JP2000044636A - Thermosetting resin composition and production of coil using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a coil subjected to an insulating treatment with a thermosetting resin composition curable at a relatively low temperature and capable of reducing the energy required for curing, prolonging the pot lift at room pressure and thereby compounding and mixing a large amount of a varnish at a time and reducing the disposed varnish. SOLUTION: This thermosetting resin composition contains (A) 40-80 pts.wt. of an unsaturated polyester resin, (B) 20-60 pts.wt. of a polymerizable monomer and (C) a crystallizable additive containing an organometallic compound or a metal in an amount of 0.1-5 wt.% [based on the total amount of the components (A) and (B)]. The metal and the metal of the organometallic compound contained in the crystallizable additive are cobalt vanadium or manganese. The content of the cobalt vanadium or manganese or the compound thereof in the crystallizable additive is within the range of 0.3-20 wt.%. Furthermore, (D) 0.5-4 pts.wt. of a peroxide curing agent is contained. The method for producing a coil comprises carrying out an insulating treatment with the above thermosetting resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition and a method for producing an insulated coil using the same.

[0002]

2. Description of the Related Art In the United States, air conditioner fans, washing machines, etc.
Insulating varnishes such as hermetic rotating machines and hermetic transformers such as small adapter transformers include phthalic acid or its derivatives,
It is often used by adding and mixing a peroxide curing agent and a curing accelerator to a varnish prepared by dissolving an unsaturated polyester resin such as bisphenol A having a benzene ring in a molecular width from an acid or alcohol as a raw material in styrene. In recent years, these electric devices have been reduced in size and weight, and performance and reliability have been required to be improved more than before, and improvement in productivity and environmental measures have been strongly demanded.

That is, conventionally, at 110 to 130 ° C., 1 to 2
Although it has been hardened and dried in a short period of time, it has been strongly required to cure at a relatively low temperature of about 60 to 80 ° C. and to reduce the energy required for hardening. But,
In order to cure at a relatively low temperature of about 60 to 80 ° C. and reduce the energy required for curing, an unsaturated polyester resin liquid is added to a curing agent capable of being cured at room temperature or an intermediate temperature and a cobalt naphthenate or the like. By adding a curing accelerator, curing can be performed at room temperature to 80 ° C.

However, the varnish has a problem that the reaction starts when the curing agent and the curing accelerator are added and mixed, and the pot life is short. Therefore, only a minimum amount of the varnish is mixed and mixed each time. The workability decreases and the reaction progresses, and the varnish which has become unusable due to the high viscosity must be discarded, and there is a problem that the waste varnish increases.

[0005]

The present invention cures at a relatively low temperature, reduces the energy required for curing, and extends the pot life at room temperature, so that a large amount of varnish can be mixed and mixed at one time. Another object of the present invention is to provide a method for producing a coil which is insulated using a thermosetting resin composition capable of reducing waste varnish.

[0006]

SUMMARY OF THE INVENTION The present invention is as follows. (1) (A) 40 to 80 parts by weight of an unsaturated polyester resin, (B) 20 to 60 parts by weight of a polymerizable monomer, (D) 0.1 to 4 parts by weight of a crystalline additive containing an organometallic compound or metal. % (Based on the total amount of the above components (A) and (B)).

(2) The thermosetting resin composition according to item (1), wherein the metal contained in the crystalline additive and the metal of the organometallic compound are cobalt, vanadium or manganese. (3) The content of cobalt, vanadium or manganese or a compound thereof in the crystalline additive is 0.3% by metal.
Item 2. The thermosetting resin composition according to item (2), wherein the content is in the range of 20 to 20% by weight. (4) The thermosetting resin composition according to any one of items (1) to (3), further comprising (D) 0.5 to 4 parts by weight of a peroxide curing agent.

(5) The crystalline additive contains a thermoplastic elastomer having a side chain having a crystallizable portion, and has a melting point in the range of 40 to 120 ° C.
The thermosetting resin composition according to any one of (4). (6) The thermosetting resin composition according to item (1), wherein the polymerizable monomer is styrene and / or a styrene derivative. (7) A method for producing a coil, comprising performing insulation treatment using the thermosetting resin composition according to any one of the above items (1) to (6).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester resin used in the present invention is obtained by reacting an acid component containing an unsaturated dibasic acid as an essential component with an alcohol component.

