperature until, until the isocyanate content reaches a figure 12-17%. Then cooled to 50-60oC and at this temperature, add 143,92 g of cresol and 48.38 per g of solvent-naphtha. The mixture is again heated to 80-100oC and kept at this temperature until, until the isocyanate content reaches a rate less than 0.2%. After this is cooled to 40-60oC. Then add 257,72 g iminodiethylamine ester from example 6, 297,62 g of cresol, 125,46 g solvent-naphtha and 1.84 g of octoate zinc and stirred for three hours.

The expiry time, DIN 53211, 4 mm, at 23oC:65 C.

The solids content (1 g, 1 h, 180oC):29.1 percent.

Example 13 (comparative)

Obtaining polyurethane varnish

At temperatures below 30oC to 21,05 g 1-methoxypropylacetate-2 add 7,21 g of 1,3-butanediol, 9,20 g of trimethylolpropane and 112,07 g of 4,4'-diphenylmethanediisocyanate. The mixture is heated under stirring up to 80-100oC and kept at this temperature until, until the isocyanate content reaches a figure 12-17%. Then cooled to 50-60oC and at this temperature, add 172,08 g of cresol and 57,84 g solvent-naphthas is e isocyanate reaches a rate less than 0.2%. After this is cooled to 40-60oC. Then add 280,12 g iminodiethylamine ester from example 7, 230,50 g of cresol, 107,78 g solvent-naphtha and 2.15 g of octoate zinc and stirred for three hours.

The expiry time, DIN 53211, 4 mm, at 23oC:63 C.

The solids content (1 g, 1 h, 180oC):29,0%.

Obtained in examples 8-13 varnish was coated wire using a standard apparatus for applying coatings.

Conditions coating:

drying oven: MAG AW/1A

temperature: 400oC

application equipment: nozzle

the wire diameter: 0.50 mm

the number of broaches: 10

magnification: 2L

Covered wire was tested according to IEC 851. The results obtained are presented in tables 2 and 3.

Obtained in examples 8-12 varnishes for coating wires according to the invention are stable in storage and compared to the standard have significantly higher adhesion to the copper wires of 0.5 mm Wire with a coating of varnish according to the invention, in terms of its resistance to thermal shock and partly also its thermoplasticity noticeably superior wire, covered tradie 153-173oC, is also higher than that presented in the comparative example. The advantage of these wires technically is especially significant, as they provide the possibility of obtaining higher thermal characteristics while maintaining a short service time. Further it should be noted that the optimum qualities can be achieved in contrast to comparative example 13 at 20% increase in feed rate. It should be noted, moreover, that when the driving speed of 60 m/min is possible to shorten the time of soldering to less than one second at 420oC, respectively, significantly reduce the temperature of the soldering bath to 375oC while maintaining the length of service. Increasing the feed rate and reduced maintenance time and reducing the bath temperature soldering represent a significant technical advantage of the invention.

Example 14

Modified 2,6-naphthaleneboronic acid THEIC-polyetherimide

Out of 72.9 g of ethylene glycol, 192,2 g THEIC, and 83.3 g of dimethyl terephthalate, 104,4 g of dimethyl ester of 2,6-naphthaleneboronic acid, to 220.1 g of anhydride trimellitic acid, 112,0 g of 4,4'-diaminodiphenylmethane to 96.8 g of distillate. If 200oC product softens 808,5 g of cresol. Chilled kretly solution diluted 288,5 g solvent-naphtha and catalyst with 11.4 g of chrisitianity.

Viscosity: 950 mPas.

The solids content (1 g, 1 h, 180oC):38,9%.

Example 15 (comparative)

THEIR-polyetherimide

Method for producing a product in one unit of 72.9 g of ethylene glycol, 194,2 g THEIS, 166,6 g of dimethyl terephthalate, to 220.1 g of anhydride trimellitic acid, 112,0 g of 4,4'-diaminodiphenylmethane and 0.7 g of Tetra-n-butylmalonate by heating to 200oC get polyetherimide resin. You get 95,1 g of distillate. The product softens at 200oC 808,5 g of cresol. Chilled kretly solution diluted 288,5 g solvent-naphtha and catalyst with 11.4 g of chrisitianity.

Viscosity: 810 mPas.

The solids content (1 g, 1 h, 180oC):39,8%.

Both varnish used for coating and tested according to IEC 851.

