DE3034536A1 - Polyamideimide resin compsn. - contains polyester resin contg. hydroxy gp. derived from terephthalic and/or isophthalic acid, for improved flexibility - Google Patents

Abstract

Polyisocyanate contg. isocyanurate ring (e.g. prepd. from 4,4'-diphenylmethane diisocyanate, 4,4'-diisocyanate by the trimerisation at 50-150deg.C. in the presence of trimerisation catalyst e.g. alkali metal acetate, Fe, Mg, Ni, Zn, Sn, Pb, V and Ti salts and organometallic cpds. and tert. amines ) (1- 30 equiv. per 100 total equiv. of isocyanate), a lactam (e.g. epsilon-caprolactam) (30-80 equiv. per 100 equiv. of total isocyanate) and polycarboxylic acid contg. acid anhydride (e.g. trimellitic anhydride) are reacted in a cresol solvent to provide polyamideimide resin contg. residual isocyanate content of 10-70%. The resin is blended with polyester resin contg. OH derived from terephthalic and/or isophthalic acid(s) as its acidic component(s). The addn. of polyester resin contg. OH derived from terephthalic and/or isophthalic acid(s) improves markedly the flexibility and softening temp. when baked at a high rate.

Description

Bes ohre ibun

The invention relates to polyamide-imide resin compositions.

Polyester type paints are currently widely used as electrical Insulating varnishes, especially as varnishes for enamelled wires, used as they balanced properties in terms of mechanical properties, electrical properties Properties, heat resistance and the like.

The current trend towards miniaturization and weight saving of electrical equipment requires that enamelled wire enamels have a good heat resistance and excellent abrasion resistance as well as excellent Have resistance to freon. As a varnish for enamelled wires with good heat resistance, abrasion resistance and resistance to freon are varnishes with high heat resistance, such as ftlyimidlacke, polyamide-imidlacke and the like, known. However, these paints have problems because they are only available in special solvents, such as N-methylpyrrolidone (NMP), are soluble as the resins themselves are expensive and the like. About the heat resistance of polyester paints So-called polyester-imide varnishes can be improved for enamelled wires have been proposed to contain imide groups in some parts of the resin component.

Polyester-imides are compared to polyesters in terms of improved heat resistance, but have disadvantages in terms of heat softening properties, the resistance to freon and the abrasion resistance. Even in the case of with tris (2-hydroxyethyl) isocyanurate modified polyester-imides, in which an improvement in heat softening properties has been sought is, these products are in terms of abrasion resistance and durability unsatisfactory compared to freon and they are not equivalent to polyamide-imides.

There are still various researches about the production of polyamide-imide varnishes with excellent heat resistance, which are used in general-purpose solvents, such as cresol, are soluble, have been carried out. It has also been suggested many times to use a lactam or the like as a reactive component (see.

e.g. JA-AS'en 29 730/71, 30 718/74, 20 993/75 and 47 157/78).

The practically obtained lactam-modified polyamide-imide which is soluble in cresol However, in terms of heat resistance, especially the breakdown temperature, considerably inferior to conventional polyamide-imides. To improve the heat softening properties it may be possible to use a polyisocyanate with an isocyanurate ring as part of a To use isocyanate compound, but such a mass is in view the heat softening properties are improved, but in terms of flexibility considerably deteriorated, as a result of which no resin valuable for practical use is obtained will. For example, if the burning time becomes long, the flexibility is lowered, although the heat softening properties are good. On the other hand, when the burning time is low, the resin cannot be polymerized enough to produce a high Molecular weight, and heat softening properties and flexibility are therefore deteriorated.

A polyamide-imide resin has already been developed that consists of a Polyisocyanate with isocyanurate rings, an aromatic diisocyanate, a lactam and an acid anhydride and that has good heat resistance and had flexibility and that was soluble in cresol. However, this resin was re the workability with problems, since there is not enough in the case of rapid burning Polymerization could be obtained that a high molecular weight and a high Breakdown temperature could be achieved. Furthermore, the flexibility was lowered.

It has been believed that the problem of the quick workability of the curing speed of the resin could be dependent. Extensive investigations have now found that the main reason for this is the slow cure rate was.

It is also already known to use a phenolic resin, an epoxy resin To use melamine resin or the like as a curing agent for linear polyamide-imides. For example, the use of melamine resins is described in JA-OS 102 278/73. Even if a melamine resin becomes a substantially linear polyamide-imide, the does not contain a polyisocyanate with isocyanurate rings as a component no improvement in flexibility and breakdown temperature is obtained. Rather, there is even a tendency that these properties are worsened, which has led to the fact that the melamine resin is not used in practice.

It was found that a polyamide-imide resin with significantly higher Heat resistance than the linear polyamide-imide by inclusion of polyisocyanate units obtain which isocyanurate rings in the resin skeleton contain. Furthermore, curing agents (crosslinking agents) for the polyisocyanate, the isocyanurate rings contains, examined.

As a result, it was found that when special components were added according to the invention to polyamide-imide resins with polyisocyanate with isocyanurate rings and lactam had been modified had significant effects, namely prevention the lowering of the flexibility and the breakdown temperature at the time of Fast machining, could be obtained without sacrificing flexibility and breakdown temperature of the enameled wires were deteriorated.

Polyamide-imide resins are still used as heat-resistant coating compositions for covering heat-resistant cooking appliances, for manufacturing internal parts used by electronic devices, magnet wires and the like. However, since General-purpose polyamide-imide resins such as HI-404, HI-600 (trademarks for products from Hitachi-Chemical Co., Ltd.), only in N-methylpyrrolidone (NMP) and similar special ones Solvents are soluble because of the use of expensive solvents significant cost problems. It is already a polyamide-imide with good heat resistance and impact resistance that is soluble in cresol. Such a polyamide-imide resin Although it can have good heat resistance and impact resistance, as well as good appearance obtained without blistering if the firing conditions are selected correctly, however, this product is relative to the general purpose resins HI-404, HI-600 and the like the surface appearance of the Inferior to coating film because on the surface is finely roughened and wrinkled.

This appears to be the basic problem of polyamide-imide resins which have been modified with polyisocyanate with isocyanurate rings and with lactam and which are soluble in cresol. This is likely due to the slow cure speed Due to extensive investigations have now shown that the fine roughening the surface and the formation of wrinkles on the surface can be improved, when adding a metal salt of Sn, Mn, Co and / or Zn to the resin.

The invention relates to a polyamide-imide resin composition comprising the following contains: (A) a polyamide-imide resin, produced by reacting a polyisocyanate, containing one or more isocyanurate rings, an aromatic diisocyanate, a lactam and a polycarboxylic acid having at least one acid anhydride group contains, in a cresol-type solvent, and (B) at least one substance from the group (1) alkoxy-modified amino resins, (2) polyisocyanates, the one or contain several isocyanurate rings, (3) phenol / formaldehyde resins, (4) epoxy resins, (5) Polyester resins which contain one or more hydroxyl groups and which are made using from terephthalic acid and / or isophthalic acid as the acid component and (6) at least one metal salt of Sn, Nn, Co and / or Zn.

Figures 1 to 3 show the relationship between the percentage Extraction and heating time at 2500C. Figure 4 shows a schematic Drawing of a device for measuring the shock temperature.

