JPS604564A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition composed of a specific unsaturated alkyd derived from tris(hydroxyethyl) isocyanurate and a poly(meth)acrylate of said isocyanurate, having excellent heat resistance and suitable as an electrical insulation coating. CONSTITUTION:The objective composition is composed of (A) an unsaturated alkyd prepared by (1) condensing (i) a polyhydric alcohol component containing >=30 equivalent% of tris(2-hydroxyethyl) isocyanurate in terms of hydroxyl equivalent (ii) an unsaturated fatty acid component containing 0.5-1.5mol of double bond based on 1mol of the component (i), and (iii) <=0.7 equivalent of an aromatic dibasic acid component based on the total hydroxyl equivalent of the component (i), and (2) reacting the condensation product with (iv) equivalent amount of an unsaturated aliphatic basic acid, and (B) the di(meth)acrylate and/ or tri(meth)acrylate of the component (i).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition with excellent heat resistance. Specifically, the present invention relates to a solvent-free resin composition that is particularly useful as an electrically insulating coating.

Currently, the commonly used electrical insulating paints include:
There are solution types dissolved in organic solvents and solvent-free types.

The majority of heat-resistant paints used in electrical equipment of class H or higher are still solution-type paints, which release large amounts of organic solvents into the atmosphere during drying or baking, resulting in air pollution and hazardous work. In addition to arousing debate over environmental issues, the reality is that it has poor adhesion at high temperatures. In addition, unsaturated polyester resins, which have traditionally been used as solvent-free products, have some degree of satisfactory coating film performance such as curability, mechanical properties, and chemical properties, but they have low heat resistance. Currently, only K, which is of type B or lower, is used. Furthermore, the use of epoxy resins known as F-type solvent-free epoxy resins is restricted due to the toxicity of the polyamine that is the curing agent.

In view of this situation, as a result of intensive study, the inventor has determined that 2.
The inventors have now completed a solvent-free resin composition that can be fully used in high-temperature heat-resistant electrical equipment and has excellent adhesion at high temperatures.

That is, a specific compound obtained by using tris(2-hydroxyethyl)in cyanurate in a specific amount or more
A resin composition whose main components are a fulkyto component and one or more selected from the group consisting of diacrylate, triacrylate, dimethacrylate, and trisacrylate of tris(2-hydroxyethyl)in cyanurate. However, the present invention was completed based on the discovery that it has particularly excellent properties such as storage stability, hardenability, heat resistance, adhesion strength, and compatibility with heat-resistant enameled wire.

That is, the present invention provides a polyhydric alcohol component (a) containing tris(2-hydroxyethyl) isocyanurate (hereinafter referred to as THEIC) in a proportion of 30 equivalents J or more in terms of the amount of hydroxyl group, the polyhydric alcohol component ( a) 0.5 to 1 mole of trihydric or higher polyhydric alcohol contained therein.
An unsaturated fatty acid component (b) having one or more double bonds in one molecule in a ratio of 5 moles and the polyhydric alcohol component (
A product obtained by condensing each component of the aromatic dibasic acid component (e) that has a carboxyl equivalent ratio of 0.7 times or less to the total hydroxyl equivalent of a) until the acid value of the product becomes 30 or less. Condensation product (d) with respect to condensation product (d)
diacrylate, triacrylate, dimethacrylate and triacrylate of THEIC, unsaturated alkyd (4) obtained by reacting an unsaturated aliphatic dibasic acid (e) having a carboxyl group equivalent in a ratio equal to or lower than the hydroxyl equivalent of d). Tris (2-
Hydroxyethyl)in cyanurate-(meth)acrylate (6) Hereinafter, it will be referred to as THEIC-(meth)acrylate. ) and, if necessary, a polymerizable monomer (Q) copolymerizable with the above component (4) and component (B).

THE used for unsaturated alkyd (5) in the present invention
The amount of IC should be at least 30 equivalents in terms of hydroxyl equivalent to the polyhydric alcohol component (a) K used, preferably at least 50 equivalents of Fi, and if it is less than 30 equivalents, the expected effect will not be obtained. .

