JP2002245856A - Resin component for electric insulation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin component for electric insulation made to improve a reactivity of unsaturated polyester used for a stabilizer made of galvanized steel plate, and made to sharply reduce a corrosiveness of galvanization caused by unreacted acryl group monomer or decomposed substance of the monomer. SOLUTION: The resin component for electric insulation uses (A) unsaturated polyester, (B) a reactive monomer selected from ester acrylate and its derivative or ester methacrylate and its derivative, (C) a hardening accelerator jointly using metallic soap and tertiary amine, and (D) a hardening agent jointly using ketone peroxide and diacrylperoxide as essential components, and the resin component is composed by mixing the reactive monomer of the (B) by 40-300 weight portion, and the hardening accelerator of the (C) by 0.1-1.0 weight portion, to the (A) unsaturated polymer of 100 weight portion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for electrical insulation for reducing corrosion of a galvanized steel case material used for a ballast for fluorescent lamps and the like. The present invention relates to a resin composition for electrical insulation, which has higher reactivity of a resin than a resin composition and reduces unreacted reactive monomers (for example, methacrylic acid (2-hydroxyethyl)) which cause corrosion.

[0002]

2. Description of the Related Art Conventionally, a resin composition containing a flexible unsaturated polyester as a main component and styrene as a reactive monomer has been used for cast insulation of a fluorescent lamp ballast housed in a case. General. However, odor often becomes a problem in the type that mainly uses styrene, and when a private house approaches a factory that manufactures stabilizers, the odor problem occurs frequently. As a countermeasure against this odor problem, acrylic acid esters or methacrylic acid esters are often used as reactive monomers, but the copolymerization reaction is less likely to occur than aromatic vinyl monomers such as styrene (that is, Low rate). In addition, due to the low reaction rate of the resin, unreacted acrylate and pyrolyzed acrylic acid corrode the galvanized case material of the ballast,
Increasingly, it becomes a tar and is extracted from the ballast and poses a problem.

On the other hand, in recent years, ballasts are often used outdoors. In this case, the temperature difference between the operation time and the stop time becomes large, and the temperature difference between seasons is large. Are increasing in many cases.

[0004] Further, even in indoor applications, ballasts have been miniaturized, and the number of times of operation and stoppage has increased, so that intense cooling heat has been added in many cases as in the case of outdoors.

[0005] Under such severe operating conditions, when an acrylic low-odor monomer having low reactivity is used for the compound, the unreacted material (acrylic monomer) is galvanized in the early stage of operation. Corrosion of materials, extraction of tar-like substances, causing electrical troubles, resin degradation due to poor reactivity and deterioration due to cold or heat, and cracks associated therewith often cause rare shot. Was.

[0006] Under such circumstances, a ballast maker demands a polyester compound for a ballast which does not impair the reliability as a ballast even if a low-odor monomer such as an acrylate ester is used.

[0007]

SUMMARY OF THE INVENTION An object of the present invention has been made in view of the above circumstances, and improves the reactivity of a compound (unsaturated polyester) used in a galvanized steel ballast. By doing so, it is intended to provide a resin composition for electrical insulation in which the corrosiveness of zinc plating due to unreacted monomers (acrylic monomers) or monomer decomposed products (acrylic acids) is significantly reduced, and the reliability of the resin is improved. Things.

[0008]

The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, as described later, an unsaturated polyester is used as a main component, an acrylic monomer is used as a main monomer, and the curing is performed. It has been found that the above object can be achieved by using a metal soap and a tertiary amine in combination as accelerators, and further combining ketone peroxide and diacyl peroxide as curing agents, thereby completing the present invention.

