JPS60118740A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful mainly as varnish for heat-resistant enameled wire, having improved flexibility and adhesivity, obtained by blending an amide-imide bond-containing polyester resin with a specific alkylphenol- formaldehyde resin. CONSTITUTION:A composition consisting of (A) a polyester resin containing an amide-imide bond in the molecule obtained by reacting an isocyanate compound with a tribasic acid anhydride and a lactam to give an amide-imide oligomer, reacting the amide-imide oligomer with a polyester resin or an alcohol component and an acid component, wherein the alcohol component is partially or totally tris-2-hydroxyethyl isocyanurate, and (B) 0.1-5wt% based on A of novolak alkylphenol-formaldehyde resin (preferably tertiary butylphenol-formaldehyde resin) having 4-10C alkyl group.

Description

[Detailed description of the invention] The present invention relates to a heat-resistant resin composition.

Heat-resistant resin compositions, especially varnishes for heat-resistant enameled wires, include polyamide-imide varnish, polyimide varnish, polyester-imide varnish, and polyamide-imide ester varnish, but polyester-imide varnish and polyamide-imide ester varnish are preferred from the viewpoint of the balance of properties and price. A large amount of fabrics made of resins made of polyester modified with imide bonds or amide-imide bonds are used.

Since polyester imide varnish and polyamide imide ester phenol are manufactured using relatively inexpensive materials,
Although it is excellent in terms of economy (price), it has somewhat poor flexibility, and there are concerns about flexibility and adhesion, especially when used as a thick film on heat-resistant enameled wire with a large wire diameter.

The present inventors have investigated improvements in the elasticity and adhesion of polyamide-imide ester phenol.

The present invention was achieved by discovering that a polyamideimide ester sweat film containing a specific type of phenolic resin has excellent flexibility and adhesion.

The present invention is directed to phospholiester resins having an amide-imide bond in two molecular chains and alkylphenol formaldehyde resins having novolac alkyl groups having 4 to 10 carbon atoms (
The present invention relates to a heat-resistant resin composition containing an alkylphenol resin (hereinafter referred to as an alkylphenol resin).

The polyester resin having an amide-imide bond in the molecular chain used in the present invention can be obtained by (1) first synthesizing an amide-imide oligomer, and (2) then reacting it with the polyester resin by heating or by heating it with an alcohol component and an acid component. Obtained by reaction.

Amidimide oligomers include incyanate compounds and tribasic acid anhydrides, cresol, and phenol.

It can be obtained by reaction in a polar solvent such as N-methylpyrrolidone. From the viewpoint of cost, phenolic solvents, particularly cresol, are preferred as the synthesis solvent. If a lactam is further used as a reaction component, phenol turbidity is less likely to occur even if the molecular weight of the amide-imide oligomer increases.
Preference is given to using lactams.

As the incyanate compound, aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate are preferred. It is better to use incyanurate ring-containing polyisocyanate as part of the isocyanate compound.

The phenol is less likely to become cloudy. As the isocyanurate ring-containing polyisocyanate, incyanurate ring-containing polyisocyanates obtained by trimerization reaction of diisocyanates such as tolylene diincyanate, 4,4'-diphenylmethane diisocyanate, and isophorodiisocyanate are used.

An example of tribasic acid anhydride is trimellitic anhydride.

Examples include butanetricarboxylic anhydride.

As a lactam, considering 1 reactivity 9 price, ε-
Caprolactam is preferred. The amount of lactam used is preferably less than 100 equivalents of the total incyanate equivalents in consideration of heat resistance. However, 1 mole of lactam is considered to be 2 equivalents.

From the viewpoint of heat resistance and flexibility, the amount of isocyanate compound and tribasic acid anhydride used is preferably such that the equivalent ratio of isocyanate group to carboxyl group is used.

0.6-1.5. More preferably, it is in the range of 0.7 to 1.15.

All raw materials may be added to the reaction at the same time.

The preparation reaction may be carried out in stages depending on the purpose.

The reaction temperature is 195 to 2
Preferably it is carried out at 20°C.

There are no particular limitations on the polyester resin that is heat-reacted with the amide-imide oligomer used in the present invention.

As the acid component used in the production of this polyester resin, it is preferable to use terephthalic acid, isophthalic acid, or derivatives thereof such as dimethyl terephthalate and dimethyl isophthalate. As the alcohol component, an alcohol having a valence of 9 or higher is usually used. Examples of dihydric alcohols include ethylene glycol, neopentyl glycol, 1.4-butanediol, and 1,6-hegizanediol.

