JPH0138128B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin composition, and more particularly to an unsaturated polyester resin composition that has excellent heat resistance and insulation properties and is suitable for use as a varnish for coil impregnation. Recent trends in electrical equipment include miniaturization and improved performance, and as a result, heat resistance of electrical insulating materials is increasingly required. Conventional heat-resistant coil-impregnated varnishes include silicone-based varnishes, diphenyl ether-based varnishes, and polyamide-imide-based varnishes, but all of them are solvent-based varnishes, and the varnish treatment process is complicated and takes a long time. In particular, for polyamide-imide varnishes, only expensive polar solvents such as N-methylpyrrolidone and N,N-dimethylacetamide can be used. There was a risk that the material would be adversely affected. Other heat-resistant resins include imide compounds represented by formula (1) obtained by reacting polycarboxylic anhydrides such as trimellitic anhydride and pyromellitic dianhydride with diamines in an organic solvent. [R ₁ is a divalent or trivalent cyclic or aromatic residue, and an anhydride-forming group is present at the 1,2-, 1,3- or Perry position. R ₂ means a divalent aliphatic or cycloaliphatic residue or an aryl group.
R ₃ is still present in the free state at the terminal or side position of the unsaturated polyester -COOH, -OH or -
means a monovalent active monofunctional residue suitable for reaction with an NH group. An imide-modified unsaturated polyester resin is known that has improved heat resistance than the conventional unsaturated polyester resin, which incorporates ] into an unsaturated polyester system (Japanese Patent Publication No. 45-28509). In addition, formulas (2) and (3) are used as a component of polyhydric alcohol when synthesizing unsaturated polyester. (R is an aliphatic or aromatic divalent group,
By using a divalent glycol compound having an imide group in the molecule (R' represents an aliphatic divalent group), imide-modified polyester resin has improved heat resistance than conventional unsaturated polyester resin. Unsaturated polyester resins are known.
No. 8995, No. 8996). However, these resins have the formula
The imide compounds shown in (1), (2), and (3) are first synthesized, and then an unsaturated polyester is synthesized as part of the alcohol and acid, which is a very complicated synthesis method. The imide-modified unsaturated polyester resin has improved heat resistance compared to general polyester resins, but it cannot be said to be sufficient. As a result of various studies, the present inventors have discovered an unsaturated polyester resin that maintains the excellent electrical and mechanical properties of conventional unsaturated polyester resins and has improved heat resistance than the above-mentioned imide-modified unsaturated polyester resins. The composition was successfully obtained. The present invention includes (a) a primary amino compound, a compound having at least one acid anhydride group or carboxyl group in addition to an acid anhydride group, an unsaturated carboxylic acid or anhydride thereof, and the total equivalent of a polyhydric alcohol component; An imide group, an isocyanurate ring, and an amide group as necessary in the molecule obtained by reacting a polyhydric alcohol containing 5 to 30 equivalents of tris-(2hydroxyethyl) isocyanurate in the absence of a solvent. 20 to 80 parts by weight of an unsaturated polyester containing, and (b)
10 to 50% by weight of the total amount of polymerizable monomers is Tris-
The present invention relates to a heat-resistant unsaturated polyester resin composition containing 80 to 20 parts by weight of a polymerizable monomer in the form of an acrylic ester or methacrylic ester of (2hydroxyethyl)isocyanuric acid. Next, materials used in the present invention will be described.
The unsaturated polyester which is the component (a) in the unsaturated polyester resin composition of the present invention is a primary amino compound, a compound having at least one acid anhydride group or carboxyl group in addition to an acid anhydride group, 5 to 30 equivalent % based on the total equivalent of unsaturated carboxylic acid or its derivative and polyhydric alcohol component
It is obtained by reacting polyhydric alcohol with tris-(2hydroxyethyl) isocyanurate in the absence of a solvent, and the specific materials for each are as follows. Primary amino compounds include 4,4'diaminodiphenylmethane, 4,4'diaminodiphenyl ether benzidine, p-phenylenediamine, m-
Phenyl diamine, xylene diamine, hexamethylene diamine, ethylene diamine, monoethanolamine, etc. are used. Compounds having at least one acid anhydride group or carboxyl group in addition to the acid anhydride group include:
Trimellitic anhydride, pyromellitic anhydride, benzophenone-2,3,2',3'-tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, etc. are used. Unsaturated carboxylic acids and their derivatives include:
Maleic acid, itaconic acid, citraconic acid, anhydrides thereof, fumaric acid, esters thereof, etc. are used. In addition to tris-(2hydroxy)isocyanurate, polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, 1,3-propenediol, 1,3-butanediol, 1,4-butanediol, 2,3
-butanediol, hexamethylene glycol,
Neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. are used. In the present invention, when the amount of tris-(2hydroxyethyl)isocyanurate added is increased, the properties are improved, but the compatibility with the polymerizable monomer becomes worse, resulting in a significantly higher varnish viscosity. Therefore, the amount of tris-(2hydroxyethyl)isocyanurate added, which gives an effect on heat resistance and can lower the viscosity below that of ordinary impregnated varnishes, is 5 to 50% relative to the total equivalent of the polyhydric alcohol component used. 30
Equivalent %. In addition, as saturated dibasic acids, phthalic acid, tetrahydrophthalic acid,
Hexahydrophthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, etc. may also be used. Other various acrylic acid and methacrylic esters can also be used. Examples of the polymerizable monomer include styrene, vinyltoluene, α-methylstyrene, paratertiary butylstyrene, chlorostyrene, divinylbenzene, diallylphthalate, methyl acrylate or methyl methacrylate, ethyl acrylate or ethyl methacrylate, lauryl acrylate or lauryl. Methacrylate, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate or 2-hydroxypropyl methacrylate, a reaction product of acrylic acid or methacrylic acid and Cardiura E (trade name manufactured by Ciel Chemical Co., Ltd.), etc. Monofunctional acrylic ester or methacrylic ester, ethylene glycol diacrylate or ethylene glycol dimethacrylate, diethylene glycol diacrylate or diethylene glycol dimethacrylate, 1,6-hexanediol diacrylate or 1,6-hexanediol diacrylate, etc. Difunctional acrylic esters or methacrylic esters, trifunctional acrylic esters or methacrylic esters such as trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, etc. alone or in combination of two or more types. Can be used. When curing the unsaturated polyester resin composition of the present invention, a radical polymerization initiator such as benzoyl peroxide, acetyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, etc. Organic peroxides commonly used in unsaturated polyester resins can be used, such as oxide, tert-butyl perbenzoate, 3,3,5-trimethyl, and 1,1-diter-butyl peroxycyclohexanone.
In some cases, for the purpose of accelerating curing and improving air drying properties of the resin composition of the present invention,
A dryer made of metal such as octate or naphthenate of cobalt, manganese, lead, etc. may be used. A polymerization inhibitor may be added, and commonly used hydroquinone, paratertiary butylcatechol, etc. are used as the polymerization inhibitor. Next, the amount of each of the above-mentioned materials used will be explained. The composition ratio of the unsaturated polyester as the component (a) and the polymerizable monomer as the component (b) of the heat-resistant unsaturated polyester resin composition of the present invention is expressed as a weight ratio of (a) the unsaturated polyester /(b) Polymerizable monomer = 20~
80/80-20 preferably (a) unsaturated polyester/(b)
Polymerizable monomer = 30-70/70-30. The radical polymerization initiator is generally used in an amount of 0.5 to 3.0 parts by weight, preferably 1.0 to 2.0 parts by weight, based on 100 parts by weight of the unsaturated polyester resin composition.
When using a metal dryer, it is usually used in an amount of 2% by weight or less based on the unsaturated polyester resin composition. Furthermore, when a polymerization inhibitor is used, it is usually used in an amount of 0.1% by weight or less based on the unsaturated polyester resin composition. The blending ratio of component (a), the unsaturated polyester synthetic material, will be described. Primary amino compound (referred to as compound ())
and a compound having at least one acid anhydride group or carboxylic acid group in addition to an acid anhydride group (hereinafter referred to as a compound ()) means that the number of amino groups in the compound () is 1, and the number of amino groups in the compound () is 1. It is preferred to use a ratio of about 1 acid anhydride group. When producing component (a), an unsaturated polyester, the ratio of the acid component to the alcohol component is preferably such that the total number of carboxyl groups/total number of hydroxyl groups is 1/1.05 to 1.5 in order to proceed with the reaction. Also, when looking at acid components, compounds (),
The blending ratio of unsaturated carboxylic acid or its derivative and saturated dibasic acid is expressed as the ratio of the number of carboxyl groups in each of them: number of carboxyl groups in the compound ()/
The ratio of the number of carboxyl groups of unsaturated carboxylic acid or its derivative/the number of carboxyl groups of saturated dibasic acid is
It is preferable to use the ratio of 15/30 to 90/0 to 100. 10 to 50% by weight of the total amount of polymerizable monomers is Tris-
It is necessary that it is an acrylic ester or a methacrylic ester of (2hydroxyethyl)isocyanuric acid. As this ester, a monoester, diester or triester of acrylic acid or methacrylic acid is used, and a mixture thereof may be used. At less than 10% by weight, sufficient air drying properties and heat resistance cannot be obtained. On the other hand, if it exceeds 50% by weight, the compatibility with unsaturated polyester and other polymerizable monomers will be poor, so if left for a long time, phase separation may occur, resulting in a highly viscous liquid or semi-solid state.