That is, the present invention relates to (A) an unsaturated polyester, (B) a reactive monomer selected from acrylic acid esters and derivatives thereof and methacrylic acid esters and derivatives thereof, (C) metal soap and A curing accelerator used in combination with a secondary amine and a curing agent used in combination with (D) a ketone peroxide and a diacyl peroxide are essential components, and the reaction of the above (B) with respect to 100 parts by weight of the above (A) unsaturated polyester 40 to 300 parts by weight of the reactive monomer and 0.1 to 1.0 part by weight of the curing accelerator of (C),
It is a resin composition for electrical insulation characterized by being blended respectively. Further, the curing agent of (D) is (A) +
0.5 to 100 parts by weight in total of (B) + (C)
It is a resin composition for electrical insulation characterized by being blended in a ratio of 2.0 parts by weight.

Hereinafter, the present invention will be described in detail.

The unsaturated polyester (A) used in the present invention is obtained by reacting an acid component with an alcohol component.
As the acidic component used here, maleic acid, maleic anhydride, unsaturated acids such as fumaric acid and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, Saturated acids such as hexahydrophthalic anhydride and adipic acid are listed, and these can be used alone or as a mixture of two or more.

The alcohol component includes propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, 1,3-butanediol,
Neopentyl glycol, glycerin, pentaerythritol, tris (2-hydroxyethyl) isocyanurate, polyether polyalcohol and the like can be mentioned, and these can be used alone or in combination of two or more.

The unsaturated polyester (A) can be modified by adding a modifying component other than the above-mentioned acid and alcohol components. Examples of modified components other than the acid and alcohol components include linseed oil, soybean oil, tall oil, petroleum resin, dicyclopentadiene, and the like, and these can be used alone or in combination of two or more.

The reactive monomer (B) used in the present invention is selected from various acrylic esters such as acrylic esters and their derivatives, methacrylic esters and their derivatives. For example, methyl methacrylate, ethyl methacrylate, methacrylic acid (2-hydroxyethyl), allyl methacrylate, and the like, and
Optionally, an alkyl methacrylate (C2-9),
Tridecyl methacrylate, stearyl methacrylate, lauryl methacrylate and the like are also used, and these can be used alone or in combination.

The total amount of the reactive monomer (B) is preferably 40 to 300 parts by weight based on 100 parts by weight of the unsaturated polyester resin (A). If the amount is less than 40 parts by weight, the viscosity is so high that workability is impaired and sufficient electrical and mechanical properties cannot be obtained. If the amount exceeds 300 parts by weight, sufficient flexibility cannot be obtained, which is not preferable.

Among the metal soaps and tertiary amines of the combination curing accelerator (C) used in the present invention, the metal soaps include cobalt soaps, and mainly include cobalt naphthenate and cobalt octylate. In addition, as the tertiary amine, dimethylaniline, dimethylparatoluidine,
Examples thereof include triethanolamine, N-ethylmethtoluidine, and tolyldiethanolamine.

The total compounding ratio of the combined curing accelerator (C) is preferably 0.1 to 1.0 part by weight based on 100 parts by weight of the unsaturated polyester (A).
If the amount is less than 0.1 part by weight, the reactivity is low and sufficient cured product properties cannot be obtained. If the amount exceeds 1.0 part by weight, the pot life becomes short, which is not preferable. The weight ratio of metal soap / tertiary amine is 1.0 / (0.5 to
1.0) is most suitable. If the ratio of the metal soap is larger than this, the pot life is shortened, and if the ratio of the metal soap is smaller than this, it does not harden sufficiently.

Of the ketone peroxide and diacyl peroxide of the curing agent (D) used in the present invention,
Examples of the ketone peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. Next, examples of the diacyl peroxide include benzoyl peroxide, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide and the like.

(D) The combined proportion of the combined curing agent is
It is desirable to add 0.5 to 2.0 parts by weight to 100 parts by weight of (A) + (B) + (C) described above. If the amount is less than 0.5 part by weight, sufficient curability (reduction of unreacted monomer) cannot be obtained. On the other hand, if it exceeds 2.0 parts by weight, the gelation time is shortened, the workability is deteriorated, and the heat generation during curing is increased, which may impair the reliability as a stabilizer.