1,6-cyclohexane dimetatool and the like are used.

Examples of trihydric or higher alcohols include glycerin,
Trimethylolpropane, tris-2-hydroxyethyl isocyanurate, pentaerythritol, etc. are used. From the viewpoint of heat resistance and abrasion resistance, it is preferable to use trihydric or higher alcohols for at least 30 equivalents of the total alcohol components.

Glycerin is recommended for crazing resistance.

From the viewpoint of heat resistance and refrigerant resistance, it is particularly preferable to use it for all or part of the tris-2-hydroxyethyl isocyanurate alcohol component.

The equivalent ratio of acid and alcohol is alcohol excess 1% to 6.
An alcohol excess of 0% is preferred. There are no particular restrictions on the method of synthesizing the polyester resin.

In the present invention, there are no particular limitations on the alcohol component and acid component that are heat-reacted with the amide-imide oligomer, but it is preferable to use those exemplified as the acid component and alcohol component of the polyester resin described above. The equivalent ratio of acid and alcohol is preferably 1% to 60% alcohol excess.

The amount of amide-imide oligomer used is 20 to 8% per molecule of polyester resin having an amide-imide bond in one molecule chain.
A range of 0% by weight is preferable in terms of heat resistance and stability of the varnish. The heating reaction of the amide-imide oligomer with the polyester resin or the acid component and the alcohol component is not particularly limited, as long as the conditions allow esterification, transesterification, amide transesterification, etc. to occur substantially. Usually, the reaction is carried out in the presence of a trace amount of an esterification catalyst such as tetrabutyl titanate, lead acetate, or dibutyltin dilaurate at a temperature in the range of 120 to 240°C. Of course, it is also possible to synthesize by adding a solvent such as cresol according to the viscosity.

The novolak alkylphenol resin used in the present invention is usually obtained by reacting formaldehyde or formalin with an alkylphenol whose alkyl group has 4 to 10 carbon atoms in the presence of an acidic catalyst. The blending ratio of formaldehyde or formalin and alkylphenol having an alkyl group of 4 to 10 carbon atoms is not particularly limited, but usually 0.0. 8-1.2
It is often carried out as around molar. Examples of acidic catalysts include hydrochloric acid, nitric acid, and phosphoric acid. Examples of alkylphenols whose alkyl group has 4 to 10 carbon atoms include tert-butylphenol, nonylphenol, octylphenol, etc., but phenol, cresol, xylene/-ruubisphenol A, etc. may also be used as part of these. do not have. Among the novolak-based alkylphenol formaldehyde resins in which the aluminum group has 4 to 10 carbon atoms, tertiary-butylphenol formaldehyde resins are preferred.

There is no particular restriction on the synthesis temperature during the synthesis of the alkylphenol formaldehyde fat, but it is usually between 90 and 240℃.
It is carried out in the range of °C. Typical novolac-based alkylphenol resins include:

For example, PR-1140, PR, -114OA, PR-
1140B (both manufactured by Hitachi Chemical).

The amount of the novolac-based alkylphenol resin is preferably 0.1 to 5% by weight, more preferably 0.5 to 2.5% by weight, based on the polyester resin having an amide-imide bond in the molecular chain. If the amount of novolac-based alkylphenol resin added is small, flexibility will not be sufficiently improved, and if the amount added is large, mechanical properties such as wear resistance will deteriorate.

The heat-resistant resin composition of the present invention is. It is produced by dissolving the above-mentioned polyester resin having an amide-imide bond in its molecular chain and a novolac-based alkylphenol resin 1]W in a solvent and adjusting the viscosity to an appropriate value.

The solvent may be any solvent that can dissolve the polyester resin having an amide-imide bond in its molecular chain and the novolak alkylphenol resin, and there is no limit to the percentage, but cresol or phenol is usually used.

Phenolic solvents such as xylenol are used.

Of course, as a co-solvent, for example xylene.

NISSEKI HISOL-1 00, 1 5 0
(Aromatic hydrocarbons manufactured by Nippon Petrochemical (KIO)), methyl ethyl ketone, dimethyl succinate, methyl calpitol, etc. may be used.

The heat-resistant resin composition of the present invention is. Contains 20 to 50% by weight of a polyester resin having an amide-imide bond in the molecular chain and a novolak-based alkylphenol resin, 8
Preferably, it contains 0 to 50% by weight of solvent.

The heat-resistant resin composition of the present invention is left as is.