As the unsaturated dibasic acid, maleic anhydride, maleic acid, fumaric acid and the like are used, and these may be used alone or in combination. As the acid component, usually, in addition to the unsaturated dibasic acid, a saturated acid is used in combination to impart properties such as flexibility, heat resistance, and chemical resistance by adjusting the amount of the unsaturated group contained. You. As a saturated dibasic acid,
Saturated dibasic acids such as phthalic anhydride, phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, adipic acid and sebacic acid. These may be used alone or in combination. It is preferable that the amount of the unsaturated dibasic acid is selected in the range of 50 to 90 equivalent% of the total acid components.

As the alcohol component, polyhydric alcohols having an ether bond such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol are preferably used. These may be used alone or in combination.

Preferably, the total alcohol component is used in the range of 1 to 1.3 equivalents per 1 equivalent of the total acid component, and dicyclopentadienyl monomalate is used in an amount of 3 to 30 equivalent% based on the total acid component. And it is preferable to use 0.1 to 0.6 mol of dicyclopentadiene with respect to 1 mol of all acid components. By using dicyclopentadienyl monomalate or dicyclopentadiene, heat resistance can be imparted to the resin, but if it is too large, flexibility tends to decrease.

The above-mentioned acid component and alcohol component are mixed, heated to 190 to 220 ° C., and subjected to a dehydration condensation reaction to obtain an unsaturated polyester resin used in the present invention.

The polymerizable monomer used in the present invention includes, for example, styrene derivatives such as styrene, chlorostyrene, divinylbenzene, tert-butylstyrene, and bromostyrene, methyl methacrylate, ethyl methacrylate, and ethyl acrylate. Methacrylic acid or acrylic acid alkyl ester such as butyl acrylate, etc., β-hydroxyethyl methacrylate, β-hydroxyethyl acrylate etc. methacrylic acid or acrylic acid hydroxyalkyl ester, diallyl phthalate, acrylamide, phenylmaleimide and the like. Can be In addition, polyfunctional methacrylic acid or acrylic acid esters such as ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylpropane trimethacrylate can also be used. Of these, styrene and styrene derivatives are preferred.

The compounding ratio of the unsaturated polyester resin and the polymerizable monomer is defined as 100 parts by weight of the total amount of the unsaturated polyester resin and the polymerizable monomer.
To 80 parts by weight and 60 to 20 parts by weight of a polymerizable monomer.
It is preferably 80 parts by weight and 40 to 20 parts by weight of a polymerizable monomer.

In the present invention, the unsaturated polyester resin is preferably used by dissolving it in a polymerizable monomer.

The composition of the present invention preferably contains a peroxide curing agent for improving the curability.
Examples of the peroxide curing agent include 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydro 0 peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like. No restrictions. When the amount of the curing agent is small, the curing takes a long time, and when the amount is large, the curing is too fast and the permeability into the device is poor. It is preferably used in the range of 0.5 to 5 parts by weight.

The organometallic compound or crystalline additive containing a metal used in the thermosetting resin composition of the present invention will be described. Crystalline additives include thermoplastic elastomers having side chains with crystallizable moieties, which contain organometallic compounds or metals.
At room temperature, the organometallic compound or metal is suppressed from exhibiting its properties due to the microcapsule effect (protection effect) of the thermoplastic elastomer, but the thermoplastic elastomer having a side chain having a portion that can be crystallized by heating. As a result, the microcapsule effect (protective effect) is released and the organometallic compound or metal exhibits its properties.

The above thermoplastic elastomer having a side chain having a crystallizable portion comprises a polymer block A having a side chain having a crystallizable portion and a polymer block B comprising an amorphous thermoplastic polymer. There is something.

The above-mentioned thermoplastic elastomer having a side chain having a crystallizable portion has a precursor of a polymer block A having a side chain having a crystallizable portion (block A precursor) and an amorphous thermosetting resin. It can be produced by reacting with a precursor of a polymer block B composed of a plastic polymer (block B precursor). The block A precursor and the block B precursor have mutually reactive functional groups. Further, the thermoplastic elastomer having a side chain having a crystallizable portion having the above is a block A precursor, a block B monomer reactive with the functional group of the block A precursor, and a block B monomer reactive with the monomer. It can also be produced by reacting, and can also be produced by reacting a block B precursor, a monomer for block A reactive with a functional group of the precursor and a monomer for block A reactive with the monomer. .