The polyisocyanate with one or more isocyanurate rings can, for example can be obtained by trimerizing a polyisocyanate compound. This reaction can be carried out in a solvent that deals with the isocyanate group does not implement. In order to effectively carry out the reaction, it is desirable to use a catalyst to be used for the trimerization of polyisocyanate compounds. The product is a polyisocyanate containing one or more isocyanurate rings, the polyisocyanate is a non-masked material. Any of any can be used as the solvent capable of dissolving the polyisocyanate compounds. Examples for such solvents are aliphatic and aromatic hydrocarbons, halogenated aromatic hydrocarbons, esters, ketones, ethers, ethylene glycol monoalkyl monoacetates, Dimethyl sulfoxide and the like.

Examples for catalysts for the trimerization of polyisocyanate compounds are alkali metal acetates, metal salts of iron, magnesium, nickel, zinc, tin, Lead, Vanadium, titanium etc., organometallic compounds such as e.g. titanium tetrabutoxide, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) undecene-7, Mannich bases of phenol, such as 2- (dimethylaminomethyl) -4, 6-dimethylphenol etc., tertiary amines, such as N, N-bis (dimethylaminoethyl) -N-methylamine, 2-dimethylaminoethanol etc., and organic carboxylates of tertiary amines.

The trimerization of the polyisocyanate compound can, for example be carried out at a temperature of 0 to 1600C.

The trimerization of polyisocyanate compounds is in practice very complicated. An isocyanate adduct is not always selectively obtained contains only one isocyanurate ring in a molecule. Furthermore, there is also a mixture obtained, the unreacted polyisocyanate and isocyanate adducts with two or contains several isocyanurate rings in one molecule. According to the invention can also such a mixture can be used. The amount of catalyst and the reaction temperature Depending on the number of isocyanurate rings present in the isocyanate adducts are selected. For example, if the reaction is carried out in such a way that the proportion of the remaining isocyanate groups is about 50%, then are preferred 0.01 to 2% by weight of a tertiary amine, based on the weight of the starting polyisocyanate, and a reaction temperature of 30 to 1500C is used.

As the starting polyisocyanate for the production of the polyisocyanate, which contains one or more isocyanurate rings, any diisocyanate compounds, which can form isocyanurate rings can be used, namely either aliphatic, alicyclic or aromatic diisocyanate compounds. If you have the Takes into account heat resistance, solubility and production cost, then preferred examples are aromatic diisocyanates, such as 4,4'-diphenylmethane diisocyanate, Tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate and the like. These compounds can be used either alone or as a mixture of two or more be used.

The polyisocyanates that contain one or more isocyanurate rings, can be used either alone or as a mixture of two or more. It is also possible to use one or more polyisocyanates that have previously been synthesized are, or one or more polyisocyanates that contain one or more isocyanurate rings and which are blocked by blocking agents such as phenol, cresol etc. after the Synthesis has been stabilized to prevent changes over time, to use. The number of isocyanurate rings in the polyisocyanate with one or several isocyanurate rings can be changed depending on the purpose, however the content of the remaining isocyanate groups is preferably in the range of 10 up to 70% (if the content of isocyanate groups in the starting diisocyanate is 100% applies). If the content is too high, the heat resistance will be lowered, while, on the other hand, if the content is too low, the flexibility is lowered.

The amount of polyisocyanate with one or more isocyanurate rings, which is used is very important for the purposes of the invention. The same goes for for the crowd of the lactam described below. It is preferred the polyisocyanate with one or more isocyanurate rings in an amount of 1 up to 30 equivalents, based on the total isocyanate equivalent. if the amount is outside of the stated range, then none will be balanced Properties of heat resistance and flexibility are obtained. On the other hand, if the amounts are too large, then due to the synthesis an increased degree of branching a gelation take place.

As lactams, just like the polyisocyanates with one or more Isocyanurate rings are important starting materials for solubilizing the end product are in a cresol type solvent, any materials can be used capable of doing so with isocyanate groups and / or acid anhydride groups to react in a cresol type solvent and which are soluble in the solvent are. Examples of suitable lactams are ε-caprolactam, dodecyllactam, etc. These Lactams can be used either alone or as a mixture.

Among these, in terms of solubility, reactivity and the production cost s-caprolactam is preferred.

It is not necessary to add the lactam in an equivalent amount of the isocyanate group (where £ -caprolactam is taken as bifunctional i.e. 1 mole is equivalent to 2 equivalents). There is no guarantee that that will Use of a larger amount of lactam for efficient absorption of the lactam leads into the skeleton of the resin formed. The lactam is used in an amount of 20th up to 90 equivalent%, based on the total isocyanate equivalent, taking into account heat resistance, flexibility and solubility. The lactam is essentially built into the resin. If the crowd is outside of the above Is within the range, a polyamide-imide resin which is balanced will not be obtained Has properties of heat resistance and flexibility and which has excellent resistance to freon and abrasion effects.

Preferred aromatic diisocyanates are 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, tolylene diisocyanate, xylylene diisocyanate, etc. be used. These diisocyanates can either be used alone or as a mixture two or more can be used.

Polycarboxylic acids which contain at least one acid anhydride group can be any carboxylic acids with an acid anhydride group that reacts with isocyanate groups and their derivatives, such as products of the following formulas: where R is hydrogen, alkyl, preferably having 1 to 8 carbon atoms, or phenyl and X is CH2, -CO-, -S02- or -0-. An example of this is trimellitic anhydride, etc. These polycarboxylic acids can be used either alone or as a mixture. If necessary, part of the polycarboxylic acid with at least one acid anhydride group can be replaced by at least one carboxylic acid dianhydride, such as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, bieyelot2,2,22-oet- (7) -en-2-carboxylic acid dianhydride and their derivatives tetracarboxylic acid (7) -en-2: 3,5: 6hydride / or by at least one aliphatic or aromatic dibasic acid, such as adipic acid, sebacic acid, etc., replaced. Among them, trimellitic anhydride is preferably used in consideration of heat resistance and production cost.

The amounts of the isocyanate component and the acid component used are preferably in the range from 1.5 to 0.7 / 1 expressed as the ratio of Carboxyl group and the acid anhydride group to the isocyanate group. In particular is a ratio of about 1/1 for obtaining a high molecular weight resin most preferable.

The reaction to produce the desired polyamideimide resin can be be carried out in such a way that all starting materials are the same Time is added and the reaction is carried out at a temperature of about 160 to 230C. A preferred process for preventing turbidity is to remove all of the isocyanate components, to introduce the lactam and the cresol-type solvent into a reactor which Mixture at a temperature of 160 to 1900C for 1 to 3 hours to let the polycarboxylic acid with at least one acid anhydride group into the reactor to give and the reaction at a temperature of 200 to 2300C for 3 to 20 hours to continue. The progress of the reaction can be monitored by measuring carbon dioxide gas bubbles, generated during the reaction and the viscosity of the reaction solution to be tracked.

To prevent changes over time and to respond to be carried out uniformly, it is advisable to use the isocyanate component beforehand to dissolve the cresol type solvent. To aid the progress of the response, Organometallic salts, e.g. tin octoate, tin octoate, cobalt octoate can be used as a catalyst etc., and tertiary amines conventionally used will.

As the cresol type solvent, cresol, phenol, xylenol, etc. be used. These solvents can be used either alone or as a mixture will. High-boiling aromatic organic compounds can be used as part of a solvent mixture Solvents such as xylene, Nisseki Hisol-100 and 150 (trademarks for aromatic Hydrocarbons from Nippon Petrochemicals Co., Ltd.), cellosolve acetate and the like, be used.

The polyamide-imide resin produced in this way, which is in a solvent is soluble of the cresol type is excellent in heat resistance and durability against freon and abrasion. It has pretty good flexibility when the resin is used alone. However, as mentioned above, the curing speed is relatively small, the disadvantage is that it is in comparison to conventional licking requires a longer burning time (i.e. the product has bad Fast editing properties). It is therefore necessary to shorten the burning time, i.e. to make hardening faster. On the other hand, if the Burning speed usually deterioration in appearance and degradation of flexibility.