It is unsuitable as a varnish for coil impregnation. Next, Examples and Comparative Examples of the present invention will be shown. Note that parts and % in Examples and Comparative Examples are parts by weight and % by weight, respectively. Comparative example 1 Maleic anhydride 98g (1 mol), phthalic anhydride
148g (1 mol), propylene glycol 167.2g
(2.2 mol) was placed in a four-necked flask, stirred under nitrogen gas blowing, kept at 180℃ for 1 hour, and then
The reaction was continued at 210°C to obtain an unsaturated polyester with an acid value of 20.0. Add 0.05% by weight of hydroquinone to 400g of unsaturated polyester,
600g of styrene was charged and dissolved to create a pale yellow homogeneous resin liquid. Varnish A was obtained by adding 1% by weight of benzoyl peroxide and 0.1% by weight of cobalt octenoate to this resin solution. Comparative Example 2 Trimellitic anhydride 38.4 g (0.2 mol), 4,
4′-diaminodiphenylmethane 19.8g (0.1mol),
110 g of N-methylpyrrolidone was charged into a four-necked flask, and the temperature was raised from room temperature to 150°C under nitrogen gas to dissolve it, followed by reaction at 170°C for 2 hours to obtain a uniform solution containing imide acid. This solution was cooled to room temperature, and added dropwise to 5 times the volume of methanol with stirring to separate the reaction product, which was then collected by filtration, thoroughly washed with methanol, and dried under vacuum heating to obtain a compound represented by the following formula. 51.8g (0.1mol) of this compound, isophthalic acid
74.7g (0.45mol), neopentyl glycol 62.4
g (0.6 mol), propylene glycol 30.4 g (0.4
mol) in a four-necked flask, heated to 160℃ under nitrogen gas blowing, reacted for 1 hour, then heated to 210℃ in 3 hours, continued reaction at 210℃, and reduced the acid value to 1. Measure every hour, and when the acid value reaches 5, lower the temperature to 160℃, and maleic anhydride 44.1
g (0.45 mol), dipropylene glycol 26.8 g
(0.2 mol) was charged and reacted at 180°C for 1 hour, then the temperature was raised to 210°C in 1 hour, and the reaction was continued at 210°C to obtain an unsaturated polyester with an acid value of 27.5. Add 0.05% hydroquinone to 400g of this unsaturated polyester, and add styrene to 400g of this unsaturated polyester.
600g was added and dissolved. The viscosity of this resin liquid is
It was 105 centipoise at 25°C. This resin liquid 100
1.0 part of benzoyl peroxide and 0.1 part of cobalt octenoate (metal content: 8%) were added to the mixture and thoroughly stirred to obtain a uniform solution varnish B. Example 38.4 g (0.2 mol) of trimellitic anhydride, 4,
4′-diaminodiphenylmethane 19.8g (0.1mol),
Charge 42.4 g (0.4 mol) of isophthalic acid, 62.4 g (0.6 mol) of neopentyl glycol, 15.2 g (0.2 mol) of propylene glycol, and 52.2 g (0.2 mol) of tris(2-hydroxyethyl) isocyanurate into a four-necked flask. The temperature was raised from room temperature to 160°C over 2 hours, then reacted at 160°C for 1 hour, then raised to 210°C over 3 hours, and the reaction continued at 210°C. The acid value was measured every hour, and when the acid value reached 5, the temperature was lowered to 160℃ and the maleic anhydride was 44.1.
g (0.45 mol), dipropylene glycol 13.4 g
(0.1 mol) was charged and reacted at 180°C for 1 hour, then the temperature was raised to 210°C in 1 hour, and the reaction was continued at 210°C to obtain an unsaturated polyester with an acid value of 28.0. Hydroquinone was added to 400 g of this unsaturated polyester () at 0.05% based on the unsaturated polyester, and triacrylate of tris-(2hydroxyethyl)isocyanuric acid (manufactured by Hitachi Chemical Co., Ltd.) was added.
FA731A) or trimethacrylate (FA731M manufactured by Hitachi Chemical) were blended as in Comparative Examples 3 to 6 and Examples 1 to 6 in Table 1. To 100 parts of this resin liquid, 1.0 part of benzoyl peroxide and 0.1 part of cobalt octenoate (metal content: 8%) were added, stirred well, and measured for characteristics. The results are shown in Table 1.

【table】

[Table] In Table 1, except for BDV residual rate, JIS C 2105
(Test method for solvent-free liquid resin for electrical insulation). The BDV residual rate is determined by measuring the dielectric breakdown after curing the test piece with a specified varnish under specified conditions in accordance with the dielectric breakdown test method of JIS C 3003 (Testing method for enamelled copper wire and enamelled aluminum wire). The retention rate was calculated. From the above results, it is clear that the resin composition of the present invention has excellent properties and workability for electrical insulation.

Claims (1)

[Scope of Claims] 1 (a) Primary amino compounds, compounds having at least one acid anhydride group or carboxyl group in addition to acid anhydride groups, unsaturated carboxylic acids or derivatives thereof, and polyhydric alcohol components It is obtained by reacting a polyhydric alcohol containing 5 to 30 equivalents of tris-(2hydroxyethyl)isocyanurate based on the total equivalent of , in the absence of a solvent. 20 to 80 parts by weight of an unsaturated polyester containing an amide group and (b) 10 to 50% by weight of the total amount of the polymerizable monomer as an acrylic ester or methacrylic ester of tris-(2-hydroxyethyl)isocyanuric acid. An unsaturated polyester resin composition containing 80 to 20 parts by weight of a polymerizable monomer.