Conditions coating:

drying oven: MAG AW/1A

temperature: 520oC

application equipment: nozzle

the diameter of wires: 0.71 mm

the unwinding speed: 32 m/min

the number of broaches: 10

the degree policemilitary 2,6 - naphthaleneboronic acid THEIC-polyetherimide. Comparative lacquer from example 15 is a traditional polyetherimide. As shown by the results, thanks to the introduction of 2,6 - naphthaleneboronic acid adhesive force with wire, as well as resistance to thermal shock significantly increased.

1. Tool coatings of the wires on the basis of polyester resins or polyetherimide resins, or consisting of a hydroxyl group of the polyol together with the isocyanate component, free isocyanate groups which completely blocked, in combination with catalysts, organic solvents and additives, characterized in that its basis is obtained from polyhydric alcohols, esterified naphthaleneboronic acid and/or its tarifitsiruemye derivatives, optionally in a mixture with other dicarboxylic acids and/or their derivatives, as well as not necessarily having in its composition kidnie group or forming kidnie group of the original substances.

2. The facility covering the wires under item 1, characterized in that it comprises a) 15-65 wt.%, preferably 25-55 wt.% polyester or polyetherimide or consisting of a hydroxyl group of the polyester together with the isocyanate component, the Torah, preferably, lead acetate, zinc acetate, titanate or organic acid, or amine catalysts and in) 35-80 wt.%, preferably 45-72 wt.% organic solvents, preferably krasilnik or Nekretnine organic solvents and diluents.

3. Tool coatings of the wires on one of the PP.1 or 2, characterized in that it comprises a) 15-65 wt.%, preferably 40-50 wt.%, in terms of the total weight of tool coatings, one or more polyester resins, or (b) 15-60 wt. %, preferably 30-50 wt.%, in terms of the total weight of tool coatings, one or more of polyetherimide or) 18-40 wt. %, preferably 25-35 wt.%, in terms of the total weight of tool coatings, one or more having in its composition a hydroxyl group of the polyol and one or more isocyanate components, free isocyanate groups are completely blocked.

4. Tool coatings of the wires on one of the PP.1 to 3, characterized in that it comprises a) 30-55 wt.% polyester or polyetherimide or consisting of a hydroxyl group of the polyester together with the isocyanate component, free isocyanate groups which completely blocked, b) 0.5 to 2, utilizatori, in) 40-67 wt.% organic solvent, preferably from among krasilnik or Nekretnine organic solvents and diluents and 0.5-5.0 wt.% phenolic resin, preferably condensation products of phenol, substituted phenols or bisphenol a with formaldehyde.

5. Tool coatings of the wires on one of the PP.1 to 4 , characterized in that as naphthaleneboronic acid use 1,4-, 1,8-, 2,3-, 2,6- naphthaleneboronic acid.

6. Tool coatings of the wires on one of the PP.1 to 5, characterized in that as other dicarboxylic acids used are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, timelineview acid, azelaic acid, sabotinova acid, maleic acid, fumaric acid, sorbic acid, phthalic acid, terephthalic acid and/or isophthalic acid.

7. Tool coatings of the wires on one of the PP.1 to 4, characterized in that the polyesters or polyetherimide, or consisting of hydroxyl group of the polyol together with the isocyanate component, free isocyanate groups which completely blocked, obtained from (a) 1-100 mol.% natalijagolosova acid and b) 0-em, as polyhydric alcohols preferably used ethylene glycol, 1,2 - and 1,3 - propylene glycol, 1,2-, 1,3 - and 1,4 - butanediol, 1,5-pentandiol, neopentylglycol, diethylene glycol, triethylene glycol and/or trioli, preferably glycerin, trimethylacetyl, trimethylolpropane or Tris (2-hydroxyethyl)isocyanurate.

9. A way of raising funds to cover the wires on one of the PP.1 to 8, characterized in that carry out the condensation reaction between naphthalenemethanol(s) acid (s) and/or its (their) tarifitsiruemye derivatives and polyhydric alcohols in an organic solvent, optionally with the use of mesotelioma or imidazoli starting substances are mixed with the catalyst, and optional phenolic resin, other auxiliary agents and additives, forming in this way the composition of the funds to cover the wires.

10. A way of raising funds to cover the wires on one of the PP.1 to 9, characterized in that the polyester resin or polyetherimide resin, or consisting of hydroxyl group of the polyester condensation in the melt and then dissolved in an organic solvent.

11. A way of raising funds to cover the wires on one of the PP.1 the performance communications group polyester condense the solvent.