In order to avoid such undesirable phenomena, the special Component (B) used as a curing agent according to the invention. The component (B) is used in an amount of preferably 1 to 300 parts by weight per 100 parts by weight of component (A) is used.

Any desired products can be used as alkoxy-modified amino resins (1) are used, which are obtained by reacting an amino compound, e.g. melamine, benzoguanamine, Urea or the like, with formaldehyde or paraformaldehyde by addition condensation reaction and by alkoxylating the resulting methylol group or groups with a Alcohol such as methanol, ethanol, propanol, butanol, or the like have been. Co-condensation polymers or mixtures thereof can also be used will. Although the reasons for this are not yet clear, are alkoxy-modified ones Benzoguanamine / formaldehyde resins, such as butylated benzoguanamine / formaldehyde resin, effective.

The effect of adding the alkoxy-modified amino resin is in the case of the polyamideimide resin used according to the invention, which is soluble in cresol, considerably. However, this effect can occur in the case of conventional polyamide-imide resins, the are soluble in NMP-type solvents are not shown. The mixed The amount of the alkoxymodified amino resin (1) in the polyamide-imide resin (A) varies according to the composition of the alkoxy-modified amino resins to be mixed together, the molecular weight and functional groups of the resin. Generally will they within the range in which no phase separation takes place, and depending on the Purpose determined. In the case of stoving enamels for wires, it is more preferred the alkoxy-modified amino resin in an amount of about 1 to 20% by weight as resin weight, based on the weight (solids content) of the polyamide-imide resin, to add. Any method can be used as the mixing method. For example, a solution of the alkoxy-modified amino resin is previously in Cresol is dissolved and the resulting mixture is poured into the polyamide-imide resin. One can also proceed in such a way that one leads to a directly heated polyamide-imide resin solution a solution of the alkoxy-modified amino resin is dropwise.

The temperature at the time of mixing is in the range of Room temperature to 2000C, where no phase separation occurs and a uniform one Mixing is possible.

As polyisocyanates that contain one or more isocyanurate rings, (2) any substances can be used that can be produced by trimerization a polyisocyanate compound. For example, a trimer is obtained by reacting an aromatic diisocyanate, in particular tolylene diisocyanate, in the presence of a tertiary amine, or a mixture of the trimer and polyisocyanates, which contain one or more isocyanurate rings are preferred.

The amount of polyisocyanate with one or more isocyanurate rings to be added (2) as the curing agent varies according to the polyfunctionality of the one to be added Polyisocyanate. However, in the case of stoving enamels for wires, it is more preferred about 1 to 20% by weight, expressed as solids content, based on the weight (solids content) of the polyamide-imide resin. Products can also be used which have previously been masked with phenol, cresol, s-caprolactam and the like. As for the method of addition, the polyisocyanate (2) can be added to the polyamide-imide resin Can be added at normal temperatures or it can be directly heated Solution of the polyamide-imide resin are added.

It is also possible to mix the resin with another resin for baking enamels for wires; e.g. a polyester resin, a polyester-imide resin, depending on the purpose to mix.

A phenol / formaldehyde resin, an alkylphenol / formaldehyde resin, a modified phenol / formaldehyde resin derived therefrom or the like can be used. Regarding the nature of these substances exist no restrictions. As modified phenol / formaldehyde resins, e.g. Amino compounds modified phenol / formaldehyde resins, such as phenol / formaldehyde resin modified with melamine, Phenol / formaldehyde resin modified with benzoguanamine, modified with urea Phenol / formaldehyde resin and the like can be used. The amino compound can also be the aforementioned alkoxy-modified amino resin.

The amount of phenol / formaldehyde resin to be mixed in varies depending on according to the molecular weight and the nature of it contained functional Groups. Usually, it is in the range where none, depending on the end use Phase separation takes place. In the case of wire stoving enamels, it is more preferred it in an amount of about 1 to 30% by weight in terms of resin weight based on the weight (solids content) of the polyamide-imide resin. What the Mixing method is concerned, the phenol / formaldehyde resin to be added is previously dissolved in cresol dissolved and the resulting mixture is added to the polyamide-imide resin. Man can also proceed in such a way that the phenol / formaldehyde resin is added dropwise to a directly heated solution of the polyamide-imide resin.

As the epoxy resin (4), bisphenol type epoxy resins such as Epikote can be used 828, 1001, 1004, 1007, etc. (manufactured by Shell Chemical Corp.), epoxy resins dated Novolak type such as DEN 438 (manufactured by Dow Chemical Co.), heterocyclic rings containing epoxy resins such as TEPIC (manufactured by Shikoku Kasei K.K., Japan), containing tris (glycidyl) isocyanurate, alicyclic type epoxy resins such as e.g. CH 221 (manufactured by UCC, Ltd.) etc. can be used.

As to the epoxy resins to be used, there are no particular ones Restrictions.

The amount of the epoxy resin to be mixed varies depending on its kind. Usually it is selected according to the end use within the range in which no phase separation takes place. This is the case, for example, with stoving enamels for More preferably, it is expressed as wires in an amount of about 1 to 30% by weight Resin weight based on the weight of the polyamide-imide resin.

As for the mixing method, that will be added Epoxy resin previously dissolved in cresol and the resulting mixture becomes the polyamide-imide resin given, or you can also proceed in such a way that the epoxy resin is added dropwise to one directly heated solution of the polyamide-imide resin. To increase the viscosity to avoid in the course of time after the addition of the epoxy resin, it is preferred to if possible, the epoxy resin immediately before use to the polyamide-imide resin admit.

It is also possible to use the polyester resin as the curing catalyst one or more hydroxyl groups or hydroxyl radicals; that by using Terephthalic acid and / or isophthalic acid has been obtained as the acid component (5) is to use. In the production of such a polyester (5), terephthalic acid is used and / or isophthalic acid used as the acid component. In such a case can instead of terephthalic acid and isophthalic acid, for example, one or more Lower alkyl esters of terephthalic acid and isophthalic acid, such as dimethyl terephthalate, Monomethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate and the like, or one or more condensates of terephthalic acid and / or isophthalic acid with a glycol such as polyethylene terephthalate, polyethylene isophthalate, etc. used will.

Acids, which are generally used for electrical Insulating varnishes can be used, e.g.

Adipic acid, succinic acid, phthalic acid, trimellitic anhydride, imidodicarboxylic acids of the formula: in which R stands for a divalent organic radical, can also be used. The imidodicarboxylic acid of the formula III can be prepared by reacting 1 mole of a diamine with about 2 moles of trimellitic anhydride, as described, for example, in JA-AS 40 113/76. As the diamine, 4,4'-diaminodiphenylmethane, m-phenylenediamine, p-phenylenediamine, 1,4-diaminonaphthalene, 4,4'-diaminodiphenyl ether, 4,41-dimethylheptamethylenediamine, hexamethylenediamine, 4,41 -dicyclohexylmethanediamine, diaminodiphenylsulfone, etc. can be used . It is of course also possible to use an imidodicarboxylic acid which has been obtained using a diisocyanate instead of a diamine.

As an alcohol component for the production of the polyester with a or more hydroxyl groups (5) can be one or more polyhydric alcohols be used. As dihydric alcohols, e.g. ethylene glycol, diethylene glycol, Neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, etc. are used will. As trihydric or higher alcohols, e.g. glycerine, trimethylolpropane, Tris (2-hydroxyethyl) isocyanurate, pentaerythritol, etc. can be used. The usage of tris (2-hydroxyethyl) isocyanurate is used in terms of heat resistance preferred.