The crystallizable part of the side chain of the polymer block A is preferably such that the DSC scan of the thermoplastic elastomer shows a very sharp melting point,
For example, the difference between the melting onset temperature and the peak temperature (Tq) in the DSC curve is 10 ° C. or less, preferably 8 ° C.
C., particularly preferably less than 6.degree. Also,
The melting point (Tq) of the polymer block A is usually (Tm + 5) ° C. or lower and (Tm−10) ° C. or higher with respect to the melting point (Tm) of the precursor or the equivalent polymer of the polymer block A. Tq is preferably from 0 to 200 ° C, more preferably from 0 to 150 ° C, especially from 0 to 120 ° C. The number average molecular weight of the polymer block A is 200,000 or less, preferably 100,000 or less, and more preferably 5 or less.
20,000 or less, more preferably 2,000 to 20,
000, especially 3,000-20,000.

Even if the polymer block A is of one type,
Two or more types may be used. In the polymer block A, the repeating unit is preferably 30 to 100%, more preferably 50 to 100%, and still more preferably 70 to 100%.
100%, particularly preferably 90 to 100%, contain crystallizable side chains. Therefore, polymer block A
May include other than the above repeating units. The crystallizable side chains are of the same or different species. When two or more polymer blocks A are present, Tq of each block may be different.

The polymer block A comprises a substituted or unsubstituted acrylate, fluoroacrylate, methacrylate, fluoromethacrylate, vinyl ester, acrylamide, maleimide, α-olefin, p-alkylstyrene, alkyl vinyl ether, alkyl ethylene oxide, alkyl phospha Polymers consisting of one or more of monomers such as zen, amino acid, polyisocyanate, polyurethane, polysilane, polysiloxane,
It is composed of a polymer containing a long-chain crystallizable group such as polyether.

The polymer block A has the general formula

Embedded image Can be broadly defined as a polymer block containing a repeating unit of Here, Y is an organic group forming a portion of the polymer skeleton, and Cy is a side chain including a crystallizable portion. The side chain Cy containing the crystallizable moiety is linked directly to the polymer backbone or to a divalent organic group or inorganic radical (eg, ester, carboxyl, amide, hydrocarbon (eg, phenylene), amino or ether linkage). Or via an ionic salt bond (eg, a carboxyalkyl ammonium, sulfonium, phosphonium ion pair).

Cy is aliphatic or aromatic and includes, for example, alkyl having at least 10 carbons, fluoroalkyl having at least 6 carbons, or p-alkylstyrene in which the alkyl contains 6 to 24 carbons. It is.

Preferred polymer blocks A are side chains containing a total of at least 5 carbon atoms in the backbone of the block, in particular 12 to 50 carbon atoms, especially 1 to
A linear substituted or unsubstituted alkyl group containing 4 to 22 carbon atoms (preferably a side chain containing a linear polymethylene moiety, or a linear perfluoropolymethylene containing 6 to 50 carbon atoms) (Including side chains). The block containing such side chains comprises one or more corresponding linear aliphatic acrylates, methacrylates, acrylamides or methacrylamides, optionally with one or more other components, preferably It is adjusted by polymerizing with a component selected from the following. Other components include other alkyl, hydroxyalkyl and alkoxyalkyl acrylates, methacrylates (eg, glycidyl methacrylate), acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, comonomers containing amine groups. Is mentioned. Acrylic acid, methallylic acid,
Maleic anhydride, acrylamide, methacrylamide, a comonomer containing an amine group, and the like have a functional group that is reactive with a compound to be incorporated into a thermoplastic elastomer, as described below, and are thus preferable in some cases. Such other components are preferably contained in an amount of 50 mol% or less, 35 mol% or less, 25 mol% or less, for example, 0 to 15 mol% based on all components.

The polymer as polymer block A used for the A block precursor or which can be formed by living polymerization includes atactic and isotactic polymers of n-alkyl-α-olefin (for example, carbon N-alkyl-α having 15 atoms
Atactic and isotactic polymers of olefins, melting points 30 ° C. and 60 ° C., respectively), polymers of n-alkyl glycidyl ethers (for example polymers of n-alkyl glycidyl ethers having 19 carbon atoms),
Polymers of n-alkyl vinyl ethers (eg, polymers of alkyl vinyl ethers having a melting point of 55 ° C. and 18 carbon atoms), and polymers of n-alkyl-α-epoxides (eg, n-alkyl-α having a melting point of 60 ° C. and 19 carbon atoms) Epoxide polymer), n-alkyloxycarbonylamide-ethyl methacrylate polymer (e.g., an alkyl compound having 18 carbon atoms, 22 carbon atoms or 22 carbon atoms having a melting point of 56C, 75C or 79C). Polymer), a polymer of n-fluoroalkyl acrylate (for example, a polymer of hexadecafluoroalkyl acrylate having a melting point of 74 ° C and 8 carbon atoms, a polymer of a mixture of fluoroalkyl acrylate having a melting point of 88 ° C and 9 to 12 carbon atoms), n -Polymers of alkyl oxazolines (eg, If the melting point is 155 ° C and the number of carbon atoms is 1,
6, a polymer obtained by reacting a hydroxyalkyl acrylate or methacrylate with an alkyl isocyanate (for example, a polymer obtained by reacting hydroxyethyl acrylate having a melting point of 78 ° C. with an alkyl isocyanate having 19 carbon atoms). A polymer obtained by reacting hydroxyethyl acrylate having a melting point of 85 ° C. with an alkyl isocyanate having 22 carbon atoms), a polymer obtained by reacting a bifunctional isocyanate, a hydroxyalkyl acrylate or methacrylate, and a primary fatty alcohol (for example, It is obtained by reacting hexamethylene diisocyanate having a melting point of 103 ° C., 2-hydroxyethyl acrylate, and an alcohol having 19 carbon atoms. Polymers, may be mentioned hexamethylene diisocyanate melting point 103 ° C., 2-hydroxyethyl acrylate and the like polymer) obtained by reacting an alcohol having a carbon number of 22.