Further, the weight ratio of ketone peroxide / diacyl peroxide is 1.0 / (0.3 to
0.7) is most desirable. If the ratio of the diacyl peroxide exceeds the above range, the gelation time will be too fast, and the workability will be poor, and the heat generated by curing will increase, possibly impairing the reliability as a stabilizer. If the ratio of diacyl peroxide is less than the above, sufficient curability (reduction of unreacted monomers) cannot be obtained.

The resin composition for electrical insulation of the present invention comprises (A)
The unsaturated polyester, the (B) reactive monomer, the (C) curing accelerator and the (D) curing agent are essential components, but other components may be used as long as they do not contradict the purpose of the present invention. Components such as a polymerization inhibitor, a colorant, an antifoaming agent, a leveling agent, and the like can be added and blended. Among them, examples of the polymerization inhibitor include quinones such as hydroquinone, p-tert-butylcatechol, and pyrogallol, and these can be used alone or as a mixture of two or more.

The resin composition for electrical insulation of the present invention comprises an unsaturated polyester (A), a reactive monomer (B), a curing accelerator (C), a curing agent (D) and other components (additives). Can be easily manufactured by uniformly stirring and mixing. The resin composition for electrical insulation manufactured in this way can be widely used in the field of electrical insulation, but is particularly used as a casting material for fluorescent ballasts to reduce corrosion of ballast case materials. It can be suitably applied even under severe heat and heat cycle conditions.

[0023]

The resin composition for electrical insulation of the present invention contains an acrylic reactive monomer (B) as compared with the conventional unsaturated polyester resin composition, and particularly contains two types of curing accelerators (metals). The degree of polymerization is improved by using the component (C) of the soap and the tertiary amine together, and further using the component (D) of two kinds (ketone peroxide and diacyl peroxide) as the curing agent. Unreacted acrylic components are less likely to remain in the cured product. Further, corrosion of the ballast case material due to unreacted acrylic components or acrylic components thermally decomposed in the initial stage of operation is reduced.

In other words, this formulation makes it difficult for the low-odor type unsaturated polyester resin to remain the acrylic component which reacts well and corrodes the case material of the ballast even if an acrylic monomer is used. This is to prevent the occurrence of corrosive substances in the case material during the operation stage, and to obtain a resin composition for electrical insulation with improved reliability as a cured product.

[0025]

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[Production of Modified Unsaturated Polyester] A-1 To 7 parts of phthalic anhydride, 54 parts of soybean oil, 14 parts of pentaerythritol, 14 parts of maleic anhydride and 11 parts of propylene glycol, 0.02 part of hydroquinone was added. The reaction was carried out at 180 to 210 ° C. to obtain a resin having an acid value of 25. The obtained resin was further blended with 0.01 part of hydroquinone.

A-2 Tetrahydrophthalic anhydride 14
, 22 parts of maleic anhydride, 24 parts of soybean fatty acid, 22 parts of ethylene glycol, 14 parts of diethylene glycol and 4 parts of glycerin were added with 0.02 part of hydroquinone and reacted at 180 to 210 ° C to obtain a resin having an acid value of 25. Was. 0.01 part of hydroquinone was further added to the obtained resin.

Examples 1 to 3 The compositions shown in Table 1 were blended and sufficiently stirred to produce a resin composition.

Comparative Example 1 The compositions shown in Table 1 were blended and sufficiently stirred to produce a resin composition.

Comparative Examples 2 to 5 The compositions shown in Table 2 were blended and sufficiently stirred to produce a resin composition.

Using the resin compositions produced in Examples 1 to 3 and Comparative Examples 1 to 5, cured products were obtained and their properties were tested. The results are shown in Tables 1 and 2. In the resin composition of the present invention, the amount of unreacted monomer (acrylic) was significantly reduced as compared with the conventional resin composition. In addition, a corroded material of the case material was not extracted in the operation stage, a good cured product was obtained, and the effect of the present invention could be confirmed.