The synthesis of the polyester with one or more hydroxyl groups (5) Can be done with excess hydroxyl groups until an OH value of preferably 60 to 200 is reached. As a catalyst for synthesis you can use commonly used materials such as lead oxide, lead acetate, tetrabutyl titanate etc., used will. With regard to these materials exist no particular limitations. The synthesis temperature is usually 150 to 3000C.

When the polyester has one or more hydroxyl groups (5) with the polyamide-imide resin is mixed, then it is mixed with a solvent that usually used in leaks for enameled wires, e.g. cresol, phenol, Xylenol, N-methylpyrrolidone, xylene, etc., dissolved in such a way that the content of non-volatile Substances is 10 to 90 wt .-%. The polyester with one or more hydroxyl groups (5) may contain a hardener commonly used in enamelled paints Wires is used, e.g.

Tetrabutyl titanate, tetraisopropyl titanate, zinc naphthenate, cobalt octoate, Block isocyanate (Desmodule-CT stable, manufactured by Japan Polyurethane Industries, Co.) or the like before mixing with the polyamide-imide resin.

The temperature at which the polyester (5) is mixed with the polyamide-imide resin is usually room temperature to about 2000C and is not particularly limited as long as uniform mixing is possible.

The amount of polyester (5) to be admixed is not subject to any particular restrictions subjected, but is usually 1 to 300% by weight, more preferably 3 to 30% by weight, based on the weight (solids content) of the polyamide-imide resin.

To increase the roughening of the fine surface or the formation of wrinkles improve, at least one metal salt of Sn, Mn, Co and Zn (6) added to the polyamide-imide resin.

Example. for such metal salts are dibutyltin laurate, dibutyltin acetate, Manganese naphthenate, manganese octoate, cobalt naphthenate, cobalt octoate, zinc naphthenate, Zinc octoate and the like. These materials are commonly used as dryers. These metal salts can be used either alone or as a mixture.

The metal salt (6) is preferably used in an amount of 0.01 to 10 Parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight, in terms of solid content, of the polyamide-imide resin is used. The mixing of the metal salt (6) with the polyamide-imide resin can be used at room temperature to about 2000C and there are no particular restrictions in this regard.

In addition to the above component (B), i.e. the alkoxy-modified one Amino resin (1), the polyisocyanate with one or more isocyanurate rings (2), the phenol / formaldehyde resin (3), the epoxy resin (4), the polyester resin with a or more hydroxyl groups using terephthalic acid and / or Isophthalic acid as the acid component, (5) and the metal salt of Sn, Mn, Co and Zn, one or more other additives, such as other polyester resins, as mentioned above, other melamine resins as mentioned above, polyethers, polyamides, e.g. Nylon-6, nylon-6,6, nylon-12, polyamideimide, polyimide, polyhydantoin, guanidine carbonate, Benzotriazole, furan resin, phenoxy resin, rubbers, e.g. telechelic rubber with an average molecular weight of several thousand, natural rubber, Acrylic rubber, Acrylonitrile / butadiene rubber, hydrin rubber, Urethane rubbers, thioether rubber, butadiene rubber, can be added to the Properties to improve. These additives can be used in an amount from 0.1 to 30 % By weight based on resin solids content can be used.

Can also be used as a drying catalyst to improve the properties tertiary amines, such as triethylamine, triethylenediamine, N-methylmorpholine, N, N-diethylethanolamine, Dimethylaniline, etc., organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate etc., can be used.

The polyamide-imide resin composition obtained in this way can be used, for example, as a lacquer by dilution with a polar solvent such as a solvent mentioned above of the cresol type, NMP, dimethylformamide, dimethylacetamide or the like into one Resin content of 20 to 40 wt .-% can be used. In such a case, under Consider resin concentration and viscosity as co-solvents Xylene, Nisseki Hisol-100 (trademark for an aromatic hydrocarbon mixture from Nippon Petrochemicals Co., Ltd.), Cellosolve acetate (trademark, ethylene glycol monoethyl monoacetate, manufactured by Dow Chemical Co.) and the like can be used.

The coating film made using such a varnish has good heat resistance, resistance to Freon (resistance to the cooling medium), flexibility and against abrasion. It has improved rapid curing properties and an improved appearance. The product therefore has a good commercial Applicability. Furthermore, the polyamide-imide resin composition containing the metal salt (6) can have a Coating film having good heat resistance, impact resistance and having a improved prevention of fine surface roughening and wrinkling result.

The polyamide-imide resin composition according to the invention with snow hardening properties, which is soluble in a cresol type solvent can mainly be used as a varnish used for enamelled wires. But it can also be used as an impregnation varnish for electrical insulation, casting varnish, means for achieving a heat-resistant Coating, as a heat-resistant paint or a heat-resistant varnish, as a heat-resistant one Film, as a heat-resistant adhesive, as a heat-resistant lamination material, as a heat-resistant complex material together with glass fibers or carbon fibers or the like can be used.

The invention is illustrated in the examples. All parts are in it and percentages are based on weight, unless otherwise specified.

Verfilelchsbeispiel 1 (1) Synthesis of the trimer of aromatic diisocyanate: Ingredients g tolylene diisocyanate 600 xylene 600 2-dimethylaminoethanol (catalyst) 1.8 The above ingredients were placed in a four neck flask transferred, which was provided with a thermometer and a stirrer. The mixture was heated to 1400C in a stream of nitrogen. The reaction took place at this temperature carried out until the isocyanate group content became 25% (the initial concentration was 48, '). The resulting product showed the absorption of the isocyanate ring at 1710 and 1410 cm 1 and the absorption of the isocyanate group at 2260 cm 1 in the infrared spectrum, (2) Synthesis of a polyamide-imide resin soluble in cresol: components g equivalent ratio Diisocyanate trimer, synthesized under (1) (50% solution) 37.0 0.11 4,4'-diphenylmethane diisocyanate 113.3 0.91 Trimellitic anhydride 96.0 1.00 s-Caprolactam 36.6 0.65 Cresol 300 Die The above ingredients except for trimellitic anhydride were combined into one Four-necked flask with a thermometer, a stirrer and a tube for the fractional distillation was provided. It was heated to 1800C under nitrogen heated to carry out the reaction at that temperature for 90 minutes. Thereafter trimellitic anhydride was added to the flask and the temperature raised 2100C increased. The reaction was carried out at 210 ° C. for 15 hours. The resin concentration became adjusted to 30% with cresol to give a varnish.

The paint had a viscosity of 250 poises. The infrared spectrum of the resin showed the absorption of the imide group at 1780 cm1 and the absorption of the Amide group at 1650 cm-1 Comparative Example 2 (1) Synthesis of butylated benzoguanamine / formaldehyde resin: Ingredients g moles benzoguanamine 37.4 0.2 paraformaldehyde (purity 80%) 30 0.8 Isobutyl alcohol 118.4 1.6 The above ingredients were placed in a 300 ml three-necked flask entered, the one with a thermometer, a condenser with a receptacle for the quantitative determination of the water and a stirrer was provided.

The temperature rose to 1000C at a rate of 5 0C per minute with stirring and the reaction continued at that temperature for 1 hour carried out. Thereafter, 50 mg of pnthalic anhydride was added to the flask and the temperature was increased to 110 ° C. While maintaining the temperature at At 1100C the dehydration was carried out under reflux. At the time of termination the dehydration reaction, the butanol was taken out of the system until the temperature in the reaction system had increased to 1300C. Than the temperature had risen to 1300C, the withdrawal of the butanol was stopped and the flask was cooled.