Preferred A block precursors are (A1) alkyl acrylate, alkyl methacrylate, N-alkyl acrylamide, N-alkyl methacrylamide, alkyl oxazoline, alkyl vinyl ether,
Alkyl vinyl ester, α-olefin, alkyl-
1,2-epoxides, and alkyl glycidyl ethers (these alkyl groups are n-alkyl groups containing 14 to 50 carbon atoms), and the corresponding fluoroalkyl monomers (these alkyl groups are 6 to 50 carbon atoms)
60 to 100% by weight of units derived from at least one monomer selected from the group consisting of: (A2) alkyl acrylate, alkyl methacrylate, N-alkyl acrylamide A unit derived from at least one monomer selected from the group consisting of alkyl vinyl ethers, alkyl vinyl ethers, and alkyl vinyl esters (the alkyl groups are n-alkyl groups containing 4 to 12 carbon atoms). -20% by weight and (A3) derived from at least one polar monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, and N-vinylpyrrolidone. The unit used is 0 5 is a polymer in a weight percent range.

The polymer block B made of an amorphous thermoplastic polymer may be of any type, but its glass transition temperature (Tgs) is lower than Tq, preferably lower than Tq by 10 ° C. or more. , More preferably at a temperature lower by at least 20 ° C. than Tq. Tgs also
It must be below the temperature at which the thermoplastic elastomer exhibits elastomeric properties, preferably below 0 ° C, more preferably below -20 ° C, even more preferably-
40 ° C. or less. The number average molecular weight of the polymer block B is preferably from 5,000 to 500,000,
It is more preferably at most 200,000, further preferably at most 100,000, particularly preferably at most 10,000.
0 to 80,000.

The polymer block B is usually preferably one kind, but may be two or more kinds. One block of the polymer block B has one or more kinds of repeating units. When two or more polymer blocks B are present, the Tgs of each block may be different.

Examples of the polymer block B include those derived from polyether (for example, derived from tetrahydrofuran and containing an aliphatic group, an aromatic group, and a mixed aliphatic aromatic group between ether bonds, for example, derived from tetrahydrofuran. Acrylate, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, acrolein, vinyl esters, and at least one alkyl having optionally copolymerizable monomers such as styrene. Including polymers having acrylate, methacrylate, acrylamide or methacrylamide as constituents), polyesters (e.g., dihydroxy compounds and dicarboxylic acids or their derivatives such as acid chlorides or esters). Derived from lactones, polyamides (e.g., derived from lactones or diamines and dicarboxylic acid derivatives such as dicarboxylic acids or acid chlorides thereof), polyurethanes (e.g., derived from dissocyanates and dihydroxy compounds or diamines) ) And polysiloxanes.

In the above-mentioned thermoplastic elastomer, the polymer block B is amorphous, but may be crystalline instead of or together with it. As the crystalline polymer block B, the same as the above-described polymer block A, or a polymer different from the polymer block A but conventionally known as a crystalline polymer can be used. In this case, the melting point Tms of the polymer block B needs to be (Tq−10) ° C. or less. Further, the polymer block B is preferably connected to two polymer blocks A. Also,
Tq and / or Tms is (Tm−10) ° C. or higher and (Tm
(m + 5) ° C. or lower, and (Tm−
5) The temperature is preferably not lower than Tm and not higher than Tm ° C.
Tq or Tms is preferably 0 to 200 ° C, more preferably 150 ° C or less, particularly preferably 1 ° C or less.
20 ° C. or less.