Polyhydric alcohols that can be used other than THEIC include:
These include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and neopentyl glycol, and trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

Examples of the unsaturated fatty acid component (b) having one or more double bonds in one molecule include drying oils or semi-drying oils such as soybean oil, linseed oil, tung oil, and castor oil; and soybean oil fatty acids;
These include drying oil or semi-drying oil fatty acids such as linseed oil fatty acid, tung oil fatty acid, and dehydrated castor oil fatty acid, and one or more of these are used. The amount used is 3% contained in the polyhydric alcohol component (a) in terms of fatty acids.
0.5 to 1.5 per mole of polyhydric alcohol
Molar amounts are preferred. If it is less than 0.5 mol, the resulting coating film will have poor flexibility and processability, and if it is more than 1.5 mol, the heating loss of the coating film will be large, making it unfavorable in terms of heat resistance.

Examples of the aromatic dibasic acid component (C) include phthalic acid, tetrabromophthalic acid, terephthalic acid, inphthalic acid, lower alkyl esters thereof, phthalic anhydride, tetrahydrophthalic anhydride, etc. Or two or more types are used.

Further, trimellitic acid, pyromellitic acid, or anhydrides thereof may be substituted and used as part of the aromatic dibasic acid component (c).

The amount of the aromatic dibasic acid component (C) used is such that the carboxyl equivalent ratio is 0.007 times or less relative to the total hydroxyl equivalent of the polyhydric alcohol component (a).

If the amount exceeds this, there will be insufficient hydroxyl groups to react with the unsaturated dibasic acid (e) necessary to obtain the unsaturated alkyd (5).

In the present invention, the polyhydric alcohol component (a), the unsaturated fatty acid component (b), and the aromatic dibasic acid component (C) are subjected to a condensation reaction until the acid value of the product becomes 30 or less. The unsaturated alkyd (5) is formed by reacting the condensation product (d) with an unsaturated aliphatic dibasic acid (e) having a carboxyl group equivalent in a ratio equal to or lower than the hydroxyl equivalent of the condensation product (d). do.

Conventional reaction conditions can be applied to these reactions.

In addition, benzoquinone, to prevent gelation during the reaction,
A polymerization inhibitor such as hydroquinone can be added prior to or during the reaction.

If the acid value of the condensation product (d) is high, exceeding 30, a resin composition with excellent performance cannot be obtained.

As the unsaturated aliphatic dibasic acid (e), maleic acid,
Examples include maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, and one or more of these may be used. The amount of unsaturated aliphatic dibasic acid (e) used is such that the ratio of carboxyl group equivalents to the condensation product (d) is equal to or less than the hydroxyl equivalent of the condensation product (d). If the amount of unsaturated aliphatic dibasic acid (e) used exceeds this amount, it will be difficult to control the condensation reaction, and the acid component will increase, resulting in a large amount of acid component remaining after the reaction. It may impair the anti-corrosion ability of the paint.

In addition, when the unsaturated aliphatic dibasic acid (e) contains an acid anhydride, it is assumed that the acid anhydride group corresponds to 2 equivalents of carboxyl group.

The amount ranges from 0.99 to 0.50.

The unsaturated alkyd (8) obtained in this manner and TH
THEIC-(meth)acrylate (B) selected from the group consisting of diacrylate, triacrylate, dimethacrylate and trimethacrylate of EIC;
The resin composition of the present invention can be obtained from these components and a polymerizable monomer (Q) copolymerizable with component (B), if necessary.

The unsaturated alkyd (5) and THEIC-(meth)acrylate (6) have a weight ratio of 20 to 95 for the former and 5 for the latter.
It is preferable that the amount is 80% by weight (however, the total is 100% by weight). Further, the polymerizable monomer (Q is used in a ratio of 0 to 100 parts by weight with respect to the total of 100 parts by weight of the unsaturated alkyd (5) and THEIC-(meth)acrylate (6).Unsaturated alkyd (5) and THEI
If the ratio with C-(meth)acrylate (b) is out of the above range, the resulting resin composition will be unfavorable in terms of viscosity and fluidity, and the cured coating film will have poor heat resistance. There is.