When the temperature dropped to 500C, that became Reaction mixture diluted with a mixed solvent of butanol / xylene (weight ratio 1/1), whereby a resin solution having a solid content of 55 'was obtained.

(2) Manufacture of a polyamide-imide resin composition, the butylated benzoguanamine / formaldehyde resin Contains: To previously heated (1000C) HI-404 (trademark for a polyamide-imide resin compound the NMP solvent series manufactured by Hitachi Chemical Co., Ltd.) became the Solution of the butylated benzoguanamine / formaldehyde resin synthesized under (1) above with stirring in an amount of 5 parts in terms of solid content per 100 Parts of HI-404, expressed as solids content, are given, giving a uniform Resin solution was obtained.

Example 1 The polyamide-imide resin used in Comparative Example 1 (2) was synthesized was heated to about 80 ° C. and compared with that in the comparative example 2 (i) synthesized solution of the butylated benzoguanamine / formaldehyde resin in an amount of 3 parts in terms of solid content per 100 parts of polyamide-imide resin, in terms of solid content, added to form a uniform polyamide-imide resin composition was obtained.

Example 2 The polyamide-imide resin synthesized in Comparative Example 1 (2) was heated to about 1500C and with that in the comparative example 2 (1) synthesized butylated benzoguanamine / formaldehyde resin solution in an amount of 5 parts, expressed as the solids content, per 100 parts of polyamide-imide resin, in terms of solid content, added to form a uniform polyamide-imide resin composition was obtained.

Example 3 (1) Synthesis of butylated benzoguanamine / formaldehyde resin: Ingredients g Mol Benzoguanamine 22.4 0.12 Melamine 10.1 0.08 Paraformaldehyde (purity 8096) 36.0 0.96 Isobutyl alcohol 116.4 1.6 The components mentioned were as in Comparative Example 2 (1) reacted with one another. The resulting resin was made with a mixed solvent of butanol / xylene (weight ratio 1/1) diluted, whereby a resin solution having a solid content of 5596 was obtained.

(2) Manufacture of a polyamide-imide resin composition, the butylated benzoguanamine / formaldehyde resin Contains: A polyamide-imide resin composition was prepared in the same manner as in Example 2 described, manufactured, with the exception that the above below (1) synthesized. butylated benzoguanamine / formaldehyde resin in an amount of 8 parts in terms of solids content was added.

The 80 resin masses (lacquers) obtained were coated on wires, to get enamelled (or insulated) wires. The properties have been tested and they are summarized in Table I.

In all examples, the enameled wires were made under the following conditions Manufactured: Furnace: vertical furnace with a height of 4.5 m Furnace temperature: entrance / center / exit = 3000C / 3500C / 4000C (in comparative examples 2 and 3 28O0C / 3000C / 32O0C) wire diameter: 1 mm, with a kind of finished drawing speed: according to Tables I, II and III The properties were tested according to JIS standard C 3003. In the case of the breakdown temperature A load of 2 kg was used, respectively the breakdown temperature and the switching temperature.

Table I Sample Comparative HI-404 Comparative Example Example Example (Example no.) Example 1 example 2 1 2 3 pulling speed (m / min) 7.5 9 10 12 10 12 7.5 9 7.5 9 7.5 9 Properties Breakdown temperature (° C) (load 2 kg) 370 310 391 390 368 371 370 365 372 368 360 362 Flexibility (wrapping around the many diameters) good cracks good good cracks cracks good good good good good good Abrasion resistance (times) (load 600 g) 102 50 202 181 45 52 101 88 92 88 90 94 Surface condition good Bubbles good bubbles good bubbles good good good good good good As with Use of HI-404 and Comparative Example 2 shows when an alkoxy-modified Amino resin to a conventionally used basically linear polyamide-imide resin is given, the breakdown temperature, the flexibility and the abrasion resistance significantly lowered when these wires are drawn at a standard pulling speed of 10 m / min.

The surface condition of the wires is determined by pulling at a pulling speed vqn 12 m / min not improved.

On the other hand, as in Comparative Example 1 and Examples 1 through 3, an alkoxy-modified amino resin to a polyamide-imide resin is given, which with a polyisocyanate that has one or more isocyanurate rings contains, and a lactam has been modified, then there will be no lowering of the Breakdown temperature, flexibility and abrasion resistance of wires, pulled at a standard speed of 7.5 m / min. Furthermore, in the case of wires with a high pulling speed of 9 m / min have been drawn (high-speed machining), almost no degradation of the Strike temperature, flexibility and abrasion resistance are observed and the surface condition is considerably improved.

The above results show that when an alkoxy-modified Amino resins s to the polyamide-imide resin, which with a polyisocyanate with an or several isocyanurate rings and a lactam have been modified, no Lowering of the breakdown temperature, the flexibility, the abrasion resistance and the like is effected and that the high-speed processability is remarkable can be improved.

Such an outstanding effect cannot only be due to a combination a conventional polyamide-imide resin with an alkoxy-modified amino resin be due.

The polyamide-imide resin composition of the present invention therefore has a very important one technical importance.

Comparative Example 3 Synthesis of a polyamide-imide resin soluble in cresol: Ingredients g equivalent ratio of diisocyanate trimers, in comparative example 1 (1) synthesized (50% solution) 33.3 0.10 4,4'-diphenylmethane diisocyanate 113.3 0.91 Trimellitic anhydride 96.0 1.00 e-Caprolaetam 36.6 0.65 Cresol 300 The above Ingredients other than the trimellitic anhydride were placed in a four-necked flask given that with a thermometer, a stirrer and a tube for the fractionated Distillation was provided. The mixture was heated to 180C under a stream of nitrogen heated to carry out the reaction at that temperature for 90 minutes. Thereafter trimellitic anhydride was added to the flask and the temperature raised 2100C increased.

The reaction was carried out at 210 ° C. for 15 hours. The resin concentration was adjusted to 3096 with cresol, whereby a varnish was obtained. The paint had a viscosity of 250 poises. The infrared spectra of the resin showed the Absorption of the imide group at 1780 cm1 and the absorption of the amide group at 1650 cm 1. When the leak was used to burn enameled wires, it was adjusted with cresol so that the solids content was 30%.

Example 4 The polyamide-imide resin synthesized in Comparative Example 3 was heated to about 1000C. For this purpose, the polyisocyanate with isocyanurate rings was used (Diisocyanate trimer) synthesized in Comparative Example 1 (1), in an amount of 3 parts in terms of solid content per 100 parts of polyamide-imide resin, in terms of solids content, added with stirring, creating a uniform Polyamide-imide resin composition having a solid content of 30% was obtained.

Example 5 The polyisocyanate synthesized in Comparative Example 1 (1) with one or more isocyanurate rings was heated in cresol beforehand to 1200C dissolved and implemented. The resulting solution became that in the comparative example 3 synthesized polyamide-imide resin in an amount of 8 parts in terms of Solids content, per 100 parts of polyamide-imide resin, expressed as solids content, given, thereby forming a uniform polyamide-imide resin composition having a solid content of 30 »was obtained.