The above-mentioned thermoplastic elastomer may optionally contain a crystalline block having no crystallizable portion and having no side chain. In this case, the melting point Tmh or glass transition point Tgh of this block is determined by the melting point Tm of the block having a side chain having a crystallizable portion.
Must be higher, not lower. Therefore,
Tm is (Tmh-10) ° C or lower or (Tgh-10) ° C
Or less, more preferably (Tmh-20) ° C or less or (Tgh-20) ° C or less,
(Tmh-40) ° C or lower or (Tgh-40) ° C or lower is particularly preferable.

In the thermoplastic elastomer used in the present invention, the polymer block A is a polymer block B
Are preferably connected at one end or both ends. The thermoplastic elastomer is composed of a polymer block A and a polymer block B, and has an ABA (triblock), (AB) _n or A _n B (where n is at least 2) structure as a polymer chain. A mixture having such a structure is also used. _An B includes various graft polymers.

In order for the thermoplastic elastomer to exhibit elastomer properties exhibiting a sharp decrease in viscosity above Tq, the polymer block B must have a melting point higher than the glass transition temperature of the polymer block B (preferably Tgs At least 10 ° C. or more). When the thermoplastic elastomer is a solid, the polymer block A is insoluble in the polymer block B and fixes the polymer block B at a temperature not higher than Tq of the polymer block A, and at a temperature not higher than Tq and not lower than Tgs. Shows elastomer properties. However, at temperatures above Tq, the viscosity of the thermoplastic elastomer drops sharply. At temperatures above Tq, polymer block A and polymer block B
Are compatible, but the higher the compatibility, the greater the decrease in viscosity.

In the thermoplastic elastomer according to the present invention, the polymer block A accounts for 2 to 90% by weight based on the total amount of the polymer blocks A and B. 10
It is preferably in the order of 90 to 90% by weight, 10 to 70% by weight, 25 to 60% by weight, and the crystallizable portion can be 65% by weight or less, 60% by weight or less. The content of the crystalline block having no crystallizable portion in the chain measurement is preferably 10% by weight or less, particularly preferably 5% by weight or less, based on the thermoplastic elastomer.

The thermoplastic elastomer according to the present invention comprises:
Precursors corresponding to each of the polymer block A and the polymer block B are prepared, and if necessary, these precursors can be functionalized, and then the precursors can be reacted to produce a polymer block. For example, an A block precursor containing at least one hydroxyl or amino group (e.g., prepared by polymerizing an alkyl monomer and a capping agent, or polymerizing an acrylic epoxide or oxazoline), and two or more B containing an isocyanate group or an acid chloride group of
It can be reacted with a block precursor.

The thermoplastic elastomer also prepares a precursor polymer corresponding to the block B, and then, if necessary, functionalizes both ends of the precursor. May be adjusted and thirst. For example, the B-butock precursor can be difunctional by way of a merbut group, and then an acrylic monomer and an initiator can be added to the bifunctional precursor to prepare block A.

In another method, the purified monomers are added sequentially to a reaction medium containing a suitable initiator. Here, this monomer is a monomer that is preferably added on the living growing polymer chain. For example, living cationic polymerization involves adding the monomers of block A followed by block B
And terminating the polymer chain by adding the monomers of block A, or by adding a series of monomers of block A and block B to prepare a block copolymer of the desired composition. Such a method may employ an H1 / 12 initiator system of the type disclosed in Macromolecules 18: 213 et seq. (1985).

The thermoplastic elastomer is prepared from an A block precursor, preferably an acrylate or methacrylate polymer having a crystallizable moiety in the side chain, and a block B monomer, preferably an alkyl acrylate or methacrylate (wherein Alkyl group is 3-8
Containing carbon atoms) can be prepared by polymerizing under conditions such that at least two A block precursor molecules are incorporated into the backbone of each polymer chain formed by the block B monomers. For example, by preparing an acrylate or methacrylate polymer having a crystallizable moiety in the side chain, capping it with mercaptoethanol, and reacting with isocyanatoethyl methacrylate, methacryloyl isocyanate, acryloyl chloride, or methacryloyl chloride. It can be functionalized and then reacted with butyl acrylate and / or similar low molecular weight acrylates. Depending on the proportion of reactants and the presence of the chain transfer agent, the ratio of block B to block A can be adjusted.

The thermoplastic elastomers according to the invention generally exhibit an elongation of 5 to 500%, for example 50 to 500%. These elastic moduli are generally between 10 and 100,00
0 psi (0.7 to 7,000 kg / cm ² ), for example, 10 to 5
0,000 psi (0.7-3500 kg / cm ² ). A
The higher the block split, the higher the modulus of elasticity.