However, if the amount of the polymerizable monomer (Q) exceeds the above range, the excellent performance of the resin composition of the present invention will not be exhibited.

As the polymerizable monomer 0, styrene, vinyltoluene,
Divinylbenzene, diallyl phthalate, diallyl isophthalate, triallyl cyanurate, triallyl isocyanurate, (meth)acrylic acid alkyl ester,
Benzyl (meth)acrylate, furfuryl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di( meth)acrylate, neobentyl glycol di(meth)acrylate, etc. can be used, and the workability, fluidity,
It is selected depending on performance such as product term workability and economic efficiency.

The unsaturated alkyd (5), THEIC-(meth)acrylate (6), and optionally the polymerizable monomer (Q) may be mixed in any order, and there is no particular restriction on the mixing device.

The resin composition of the present invention obtained by further Vtl is as follows:
Common radical polymerization initiators, such as penzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide,
Using t-butyl hydroperoxide, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, t-butyl perbenzoate, etc., and if necessary together with a radical polymerization initiator, e.g. , cobalt octenoate, cobalt nanthenate, iron octenoate, manganese octenoate, organic metal salts such as vanadium octenoate, organic amines such as N,N-dimethylaniline, and other accelerators are added to cure at room temperature or in a heating oven. It can be cured by methods such as , infrared curing, and high frequency heating curing.

Further, this resin composition can be cured by ultraviolet rays by adding a conventional photosensitizer such as benzophenone, benzoin, benzoin ethyl ether, dimethylacetophenone, etc. Alternatively, ultraviolet curing and heat curing can be used together. It is also possible to perform electron beam curing.

The resin composition of the present invention contains conventional additives, such as leveling agents, antifoaming agents, thixotropic agents such as silicic anhydride fine particles, fillers such as calcium carbonate, clay, glass powder, mica powder, and microballoons. , color pigments, flame retardants, stabilizers, etc. can also be effectively used.

The resin composition of the present invention can be used as a resin for impregnating electric appliances such as motor parts and transformer parts, and as an insulating phenol for dipping, as well as for impregnating various inorganic and organic cloth tubes, tapes, etc. It is also useful as a coating for heat-resistant metals, heat-resistant engineering plastics, and ceramics.

The invention will be explained in more detail by the following examples.

Example 1 In a four-piece flask equipped with a thermometer, a stirring device, a condenser, a distilled water receiver, and an inert gas inlet tube, Inol 307 and isophthalic acid 1662 were charged, and heated with a mantle heater under a nitrogen stream. Stir while heating. Temperature is 210-2
The temperature was gradually raised to 20°C, and the reaction proceeded while distilling off the distillate outside the system. When the acid value of the reactant reached 13, heating was stopped and the mixture was cooled to 130°C.

followed by 200 ppm of hydroquinone and 1 ml of fumaric acid.
16 g was added, the temperature was raised to 180°C, and the reaction was further carried out while distilling off the distillate. When the acid value of the reactant reached 20, heating was stopped. 0.01 parts of hydroquinone and 15 parts of styrene were added to 50 parts of the obtained condensation product and mixed and dissolved homogeneously to form a resin composition (1
) was obtained.

Add 1 part of L-butylperoxy-2-hexanoate to 100 parts of this resin composition fil, and place it on an aluminum plate for 11 minutes.
was cured at 100°C for 1 hour and then at 150°C for 2 hours to obtain a tough cured coating. This cured coating was heated to 250 ml.
When the weight loss rate was measured after 1 day and 10 days after being left in a constant temperature chamber at ℃, it was 8 qb after 18 days and 4% after 110 days, and no abnormality was observed on the film surface even after 10 days, making it useful as a heat-resistant paint. It was something.