The remaining 2HEMA (methacrylic acid (2
-Hydroxyethyl)) is a gas chromatography method using C-R17A manufactured by Shimadzu Corporation according to the following procedure.

(1) The cured product is cut into small pieces with a hammer or a cutter.

(2) The small pieces are finely ground with an agate mortar.

(3) About 0.1 g of the crushed sample is weighed with a precision balance. (Ssp W) (4) To this, add 20 ml of methylene chloride, and add
h extraction is performed.

(5) After extraction, about 0.03 g of an internal standard substance (n-dodecane) is weighed with a precision balance. (Sis
W) (6) 2HEMA, n-
Weigh about 0.03 g of dodecane on a precision balance. To this, 20 ml of methylene chloride is added to prepare a sample for a correction coefficient.

(F2HEMA W = g) (fis
W = g) (7) The sample for the correction coefficient and the extract are analyzed under the following GC conditions. The injection amount is 2 μL.

Column: UA-1 (Frontier Lab)
30M-1.0FI. D 0.25mmφ, FILM
1.0 μm.

Temperature: INJ = 150 ° C., COL = 150
° C, DET = 240 ° C.

Gas: helium 400 kgf / cm ² (8) A correction coefficient F is obtained by the following equation.

F = ｛(f2HEMA W) / (fis
W) {/ {(f2HEMA A) / (fis A)} f2HEMA A = AREA area of 2HEMA obtained by GC analysis of correction coefficient sample fis A = n-dodecane obtained by GC analysis of correction coefficient sample (9) The residual 2HEMA content is determined by the following formula.

Residual 2HEMA (%) = ｛(s2HEMA
A × F × sis W) / (sis A)｝ / (ssp
W) × 100 s2HEMA A = 2HE obtained by GC analysis of the extract
AREA area of MA sise A = AREA area of n-dodecane obtained by GC analysis of extract

[Table 1] * 1: Gas chromatography method * 2: Extraction conditions were 120 ° C. × 200 h, and the number of ballasts from which black matter was extracted was regarded as the number of defectives.

[0043]

[Table 2] * 1: Gas chromatography method * 2: Extraction conditions were 120 ° C. × 200 h, and the number of ballasts from which black matter was extracted was regarded as the number of defectives.

[0044]

As is clear from the above description and Tables 1 and 2, the resin composition for electrical insulation of the present invention has much less unreacted monomer compared to conventional products, It does not extract the corrosive substance of the case agent in the above, and is excellent in crack resistance, and is suitable for casting electric insulation equipment such as a fluorescent light ballast.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J015 CA06 CA11 4J027 AB02 AB06 AB07 AB08 AB15 AB16 AB17 AB18 AB19 AB23 AB24 AB25 AB26 BA07 BA08 BA12 CB03 CB07 CD08 5G305 AA13 AB15 AB27 BA09 CA12 CB08 CB14 CB16 CB27 CD08

Claims (2)

[Claims] 1. A reactive monomer selected from (A) an unsaturated polyester, (B) an acrylate and its derivative, and a methacrylate and its derivative,
(C) a curing accelerator using a combination of a metal soap and a tertiary amine,
(D) A curing agent using a ketone peroxide and a diacyl peroxide in combination is an essential component, and the reactive monomer of (B) is 40 to 300 parts by weight based on 100 parts by weight of the unsaturated polyester (A). A resin composition for electrical insulation, wherein the curing accelerator of (C) is blended in an amount of 0.1 to 1.0 part by weight. 2. The method according to claim 1, wherein the curing agent (D) is (A) + (B) +
The resin composition for electrical insulation according to claim 1, wherein the composition is blended in a ratio of 0.5 to 2.0 parts by weight based on 100 parts by weight of the total of (C).