The thermoplastic elastomer contains 2 to 90% by weight, preferably 10 to 70% by weight, particularly preferably 25 to 60% by weight of the block A. When the thermoplastic elastomer of the present invention is cooled from above Tq to substantially below Tq, it does not crystallize immediately upon reaching the Tq temperature. There is a delay before crystallization occurs. Recrystallization time measured as described above (XL
Time) is a measure of that delay, but it should be shown that as Tq rises above the measured temperature, the time to recrystallization generally decreases. The preferred delay length is
Varies by application.

The number average molecular weight (M
n) is generally from 5,000 to 800,000, preferably from 10,000 to 800,000, for example from 5,000 to 800,000.
400,000, especially 10,000 to 200,000. The Mw / Mn ratio is generally 1 to 15, for example, 2 to 4.

In the present invention, the thermoplastic elastomer is
It is combined with the second component which is a curing accelerator. "Combined" is used in a broad sense. For example,
The second component is a solid composition, preferably uniformly dispersed in the thermoplastic elastomer, wherein the thermoplastic elastomer surrounds the second component, which may be in the form of small particles, and is preferably encapsulated. . The amount of thermoplastic elastomer in the composition is generally at least 10% by weight, preferably at least 15% by weight, more preferably at least 20% by weight, based on the total amount of thermoplastic elastomer and second component. %. Further, the second component may be bonded to the thermoplastic elastomer by an ionic bond or the like. In this case, as in the above, the thermoplastic elastomer surrounds the second component, and is preferably encapsulated. ing.

As the above-mentioned curing accelerators, organometallic compounds which are the most common as curing accelerators for unsaturated polyester resins and vinyl ester resins, for example, metal soaps (fatty acids such as acetic acid, octenoic acid, stearic acid and the like) Naphthenic acid Mg, Ca, Zn, AL, V, Cr, Mn, F
metal salts of metals such as e, Co, Ni, Pb, Cu, Zr,
Particularly preferred are cobalt salts and manganese salts), and organometallic complexes (such as acetylacetone complexes of transition elements such as cobalt acetylacetonate and manganese acetylacetonate) and the like, which are bonded to the thermoplastic elastomer by ionic bonds or the like. As the second component, Mg, Ca, Z
n, AL, V, Cr, Mn, Fe, Co, Ni, Pb,
There are metals such as Cu and Zr or their ions.

The crystalline additive of the present invention is a combination of the thermoplastic elastomer and the second component, which is prepared by mixing the organometallic compound while the thermoplastic elastomer is melted or by mixing and reacting. After that, it can be produced by cooling. As a result, the polymer block A in the crystalline additive fixes the polymer block B by crystallization below its melting point, and thus plays a role of a shell material, and is incorporated with the incorporated organometallic compound or ionic bond. Since the activity of the metal is suppressed, the function of accelerating the curing reaction in the presence of the organic peroxide as the curing agent is greatly reduced, and the presence of the accelerator can be ignored in practice. On the other hand, the thermoplastic elastomer has Tq
When heated to the above temperature, the crystallization is broken and the polymer block A and the polymer block B become compatible with each other, so that they exhibit fluidity. For this reason, the function as a shell material is lost, and the organometallic compound having the side chain having a crystallizable portion and incorporated into the polymer block A and / or the polymer block B made of an amorphous thermoplastic polymer or The activity of the metal bonded by ionic bonding or the like is greatly expressed. As a result, the effect of accelerating the curing reaction in the presence of the organic peroxide is rapidly generated.

As the metal in the crystalline additive or the metal of the organometallic compound, cobalt, vanadium or manganese is particularly preferred. The content of the metal or organometallic compound in the crystalline additive is preferably 0.3% by weight or more in terms of metal based on the entire crystalline additive, and the upper limit is 20%.
Weight percent is sufficient.

The melting point of the thermoplastic elastomer can be appropriately selected according to the use conditions of the resin composition for a molding material in the present invention.

Further, the melting point of the crystalline additive (the melting point of the thermoplastic elastomer) in the present invention is, specifically, polyalkyl which constitutes a side chain having a crystallizable portion bonded to the side chain of the polymer block A. By changing the number of carbon atoms of an alkyl group in a polymer such as acrylate or polyalkyl methacrylate within the range of 12 to 22, the melting point measured by a differential scanning calorimeter or the like from 0 ° C. to about 2 ° C.
The temperature can be arbitrarily selected within the range of 00 ° C., but is set at 150 ° C. or lower for curability at a lower temperature.
C. or lower, more preferably 100 ° C. or lower. Further, the melting point is preferably 40 ° C. or higher from the viewpoint of stability at low temperatures. Commercial products of such crystalline additives include Intelimer 6050 (melting point about 65 ° C.), Int.
elimer 6054 (melting point about 65 ° C), Intelimer 216-
88 (melting point about 95 ° C), Intelimer 216-17 (melting point about 55 ° C), Intelimer 205-108 (melting point about 45 ° C)
° C), Intelimer 175-203 (melting point about 65 ° C) and the like (all are trade names of Landec Corporation).