 

Same patents:

The invention relates to the insulation of the surfaces of metal products, mainly jewelry, at local, predominantly electrochemical and chemical processes, and is intended for use in the jewelry industry, instrument-making, machine-building and local industry

The invention relates to electrical engineering, and in particular to compositions insulating coatings and impregnation of windings of electrical machines and devices operating at high temperatures

The invention relates to the production of insulating coatings on electrical steel used in the magnetic circuits of electrical machines, apparatus and instruments

The invention relates to the production of electrical insulating varnishes for coating of enamel wires and reduces the emission of harmful volatile substances by increasing the solids to increase the mechanical strength and breakdown voltage of insulation, as well as to expand the raw material base

The invention relates to film-forming compositions and methods of formation of these silicate dielectric layers on semiconductor structures, ceramic and glass plates and can be applied in electronics, in particular, in the manufacture of semiconductor integrated circuits methods of planar technology

The invention relates to the field of polymer chemistry, namely to photopolymerizable dielectric compositions (FDC) used in electronic industries for production of lacquer coatings on circuit boards for the purpose of electrical insulation of the components and protect them from external factors

FIELD: polymer materials.

SUBSTANCE: insulating varnish for coating enameled wires contains polyesteramide resin cresol solvent, petroleum solvent, and tetrabutoxytitanium, said cresol solvent being the one recovered by treatment coal oil and consisting of phenol, o-, m-, and p-cresols, and xylenols, which has following fraction composition (by volume): up to 180°C not more than 3%, 190-205°C at least 70% and up to 210°C at least 85%.

EFFECT: lowered cost price of varnish and improved quality of finished product.

1 tbl, 9 ex

FIELD: polymer materials.

SUBSTANCE: insulating varnish for coating enameled wires contains polyester resin, titanium catalyst, and organic solvents, titanium catalyst being, in particular, tetrabutoxytitanium and organic solvents being petroleum solvent and cresol solvent recovered by treatment coal oil and consisting of phenol, o-, m-, and p-cresols, and xylenols, which has following fraction composition (by volume): up to 180°C not more than 3%, 190-205°C at least 70% and up to 210°C at least 85%.

EFFECT: lowered cost price of varnish and improved quality of finished product.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed insulating coating composition, containing bitumen in amount 90-100 wt fractions, fluorocarbon polymer 32 LN in amount 10-15 wt fractions, butyl acetate in amount 40-45 wt fractions, acetone in amount 40-45 wt fractions and mica in amount 2-3 wt fractions.

EFFECT: improved insulating properties, mechanical strength and chemical stability.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: varnish contains a varnish base, a functional additive which increases coating hardness, siccative HF and methyl ethyl ketoxime radical polymerisation inhibitor. The varnish base is an oligomer with strongly polar chromane rings. The oligomer is obtained by reacting tung oil and 101L phenol-formaldehyde resin, taken in equivalent ratio of 1:0.15-0.18, respectively, while heating said mixture for 60 minutes at temperature 160C. After extracting water, temperature is raised to 182C until achieving viscosity of 25-36 s. The oligomer is added to the composition in 50% xylene solution. The functional additive used is rosin ester with glycerine. Components are in the following ratio, wt %: oligomer - 31.0-36.2, rosin ester with glycerine - 9.0-3.8, siccative HF - 2.00, methyl ethyl ketoxime - 0.60, xylene - the balance.

EFFECT: wider raw material base, replacing molten amber, which is not produced on an industrial scale, with rosin ester with glycerine, high content of non-volatile substances, elasticity and electrical strength of the coating.

1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of nanomaterials in wire enamel for improving thermal properties of enamel. The nanomodified wire enamels are usually used in making insulated winding wire. The polymer base of wire enamel is selected from a group comprising polyamideimide, polyester, polyesterimide, polyurethane and mixtures thereof. The nanomaterial is selected from a group comprising nano-oxides, metal nano-oxides, metal oxides or hydroxides of aluminium, tin, born, germanium, gallium, lead, transition metals, lanthanides, actinides and mixtures thereof. The nanomaterial is also selected from a group comprising nano-oxides, metal nano-oxides, metal oxides and hydroxides of aluminium, silicon, titanium, zinc, yttrium, vanadium, zirconium, nickel and mixtures thereof. After applying enamel on the wire and curing thereof, the wire exhibits improved thermal and mechanical properties.

EFFECT: improved thermal properties of enamel.

8 cl, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention can be used in producing wires with enamel insulation for motors, coils and transformers. The wire enamel contains binder, an organic solvent, auxiliary substances and additives, an adhesion promoter selected from imidazole, pyrrolidone, amidocarboxylic acids, derivatives thereof and mixtures thereof. The method of coating electric wires with the enamel involves providing an electric wire, applying the enamel and curing.