The resin compositions (paints) obtained in this way were coated onto wires. The properties were tested and are summarized in Table II. Tabel II Sample (Example No.) Comparative Example 4 Example 5 Example 3 Pull Speed (m / min) 7.5 9 7.5 9 7.5 9 Properties Breakdown temperature (° C) (load 2 kg) 370 310 370 372 370 367 Flexibility (wrapping around the diameter) good Cracks good good good good Abrasion resistance (times) (load 600 g) 102 50 110 95 104 100 Surface condition good bubbles good good good good The comparative example 3 and Examples 4 and 5 show that when a polyisocyanate is added with a or more isocyanurate rings to a polyamide-imide resin, which with a polyisocyanate has been modified with one or more isocyanurate rings and a lactam, no lowering of the breakdown temperature, the flexibility, the abrasion resistance is observed on wires drawn at a standard pulling speed of 7.5 m / min have been drawn. Furthermore, it is shown that with wires that with high pulling speed of 9 m / min (high speed machining), almost no degradation the breakdown temperature, flexibility and abrasion resistance occurs and that the surface condition has been greatly improved.

The above results show that when a polyisocyanate is added with one or more isocyanurate rings to the polyamide-imide resin, which is with a Polyisocyanate with one or more isocyanurate rings and modified with a lactam has been, no lowering of the breakdown temperature, the flexibility, the Abrasion resistance and the like takes place. Furthermore, the high-speed workability can be significantly improved. Thus, the polyamide-imide resin composition, which in one Solvent of the cresol type is a very important one according to the invention technical importance.

Comparative Example 4 (1) Synthesis of a polyamide-imide resin soluble in cresol: Components g equivalent ratio of diisocyanate trimers, synthesized in Comparative Example 1 (1) 50% Solution) 33.3 0.10 4,4'-diphenylmethane diisocyanate 113.3 0.91 trimellitic anhydride 96.0 1.00 # -Caprolactam 36.6 0.65 Cresol 340 The above ingredients with Except for the trimellitic anhydride, were placed in a four-necked flask, the with a thermometer, a stirrer and a tube for fractional distillation was provided. The mixture was heated to 1800C in a nitrogen stream to initiate the reaction to be carried out at this temperature for 90 minutes.

Thereafter, trimellitic anhydride was added to the flask and the Temperature was increased to 2100C. The reaction was carried out at 210 ° C. for 15 hours. The resin concentration was adjusted to 30% with cresol, resulting in a leak became. The leak had a viscosity of 250 poises. The infrared spectrum of the resin showed the absorption of the imide group at 1780 cm-1 and the absorption of the amide group at 1650 cm (2) synthesis of the phenol / formaldehyde resin: components g equivalent ratio Cresylic acid 425 1.17 formaldehyde (37% aqueous solution) 303 1.00 triethanolamine 5 The above ingredients were placed in a four neck flask given, which is provided with a thermometer, a stirrer and a reflux condenser was. The mixture was refluxed with stirring at 980 ° C. for 90 minutes. Thereafter the reflux condenser was removed and the reaction proceeded under reduced pressure from 30 to 50 mm Hg at 50 ° C for 5 hours. Thereupon became the resulting Resin diluted with 450 g of cresylic acid, creating a phenol / formaldehyde resin solution was obtained.

Example 6 The polyamide-imide resin synthesized in Comparative Example 4 (1) was heated to about 1000C. To this end, that synthesized in Comparative Example 4 (2) was synthesized Phenol / formaldehyde resin in an amount of 3 parts expressed as solids content, while stirring per 100 parts of polyamide-imide resin, expressed as solids content, added, whereby a uniform polyamide-imide resin composition was obtained.

Example 7 The polyamide-imide resin synthesized in Comparative Example 4 (1) was heated to 80.degree. C. and for this purpose that was synthesized in Comparative Example 4 (2) Phenol / formaldehyde resin in an amount of 8 parts expressed as solids content, per 100 parts of polyamide-imide resin, expressed as solids content, added with stirring, whereby a uniform polyamide-imide resin composition was obtained.

Film formation method and extraction method The polyamide-imide resin compositions (Paints) of the comparative example 4 (1) and Examples 6 and 7 were adjusted so that their non-volatile content was 30g, and they were onto steel plates previously bonded and polished with sandpaper (400 CW) (Thickness 0.8 mm) stacked to a thickness of 0.30 mm. The coated panels were placed in a hot air blowing oven at 2500C and they were 15 min, 30 min and dried and baked for 45 minutes, respectively, to obtain film-coated panels. About 1 g of the coated film was peeled off from each film-coated plate, placed in a flask equipped with a condenser and immersed in 50 g of cresol. Thereafter, heat treatment was carried out at 1000 ° C. for 5 hours. After treatment the solution was filtered with a glass filter (3G - 2) and it was washed with methanol washed. The filtration residue (undissolved matter) was left in a dryer dried under reduced pressure for 8 h at 1000C and weighed to determine the percentage extraction to investigate. The results obtained are shown in FIG.

From Figure 1 it can be seen that the percentage extraction of the examples 6 and 7 in comparison with Comparative Example 4 (1) within a short period of time was diminished. This means that the addition of phenol / formaldehyde resin to the Polyamide-imide resin imparts rapid curing properties to the polyamide-imide resin composition. The polyamide-imide resin composition according to the invention therefore has in technical fields where high speed machinability is required, a large technical one Value.

Example 8 The polyamide-imide resin synthesized in Comparative Example 4 (1) became heated to about 800C and coated with an epoxy resin (Epikote 828, manufactured by Shell Chemical Corp.) in an amount of 5 parts in terms of solid content per 100 parts of polyamide-imide resin, expressed as solids content, added with stirring, whereby a uniform polyamide-imide resin composition was obtained.

Example 9 The polyamide-imide resin synthesized in Comparative Example 4 (1) was heated to 1000C. For this purpose, an epoxy resin (Epikote 1007, manufactured by Shell Chemical Corp.) in an amount of 15 parts in terms of solids content, per 100 parts of polyamide-imide resin, expressed as solids content, added with stirring, whereby a uniform polyamide-imide resin composition was obtained.

Example 10 The polyamide-imide resin synthesized in Comparative Example 4 (1) was heated to 1000C and made with a novolak type epoxy resin (DEN 438) from Dow Chemical Co.) in an amount of 10 parts in terms of solids content, per 100 parts of polyamide-imide resin, expressed as solids content, added with stirring, whereby a uniform polyamide-imide resin composition was obtained.

Example 11 The polyamide-imide resin synthesized in Comparative Example 4 (1) was heated to 800C. For this purpose, an epoxy resin of the alicyclic type (CH 221, manufactured by UCC, Ltd.) in an amount of 5 parts as solids content, per 100 parts of polyamide-imide resin, expressed as solids content, added with stirring, thereby obtaining a uniform polyamide-imide resin composition became.

Film formation method and extraction method The polyamide-imide resin compositions (Leaks) of Comparative Example 4 (1) and Examples 8 to 11 were adjusted so that that they had a non-volatile content of 30%. they were on steel plates (0.8 mm thick) previously bonded and polished with sandpaper (400 CW) applied in a thickness of 0.30 mm. The coated panels were in a Put a hot air blow oven at 2500 C and they were dried for 15 minutes, 30 minutes and 45 minutes, respectively and burned. This gave panels coated with film. Of each film-coated plate, about 1 g of the coated film was peeled off, in placed in a flask equipped with a condenser and immersed in 50 g of cresol. Thereafter, heat treatment was carried out at 1000 ° C. for 5 hours. After treatment the solution was filtered off with a glass filter (3G - 2) and it was washed with methanol washed. The filtration residue (undissolved material) was at 1000C in one Dryer dried under reduced pressure for 8 hours and weighed to the percentage Determine extraction. The results are compiled in FIG.

Figure 2 shows that the percentage extraction of Examples 8 to 11 in a short period of time as compared with Comparative Example 4 (1) is. This means that the addition of epoxy resin to the polyamide-imide resin the Polyamide-imide resin compound imparts rapid curing properties. Thus, the invention has Polyamide-imide resin composition in fields where high-speed machinability is required a great technical value.