Or titanium compound, polyisocyanate generator, organic acid metal salt, polyamide resin as necessary. Additives such as polyesterimide resin, polyhyguntoin resin, alkoxy-modified amino resin, polysulfone resin, etc. are added at a ratio of 0.1 to 25% by weight based on the resin content, and then coated directly or together with other insulating films on the electrical conductor and baked. It is said to be enamelled wire.

When manufacturing enamelled wire, the conditions normally used are adopted, and there are no particular restrictions.

The heat-resistant resin composition thus produced can also be used as a heat-resistant paint.

The present invention will be explained below with reference to Examples and Comparative Examples.

Comparative Example 1 Synthesis components of incyanurate ring-containing polyisocyanate Gram tolylene diisocyanate 600 Xylene 600 2-dimethylaminoethanol (catalyst) 1.8 Place the above ingredients in a four-bottle flask equipped with a thermometer and a stirrer,
The temperature was raised to 140°C in a nitrogen stream.

The reaction was continued at the same temperature until the content of incyanate groups (initial concentration: 48% by weight) reached 25% by weight. The infrared absorption spectrum of this substance has 1710 cm-1,1410
Absorption of incyanurate ring was observed at cm-', 2
Absorption of incyanate groups was observed at 260 cm-'.

Comparative Example 2 Synthetic components of novolac-based butylphenol resin Gram tertiary butylphenol 136 Formalin (37% solution) 81 Hydrochloric acid (38% solution) 0.036 Place the above ingredients in a four-bottle flask equipped with a thermometer and a stirrer. While stirring at 90-100°C.

Reflux the water and keep warm for 5 hours. Then lower the temperature.

Stop stirring and let stand. Then, the upper aqueous layer of the contents separated into two layers was removed, stirring was started again, dehydration was carried out under reduced pressure, and the temperature was raised to 190°C to react until the softening point of the contents reached 130°C. advanced. When the contents were cooled, a yellow solid resin was obtained.

Comparative Example 3 Synthesis of polyamide-imide ester resin (1) Synthesis of polyamide-imide oligomer ε-Caglolactam 62.2 1.10 Trimellitic anhydride 19
8.7 2.07 Cresol 450.0 Xylene 20.0 Thermometer the above components except trimellitic anhydride.

The mixture was placed in a fourth flask equipped with a stirrer and a 9-fraction distillation tube, and the temperature was raised to 170°C in a nitrogen stream to carry out the reaction for 60 minutes. Then add trimellitic anhydride and reduce the temperature to 205
The reaction was carried out in a trench where the temperature of the cresol solution with a resin content of 25% by weight was raised to 130 seconds at 25°C.

(2) Synthetic components of polyamide-imide ester resin
Gram Equivalent Dimethyl Terephthalate 116.4 1.2 Tris-
2-Hydroxyethyl 130.5 1.5-Isocyanurate Tetrabutyl Titanate 0.5 Further, the above components were added, the temperature was raised to 200°C, kept for 1 hour, and then cooled, and then cresol/xylene was added. It was diluted with a -7/3 (weight ratio) solution until the Gardner number of seconds at 30°C was 50 seconds. Next, 13g of tetrabutyl titanate.

189% of zinc naphthenate was added. The nonvolatile content of the obtained resin composition was 35% by weight (200°C for 2 hours), 30
The viscosity at °C was 46 poise.

Comparative Example 4 Resin composition x, ooog produced in the same manner as Comparative Example 3
In addition, PR-2084 (resol type phenolic resin solution, non-volatile content 50% 1 manufactured by Hitachi Chemical (KK)) 14
g was added to prepare a new resin composition. The nonvolatile content of the obtained resin composition was 35% by weight (200°C for 2 hours), and the viscosity at 30°C was 42 poise.

Example 1 50 g of novolac-based butylphenol resin produced in Comparative Example 2 and 50 g of cresol were heated at 90°C for 1 hour + 1 J]4
A homogeneous butylphenol resin solution was obtained by stirring.

Resin composition 1.0009 produced in the same manner as Comparative Example 3
Further, 4 g of the above butylphenol resin solution was added to prepare a new resin composition. The nonvolatile content of the obtained resin composition was 35% by weight (200°C-2h), 30% by weight (200°C-2h)
The viscosity at °C was 44 poise.

Example 2 (1) Synthesis of polyamideimide oligomer ε-caglolactam 25.4 0.45 Trimellitic anhydride 97
．． 9 1.02 Cresol 193.0 Xylene 1000 Place the above-mentioned source meter and a stirrer into a fourth flask equipped with a fractionator tube, raise the temperature to 207°C in a nitrogen stream, and reduce the resin content to 25% by weight. The reaction was carried out until the Gardner seconds of the cresol solution reached 150 seconds.