The amount of the crystalline additive used is based on 100 parts by weight of the total amount of the unsaturated polyester resin and the polymerizable monomer.
It is preferable to use 0.1 to 4 parts by weight,
More preferably, 1.5 parts by weight are used. If the amount is too small, the effect of the present invention is not sufficient to obtain the fast-curing property at the time of curing, and if the amount is more than the above range, the accelerating effect is saturated and the added amount is increased. However, not only is it not possible to obtain a rapid curing property corresponding to the above, but also the cost is undesirably high. The crystalline additive is dispersed in the thermosetting resin composition of the present invention at a temperature lower than its melting point. It is particularly preferable that the crystalline additive is dissolved in the thermosetting resin composition by heating the thermosetting resin composition to a temperature equal to or higher than the melting point of the crystalline additive. The resin composition according to the present invention may be used in combination with a colorant, an inorganic filler and an anti-settling agent.

The viscosity of the thermosetting resin composition of the present invention is 0.1.
01 to 3 Pa · s (25 ° C.) is preferred. As a method of insulating the coil with the thermosetting resin composition of the present invention, immersion impregnation, drop impregnation, or the like is performed. Curing reaction temperature is 60 ~
100 ° C. is preferred.

[0052]

Next, the present invention will be described with reference to examples, but the present invention is not limited by these examples. In the following examples, “parts” means “parts by weight” unless otherwise specified.

Example 1 8 mol of dicyclopentadiene and 8 mol of maleic acid were charged into a synthesis kettle, and further, hydroquinone was charged at 0.02% by weight of the total weight of the above two substances, the temperature was raised to 70 ° C., and water was added at 0.
4 mol was added. Further, 0.4 mol of water was added, the temperature was raised to 140 ° C. while paying attention to the heat of reaction, the reaction was carried out at 140 ° C. for 1 hour, and then the temperature was lowered to 100 ° C. or less. Next, 1 mol of ethylene glycol, 10 mol of 2,2'-oxydiethanol, 1 mol of phthalic anhydride, and 5 mol of maleic anhydride were charged and synthesized at 205 ° C. for 9 hours. When the acid value became 25 or less, the reaction was carried out. Was completed to obtain an unsaturated polyester resin. 70 parts of the obtained unsaturated polyester resin and 30 parts of styrene were mixed at 80 ° C. for 1 hour to obtain an unsaturated polyester resin liquid A.

100 parts of unsaturated polyester resin solution A, 3 parts of cumene hydroperoxide as a peroxide, and Intelimer 6054 as a crystalline additive (trade name of Landec Corporation, cobalt content: 4% by weight, melting point: 65) C) is mixed to obtain a uniform resin composition without sedimentation of the mixed components.

The appearance, gel time, and the like of the obtained resin composition
Table 1 shows the results of measuring the pot life and the helical coil adhesive strength.

<Test Method> Appearance The liquid appearance was visually determined. 2. Gel time According to the test tube method specified in J1SC2105,
The measurement was performed at 60 ° C, 80 ° C, and 100 ° C. 3. Pot life As in the case of gelation time, place 70 mm from the bottom in a test tube of 18 mm in diameter.
mm, put the resin composition, seal, leave at 23 ℃,
The liquid flow of the resin string composition was confirmed at predetermined time intervals. The point at which the liquid flow became non-uniform was determined as pot life.

4. Helical Coil Adhesion A test was performed according to the helical coil adhesion test of J1SC2105. However, a test piece was prepared using an esterimide wire having a diameter of 1.0 mm as a wire and a mandrel having a diameter of 50 mm. Varnish treatment is Jls C 2
The treatment is carried out by the twice treatment method specified in 105, and the curing temperature is 80
° C, the first curing time was 15 minutes, and the second curing time was 30 minutes. Five tests were performed at 23 ° C. and 155 ° C., respectively, and the average value was taken.