Comparative Example 5 Synthesis of polyamide-imide resin soluble in cresol: Ingredients g equivalent ratio of diisocyanate trimers, synthesized in the comparative example 1 (1) (solution above) 30.0 0.09 4,4'-diphenylmethane diisocyanate 113.3 0.91 trimellitic anhydride 96.0 1.09 £ -Caprolactam 36.6 0.65 Cresol 300 The above ingredients with Except for the trimellitic anhydride were placed in a four-necked flask, the with a thermometer, a stirrer and a tube for fractional distillation was provided. The mixture was heated to 1800C in a nitrogen stream to initiate the reaction to be carried out at this temperature for 90 minutes.

Thereafter, trimellitic anhydride was added to the flask and the Temperature was increased to 2100C. The reaction was carried out at 210 ° C. for 15 hours. The resin concentration was adjusted to 30% with cresol, whereby a varnish was obtained became. The paint had a viscosity of 250 poises. The infrared spectrum of the resin showed the absorption of the imide group at 1780 cm and the absorption the Amide group at 1650 cm 1. When using the lacquer for firing enamelled Wires it was adjusted with cresol so that the solids content was 30%.

COMPARATIVE EXAMPLE 6 Synthesis of the polyester: Ingredients g equivalent gram Dimethyl terephthalate 517.9 5.34 tris (2-hydroxyethyl) isocyanurate 381.6 4.38 Ethylene glycol 100.5 3.24 Tetrabutyl titanate (catalyst) 1.0 Cresol 176.5 The above Ingredients were placed in a four-neck flask, which was measured with a thermometer, a stirrer and a tube for the fractional distillation was provided. That The mixture was reacted at 180 to 2200C under a stream of nitrogen, whereby a Resin with an OH number of 175 was obtained.

Cresol was added to the resin produced so that a varnish with a resin content of 30%.

COMPARATIVE EXAMPLE 7 A polyester varnish (WH-407, manufactured by Hitachi Chemical Co., Ltd.), which is made from terephthalic acid, glycerin and ethylene glycol was used.

Comparative Example 8 A polyester varnish (Isomid, manufactured by Nisshoku Schenectady Co., Ltd.), made from terephthalic acid, imidodicarboxylic acid, tris- (2-hydroxyethyl) isocyanurate and ethylene glycol were used.

Example 12 The polyamide-imide resin synthesized in Comparative Example 5 was heated to about 1500C and synthesized with that in Comparative Example 6 Polyester resin in an amount of 10 parts in terms of solid content per 100 parts of polyamide-imide resin, expressed as solids content, added with stirring, whereby a uniform polyamide-imide resin composition was obtained.

Example 13 About the polyamide-imide resin synthesized in Comparative Example 5 in an amount of 100 parts in terms of solid content, WH-407 des Comparative Example 7 in an amount of 10 parts in terms of solid content, to obtain a uniform polyamide-imide resin composition.

Example 14 About the polyamide-imide resin synthesized in Comparative Example 5 in an amount of 100 parts in terms of solid content, isomide des Comparative Example 8 in an amount of 5 parts in terms of solid content, given, whereby a uniform polyamide-imide resin composition was obtained.

Vm the improvement of the rapid curing properties by adding A polyester resin to the polyamide-imide resin were films from the paints of Comparative Example 5 and Examples 12 and 13. From the paints of Comparative Example 5 and Examples 12 and 14 became enameled wires formed, whereby the burning times were varied.

The percent extraction by cresol was measured on the films. The properties of the enamelled wires were measured in practice.

1) Film formation and extraction method The polyamide-imide resin compositions (Paints) of Comparative Example 5 and Examples 12 and 13 were adjusted so that that their non-volatile content was 30%.

They have been previously bonded and polished with sandpaper (400 CW) Steel plates (thickness 0.8 mm) applied in a thickness of 0.30 mm. Each coated Plate was placed in a hot air blowing oven at 2500C and 15 min, 30 min and Dried and baked for 45 minutes, whereby film-coated panels were obtained. Approximately 1 g of coated film was peeled off from each film-coated panel, placed in a flask fitted with a condenser and in 50 g of cresol immersed. Thereafter, heat treatment was carried out at 1000 ° C. for 5 hours.

After the treatment, the solution was filtered with a glass filter (3G - 2) filtered and washed with methanol. The filtration residue (undissolved material) was dried at 1000C in a reduced pressure dryer for 8 hours and weighed to determine percent extraction. The results obtained are compiled in Figure 3.

2) Properties of the enamelled wires The properties of the enameled Wires obtained in Comparative Example 5 and Examples 12 and 14 were measured. They are summarized in Table III. Table III Sample (Example No.) Comparative Example 12 Example 14 drawing speed (m / min) 7.5 9 7.5 9 7.5 9 Properties Breakdown temperature (° C) (load 2 kg) 370 310 370 360 372 370 flexibility (wrapping a lot around the diameter) good cracks good good good good Abrasion resistance (times) (load 600 g) 98 42 92 89 90 85 the end It can be seen from Figure 3 that in the case of polyamide-imide resin that is mixed with a polyisocyanate has been modified with one or more isocyanurate rings and a lactam, a cresol extraction of 30% or less can only be obtained by reaching 45 heated to 250 ° C for min or more. In contrast, in the case of Examples 12 and 13, in which polyester resins with one or more hydroxyl groups are obtained under Use of terephthalic acid and / or isophthalic acid as the acid component to which Polyamide-imide resin added, a cresol extraction of 3096 or less can easily be obtained by heating at 2500C for only 15 minutes. This clearly shows that the addition of polyester resin with one or more hydroxyl groups obtained using terephthalic acid and / or isophthalic acid as the acid component, the rapid curing properties of the polyamide-imide resin are improved.

As further shown in Table III, in the comparative example 5 if. the wire is drawn at a drawing speed of 9 m / min, at a relatively short burning time, the breakdown temperature, flexibility and abrasion resistance considerably decreased, while in the case of Examples 12 and 14 there was almost no decrease the breakdown temperature, the flexibility and the abrasion resistance are observed became. This also shows that the addition of polyester resin with one or more Hydroxyl groups obtained using terephthalic acid and / or isophthalic acid as an acid component that improves the rapid curing properties of the polyamide-imide resin.

The invention is therefore in terms of improving workability of polyamide-imide resins is very effective and it has a very important technical importance.

COMPARATIVE EXAMPLE 9 Synthesis of a polyamide-imide resin soluble in cresol: Ingredients g equivalent ratio of diisocyanate trimers, synthesized in the comparative example 1 (1) (50% solution) 407 0.10 4,4'-diphenylmethane diisocyanate 1120 0.90 trimellitic anhydride 960 £ 1.00 -Caprolactam 366 0.65 Cresol 3100 The above ingredients except of the trimellitic anhydride were placed in a four-necked flask fitted with a Provided thermometer, a stirrer and a tube for the fractional distillation was. The mixture was heated to 180.degree. C. under a stream of nitrogen to initiate the reaction to be carried out at this temperature for 90 minutes. Thereafter it became trimellitic anhydride added to the flask and the temperature raised to 210C. The response was Carried out at 210 ° C. for 15 hours. The resin content was adjusted to 3096 with cresol, whereby a varnish was obtained. The paint had a viscosity of 250 poises. The infrared spectrum of the resin showed the absorption of the imide group at 1780 cm 1 and the absorption of the amide group at 1650 cm 1.