In addition, a metal plate coating test was conducted according to the JIS C2105 electrical insulation solvent-free resin test method, and a smooth, strong, and adhesive coating was obtained, with a dielectric breakdown voltage of 10 kV 10° 1 mm, a volume resistivity of 2 x 1015 Ωα, and an ice-making test. It had a volume resistivity of lX 10'' Ωα, and was effective as an electrically insulating paint.

Comparative Example l To 50 parts of the condensation product obtained in Example 1, 0.01 part of hydroquinone, 30 parts of diethylene glycol dimethacrylate, 10 parts of diallyl phthalate, and 10 parts of styrene were added and uniformly dissolved. The weight loss rate due to continuous heating at 250° C. after curing under the same conditions as above was 1711 after 18 days and 25 days after 10 days, indicating a weight loss about twice that of the cured product of Example 1.

Comparative Example 2 Using the apparatus of Example 1, phthalic anhydride 2962, maleic anhydride 1961F, and dipropylene glycol 59
0 g was charged and dehydrated and condensed at 210 to 220° C. under a nitrogen stream to obtain a condensation product with an acid value of 31.

Hydroquinone o, o for 50 parts of condensation product with
1 part,) 1Jx(2-hydroxyethyl)incyanium triacrylate 30 parts, diallyl phthalate 5
15 parts of styrene and 15 parts of styrene were added thereto, and the mixture was dissolved in water to obtain a cured coating film under the same curing conditions as in Example 1. The weight loss rate of this cured coating film by continuous heating at 250°C is 14 after 18
However, after 10 days, the number was 22, which was a large value.

Example 2 522 F, ethylene glycol 252 and isophthalic acid 2162 were charged and dehydrated and condensed in the same manner as in Example 1. When the acid value reached 11, maleic anhydride 1402
was added to continue the reaction, and condensation reached an acid value of 18. 0.0 parts of hydroquinone per 50 parts of the condensation product obtained
A resin composition (2) was obtained by uniformly mixing and dissolving 1 part of Tris (2 parts), 10 parts of diallyl isophthalate, and 30 parts of diethylene glycol dimethacrylate. When cured under the same conditions as in Example 1, a tough film was obtained.

In addition, a resin composition (ISOMID) (made by Schenectady Co., Ltd., polyester imide paint), which is commercially available as a heat-resistant enameled wire of class H or higher, is baked on top of one diameter isomid wire, is coated with a resin composition ( 2) was applied by impregnation and hardened by baking. The test pieces thus obtained were continuously heated in a thermostatic chamber at 250° C. and the deterioration of dielectric breakdown voltage over time was measured, as shown in the following table.

,,,/ 1/- As is clear from the table above, the level of heat-resistant aging of the H-type enameled wire is sufficiently maintained, and the resin composition of the present invention also has excellent compatibility with the heat-resistant enameled wire. It was sufficiently useful as electrical insulation for Class H.

Claims (1)

[Claims] 1. A polyhydric alcohol component (a) containing 30 or more equivalents of (2-hydroxyethyl)in cyanurate based on 1 equivalent of hydroxy), the polyhydric alcohol component (
a) Unsaturated fatty acid component having one or more double bonds in one molecule at a ratio of 0.5 to 1.5 mol per mol of trivalent or higher 3° polyhydric alcohol contained in a) (b) ) and the aromatic dibasic acid component (e) which has a carboxyl equivalent ratio of 0.7 times or less to the total hydroxyl equivalents of the polyhydric alcohol component (a), if the acid value of the product is 30 Condensation product (d) obtained by condensation reaction until the following
An unsaturated alkyd, tris(2-hydroxyethyl), obtained by reacting an unsaturated aliphatic dibasic acid (e) with a carboxyl group equivalent in a ratio equal to or less than the hydroxyl equivalent of the condensation product (d). Tris(
A resin composition consisting of a polymerizable monomer (Q) copolymerizable with 2-hydroxyethyl)in cyanurate (meth)acrylate a3) and, if necessary, the above component (5) and component (B).