Example 2 In Example 1, Intelimer 60 was used as a crystalline additive.
54 (trade name of Landec Corporation, cobalt content: 4% by weight, melting point of crystallized polymer: 65 ° C)
The same operation as in Example 1 was carried out except that 0.6 parts was changed to 1.2 parts of Inte1imer 6050 (trade name of Landec Corporation, cobalt content: 2% by weight, melting point of crystallized polymer: 65 ° C.), and the resin composition was changed. The product was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 In Example 1, Intelimer 6 was used as a crystalline additive.
054 (brand name of Landec Corporation, cobalt content: 4% by weight, melting point: 65 ° C)
The procedure was performed in the same manner as in Example 1 except that r175-203 (trade name of Landec Corporation, vanadium content: 1% by weight, melting point of the crystallized polymer: 65 ° C) was used. The results are shown in Table 1.

Example 4 70 parts by weight of ethylene glycol monomethyl ether and 50 parts by weight of toluene were charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer, and heated to 80 ° C. under a nitrogen gas atmosphere. And maintain the reaction temperature at 80 ± 2 ° C. for 4 hours.
Parts by weight, 15 parts by weight of methacrylic acid, 15 parts by weight of methyl methacrylate, 10 parts by weight of ethyl acrylate, and 2 parts by weight of 2,2'-azobis (isobutyronitrile) were added dropwise. After completion of the dropwise addition, stirring was continued at 800 ° C. ± 2 ° C. for 6 hours to obtain a crystalline vinyl copolymer having a weight average molecular weight of about 30,000 and an acid value of 97.8 mgKOH / g. Next, 7 parts by weight of manganese (III) acetylacetone was added, and the mixture was stirred at 80 ° C. ± 2 ° C. for 1 hour, transferred to a flat vat, and scattered with a dryer at 60 ° C. ± 2 ° C. for 48 hours. did. Thereafter, the mixture was pulverized with a pulverizer to obtain a crystalline additive A. Example 1 is the same as Example 1 except that the above crystalline additive A was used in place of Intelimer 6054 (trade name of Landec Corporation, cobalt content: 4% by weight, melting point: 65 ° C) as the crystalline additive. Performed according to 1. The results are shown in Table 1.

Comparative Example 1 A resin composition was prepared by removing a block copolymer of the crystallized polymer having a specific melting point and the amorphous polymer having a specific glass transition temperature of Example 1 except for Inteimer 6054 as a cobalt compound. Hereinafter, the same evaluation as in Example 1 was performed, and the results are shown in Table 1.

Comparative Example 2 Inteimer 6054 (trade name, manufactured by Landeck Corporation, cobalt content) was used as a cobalt compound in the block copolymer of the crystallized polymer having a specific melting point and the amorphous polymer having a specific glass transition temperature in Example 1. :
0.6 parts of 4% by weight, melting point of the crystallized polymer: 65 ° C.) was used as a resin composition with 0.27 parts of manganese naphthenate (cobalt content: 6% by weight), and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[0063]

[Table 1]

[0064]

The thermosetting resin composition of the present invention has a composition of 60 to 60.
It cures even at a relatively low temperature of about 80 ° C, reduces the energy required for curing, and extends the pot life at room temperature. Therefore, it is possible to mix and mix a large amount of varnish at a time and reduce waste varnish. Electrical equipment can be manufactured. Further, the coil according to the present invention can be manufactured by a method which has a high working efficiency and a small amount of wasted insulating material in consideration of the environment in manufacturing the coil.

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Claims (7)

[Claims] (A) an unsaturated polyester resin (40 to 8)
0 parts by weight, (B) 20 to 60 parts by weight of a polymerizable monomer,
(C) Crystalline additive containing organometallic compound or metal
A thermosetting resin composition containing 1 to 5% by weight (based on the total amount of the components (A) and (B)). 2. The thermosetting resin composition according to claim 1, wherein the metal contained in the crystalline additive and the metal of the organometallic compound are cobalt, vanadium or manganese. 3. The thermosetting resin composition according to claim 2, wherein the content of cobalt, vanadium, manganese or a compound thereof in the crystalline additive is in the range of 0.3 to 20% by weight in terms of metal. 4. The method according to claim 1, further comprising:
The thermosetting resin composition according to any one of claims 1 to 3, which contains 4 parts by weight. 5. The crystalline additive comprises a thermoplastic elastomer having a side chain having a crystallizable portion, and has a melting point of 4.
The thermosetting resin composition according to any one of claims 1 to 4, which is within a range of 0 to 120 ° C. 6. The thermosetting resin composition according to claim 1, wherein the polymerizable monomer is styrene and / or a styrene derivative. 7. A method for producing a coil, comprising performing insulation treatment using the thermosetting resin composition according to claim 1.