EFFECT: improved adhesion of the enamel to electric wires.

20 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of electrically insulating lacquer for coating metal bases. Said lacquer contains (wt %): epoxy-diane resin 7-7.4, polyphenyltetraepoxy siloxane - 2.4-3, alkyd-epoxy resin VEP-0179 - 2.4-3.8, triethylamine - 0.16-0.28, acetone - 20.1-23.6, distilled water - the balance. To apply the lacquer onto a metal substrate, two electrodes - the article-electrode and an auxiliary electrode - are immersed in said lacquer. Positive potential is applied across the article-electrode relative the second auxiliary electrode and with current density of 0.2-1.5 mA/cm2 for 5-15 s, a dense homogeneous electrophoretic film-forming precipitate is electrically deposited on the article-electrode. The article is then placed in a heating cabinet for 30-50 s in which there is a vacuum of 50-60 torr and temperature of 30-40C. The article is then held in a furnace for 1-1.5 min at temperature of 400-500C.

EFFECT: inventions reduce emissions of harmful volatile substances, increase mechanical strength and breakdown voltage of the electrical insulation, enable to deposit a dense, homogeneous and quality film layer without using any mechanical devices.

2 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to obtaining electroinsulating varnishes for covering metal bases, for instance, copper wires, starter slots and electric motor armatures, conductors of printed circuit boards, etc. Method of application of electroinsulating coating on metal substrate includes preparation of electrophoretic composition based on varnish PE-939 of grade B, for which purpose it is mixed with 1% ammonia solution, ethylcellosolve and dioxane, after which into prepared electrophoretic solution submerged are two electrodes at distance 10-30 mm, one of which is electrode-product and the other is auxiliary electrode; positive potential relative to second auxiliary electrode is supplied to said electrode-product, and dense homogeneous electrophoretic sediment of film-forming is electrically precipitated on product at current density 2-10 mA/cm2 for 10-20 s, after that, electrode-product is removed from varnish, placed into heat chamber, 50-60 Torr vacuum and temperature 30-40C are created in heat chamber, and electrode-product is kept at said temperature for 20-40 s, after that said electrode-product is removed from heat chamber and placed into oven, inside which temperature 350-450C is created, and electrode-product is kept in oven for 60-90 s, after which electrode-product is removed from oven.

EFFECT: method provides increase of quality and exploitation reliability of insulating coating: specific volume resistance, resistance to chemical reagents, elasticity, electric and mechanical strength.

FIELD: metallurgy.

SUBSTANCE: invention relates to chrome-free material for an insulation coating of non grain-oriented electrical steel. Material contains the following components with the corresponding weight fractions: primary acid salt of metal of phosphorus acid in the volume of 100 fractions, epoxy resin in the volume of 10-60 fractions, a drying agent - naphthenate or a drying agent - salt of metal of isooctane acid in the volume of 0.001-10 fractions, an organic solvent in the volume of 0.001-100 fractions and clean water in the volume of 60-2000 fractions. As primary acid salt of metal of phosphorus acid there used is Al(H2PO4)3, Mg(H2PO4)2, Ca(H2PO4)2, Zn(H2PO4)2. As epoxy resin there used is water-soluble epoxy resin or an epoxy resin emulsion.

EFFECT: after chrome-free material of an insulation coating is applied to non grain-oriented electrical steel, it has highly transparent appearance, excellent insulation properties, corrosion resistance, adhesion ability, weldability and processibility, which eliminates demerits inherent in existing chrome-free coatings, for example adhesiveness and bad wear resistance, as well as meets environmental protection requirements.

5 cl, 4 tbl

FIELD: electricity.

SUBSTANCE: invention relates to electric engineering, and more specifically to compositions of insulating coatings and impregnation compounds for windings of electrical machines and mechanisms operated at high temperatures and intended mainly for application of coating by dipping. Impregnating insulating enamel includes polymethylphenylsiloxane lacquer, metal oxides, acrylate copolymer, butyl acetate, silicone antifoamer, rheological additive with thixotropic effect and aromatic solvent.

EFFECT: coatings are obtained with electric strength of enamel film at AC voltage (50 Hz) at temperature of 15-35C and relative humidity of 45-75% equal to at least 60 kV/mm and specific volume resistance of enamel film in initial state at temperature of 15-35C relative humidity of 45-75% equal to at least 1,01012 Ohmcm.

1 tbl

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