(2) Synthesis of polyamideimide ester resin Dimethyl terephthalate 150.4 1.55 Ethylene glycol 16.6 0.53 Tetrabutyl titanate 0
．． 4 Further, add the above ingredients, raise the temperature to 195°C, keep it warm for 1 hour and 30 minutes, cool it, and then add cresol/
It was diluted with a solution of xylene = 7/3 (ffilt ratio) until the Gardner number of seconds at 30°C was 35 seconds. Next, 11g of tetrabutyl titanate and 15g of zinc nanthenate.
, novolac-based butyl phenol resin PR-1140
(manufactured by Hitachi Chemical Co., Ltd.) 14 g was added. The nonvolatile content of the obtained resin composition was 35% by weight (200°C for 2 hours).

The viscosity at 30°C was 32 poise.

Example 3 (1) Synthesis of polyamide-imide oligomer Acid Content Gram Equivalent ε-caglolactam 31.1 0.55 Trimellitic anhydride 97.9 1.02 Cresol 262.0 Xylene 10.0 The above components except trimellitic anhydride were heated at different temperatures. Total.

The mixture was placed in a fourth flask equipped with a stirrer and a 9-fraction distillation tube, and the temperature was raised to 150°C in a nitrogen stream to carry out the reaction for 60 minutes. Then add trimellitic anhydride and reduce the temperature to 205
℃ and kept warm for 10 hours.

(2) Synthesis of polyamideimide ester resin Dimethyl terephthalate 110.0 1.13 tris-2-hydroxye 110.5 1.27 tylisocyanurate ethylene glycol 4.0 0.13 tetrabutyl titanate 0.4 Furthermore, the above components After adding phenol/Hz-
It was diluted with a solution of 100 (manufactured by Nippon Petrochemical Co., Ltd.)-6/4 (weight ratio) until the Gardner time at 30° C. reached 30 seconds.

Then tetrabutyl titanate) 209. Zinc naphthenate"9 + novolac type butyl phenol resin P-1
15 g of 140B (manufactured by Hitachi Chemical Co., Ltd.) was added to obtain a resin composition.

World comparison example 3. Comparative example 4. Example 1. Example 2 and Example 3
The resin composition obtained in step 1 was baked onto a copper wire having a diameter of 1+mu with a type 0 finish to obtain an enameled wire, and the characteristics of the enameled wire were measured. The results are shown in Table 1.

From Table 1, Comparative Example 3. Comparative example 4. Example 1. Comparing Example 2 and Example 3.

(1) Comparative example 3 using the same polyamideimide ester resin. Looking at Comparative Example 4 and Example 1, the flexibility (3 x good → IX good) and the winding property after deterioration (2 x good → 1
× Good), thermal shock resistance (3 × Good → 1 × Good), adhesion (10
The properties related to flexibility (~15-→5 mm) are significantly improved, and the properties related to heat resistance such as softening resistance and deterioration resistance do not deteriorate.

(2) Examples 2 and 3 also have good flexibility, wrapability after deterioration, thermal shock resistance, and adhesion.

I understand that.

As described above, the heat-resistant resin composition of the present invention is as follows.

Compared to conventional compositions, it has good flexibility and adhesion, and has significantly improved resistance to stretch and impact during coil winding, and thermal stress during heat cycling, making it suitable for industrial use. It has great significance.

Claims (1)

[Claims] 1. A polyester resin having an amide-imide bond in the molecular chain and a novolac-based alkyl group having 4 to 1 carbon atoms
A heat-resistant resin composition containing 0 alkylphenol formaldehyde resin. 2. The polyester resin having an amide-imide bond in the molecular chain is a resin obtained using an amide-imide oligomer obtained by reacting an isocyanate compound, a tribasic acid anhydride, and a lactam. Heat-resistant resin composition. 3. The number of carbon atoms in the novolak alkyl group is 0.1 to 5.0% by weight of the alkylphenol formaldehyde resin based on the polyester resin having amide-imide bonds in the 7 molecular chains.Claim 1 The heat-resistant resin composition according to item 1 or 2. 4. Part or all of the alcohol component of the polyester resin having an amide-imide bond in the molecular chain, i. The heat-resistant resin composition according to item 3. 5. The heat-resistant resin according to claim 1, 2, 3, or 4, wherein the alkylphenol formaldehyde resin in which the novolac alkyl group has 4 to 10 carbon atoms is a tert-butylphenol formaldehyde resin. Composition.