Examples 15 to 18 To 100 parts, expressed as the solids content, Polyamide-imide resin synthesized in Comparative Example 9 was the individual metal salts listed in Table IV were added, whereby a varnish was obtained.

Table IV Example Metal Salt Quantity No. (parts) 15 Zinc naphthenate 2.0 16 cobalt octoate 0.5 17 dibutyltin laurate 0.5 18 manganese naphthenate 1.0 after defoaming of the paints of Comparative Example 9 and Examples 15 to 18 were these paints 0.325 mm thick on bonded steel plates (0.775 mm thick) with Sandpaper (400 CW) had been polished. The individual coated Plates were dried and baked for 30 minutes at 2500C, thereby film-coated Plates were obtained.

For these film-coated panels, the strike-through temperature (as an index of heat resistance), the Erichsen test value (as an index for flexibility) and the impact strength (impact strength test by the du Pont method) were measured. The appearance of the surface was evaluated with the naked eye.

The results are shown in Table V. Tabel V Example No. Comparative Example 15 Example 16 Example 17 Example example 9 18 Breakdown temperature * 1 (° C) 370 368 371 370 370 Erichsen test * 2 (mm) 70 72 70 68 72 Impact strength (cm) (du Pont method, load 1 kg, core size of the impact element 0.3 cm) 35 35 35 35 35 Appearance fine roughening - no roughening of the surface and none Wrinkle roughening of the formation surface, wrinkling Footnote: * 1: Breakdown temperature: The film-coated plate was placed in the device shown in Figure 4, to measure the breakdown temperature. In FIG. 4, the reference number denotes 1 a load (2 kg), the reference number 2 metal support parts, the reference number 4 the Sample (film-coated plate with a thickness of 0.775 mm), the reference number 4 the coated surface, the reference number 5 a steel ball (diameter 5 mm), the reference number 6 a sealing ring, the reference number 7 a steel plate (0.8 mm thick), the reference numeral 8 an insulation plate (glass cloth) and the reference numeral 9 an AC power source (100 V).

* 2: Erichsen test according to JIS standard B 7777. The larger the values, the better the flexibility.

From Table V it can be seen that the polyamide-imide resin that is used with modified a polyisocyanate with one or more isocyanurate rings and a lactam and which is soluble in cresol before mixing with a metal salt good heat resistance (breakdown temperature), good impact resistance, has good flexibility (Erichsen test, impact test), but looks bad, i.e., has a fine surface roughening and wrinkling in the surface. In contrast, Examples 15 to 18, in which various kinds of Metal salts according to Table V to which the polyamide-imide resin were added, good results not only in terms of heat resistance, impact resistance and flexibility, but also in terms of surface appearance. This clearly shows that the addition of special metal salts to the coated polyamide-imide resin Improved surface.

The polyamide-imide resin composition according to the invention can therefore be used with good success be applied to heat-resistant cooking appliances, magnet wires, etc.

Claims (19)

Polyamide-imide resin composition and its use Patent claims 1. Polyamide-imide resin composition, in that it contains: (A) a polyamide-imide resin, produced by reacting a polyisocyanate with one or more isocyanurate rings, an aromatic diisocyanate, a lactam and a polycarboxylic acid with at least an acid anhydride group in a solution by means of CresoltyD and (B) at least one substance from group (1) an alkoxy-modified amino resin, (2) a polyisocyanate with one or more isocyanurate rings, (3) a phenol / formaldehyde resin, (4) an epoxy resin, (5) a polyester resin with one or more hydroxyl groups, obtained using terephthalic acid and / or isophthalic acid as the acid component, and (6) at least one metal salt of Sn, Mn, Co and / or Zn. 2. polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z e i c h n e t that the polyisocyanate is made up of one or more isocyanurate rings 4,4'-diphenylmethane diisocyanate, 4.41 diphenyl ether diisocyanate, tolylene diisocyanate or xylylene diisocyanate has been obtained. 3. polyamide-imide resin composition according to claim 1 or 2, characterized g e k e It is noted that the polyisocyanate has one or more isocyanurate rings contains residual isocyanate groups in an amount of 10 to 70%. 4. polyamide-imide resin composition according to claim 1, characterized g e k e n n z e I do not know that the lactam is £ -CaprO-lactam. 5. polyamide-finide resin composition according to claim 1 or 4, characterized g e k e It is not noted that the lactam in an amount from 20 to 90 Equivalent%, based on the total isocyanate equivalent, has been used. 6. polyamide-imide resin composition according to claim 1, 2 or 3, characterized g e k It is noted that the polyisocyanate has one or more isocyanurate rings in an amount of 1 to 30 equivalents-96, based on the total isocyanate equivalent, has been used. 7. polyamide-imide resin composition according to claim 1, characterized g e k e n n z e i c h n e t that the polycarboxylic acid with at least one acid anhydride group is trimellitic anhydride is. 8. polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z e i c h n e t that as component (B) an alkoxy-modified amino resin in one Amount from 1 to 20 parts by weight, expressed as the solids content per 100 parts by weight, in terms of the solid content of the polyamide-imide resin has been used. 9. polyamide-imide resin composition according to claim 1 or 8, characterized g e k e It is noted that the alkoxy-modified amino resin is an alkoxy-modified one Benzoguanamine / formaldehyde resin is. 10. Polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z E i c h n e t that as component (B) a polyisocyanate with one or more Isocyanurate rings in an amount of 1 to 20 parts by weight, expressed as solids content, per 10q parts by weight, expressed as the solids content, of the polyamide-imide resin has been used. 11. Polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z E i c h e t that as component (B) a phenol / formaldehyde resin in an amount from 1 to 30 parts by weight, expressed as solids content, per 100 parts by weight, in terms of the solid content of the polyamide-imide resin has been used. 12. polyamide-imide resin composition according to claim 1 or 11, characterized g e k It is noted that the phenol / formaldehyde resin is phenol / formaldehyde resin, an alkylphenol / formaldehyde resin or a phenol / formaldehyde resin that is associated with a Amino compound has been modified is. 13. Polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z E i c h e t that as component (B) an epoxy resin in an amount of 1 to 30 Parts by weight in terms of solids content per 100 parts by weight as the solid content, of the polyamide-imide resin has been used. 14. Polyamide-imide resin composition according to claim 1 or 13, characterized g e k Note that the epoxy resin is a bisphenol type epoxy resin, an epoxy resin novolak type, an alicyclic type epoxy resin, or a heterocyclic type Ring containing epoxy resin. 15. Polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z E i c h n e t that as component (B) a polyester resin with one or more Hydroxyl groups obtained using terephthalic acid and / or isophthalic acid as the acid component, in an amount of 1 to 300 parts by weight, expressed as solids content, per 100 parts by weight, expressed as solids content, of the polyamide-imide resin has been used. 16. Polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z e i c h e t that as component (B) a metal salt of Sn, Mg, Co or Zn in an amount of from 0.01 to 10 parts by weight per 100 parts by weight, expressed as Solid content of the polyamide-imide resin has been used. 17. Polyamide-imide resin composition according to claim 1 or 16, characterized g e k It is noted that the metal salt of Sn, Mg, Co or Zn is dibutyltin laurate, Dibutyltin acetate, manganese naphthenate, manganese octoate, cobalt naphthenate, cobalt octoate, Zinc naphthenate or zinc octoate. 18. Polyamide-imide resin composition according to claim 1, characterized in that g e k e n n z e i c h e t that the component (A) in an amount of 100 parts by weight and that component (B) has been used in an amount of 1 to 300 parts by weight is. 19. Use of the polyamide-imide resin composition according to claim 1 for production of electrical conductors with an insulating coating.