JP4697511B2 - Resin composition, resin composition for electrical insulation, and method for producing electrical equipment insulator - Google Patents

Description

  The present invention relates to a resin composition, a resin composition for electrical insulation, and a method for producing an electrical equipment insulator. More specifically, a non-or low-reactive diluent-containing resin composition as an impregnation, casting and coating composition used for electrical and electronic components and as a carrier material for sheet-like insulating materials, for electrical insulation The present invention relates to a resin composition and a method for producing an electrical equipment insulator.

In recent years, in the field of chemical industry, various environmental technologies have been actively researched and developed for safer products and products with less environmental pollution. For example, low-solvent-free resins and water-soluble resins There is sex type resin. On the other hand, electric devices such as motors and transformers are treated with an electrically insulating resin composition for the purpose of fixing or preventing rusting of iron cores, insulating or fixing coils.
As the resin composition for electrical insulation, a composition of an unsaturated polyester resin having an excellent balance of curability, air drying, electrical insulation, stability, economy and the like is widely used.

  The resin composition for electrical insulation is divided into a liquid type and a powder type. The liquid type is prepared by dissolving a synthetic resin in a diluent and adjusting the viscosity so that it can be easily worked. The liquid type is classified into a solvent type, a solventless type, and a water-soluble type depending on the type of the diluent. Since some or all of these diluents are volatilized during the electrical insulation process, an anti-scattering process is performed using a catalytic combustion apparatus or the like. However, some or all of the amount may be scattered in the atmosphere, and there is concern about the impact on the environment. For these reasons, in recent years, reduction of the VOC amount in the resin composition has been eagerly desired.

Therefore, the following resin compositions for electrical insulation have been used so far for the purpose of reducing VOC generated during electrical insulation treatment.
(1) Method using water-soluble resin composition for electrical insulation to make most of the diluent water (water-solubilization)
(2) Method for eliminating diluent using powdery resin composition for electrical insulation (powdering)
(3) High solidification of resin composition for electrical insulation by methods of increasing resin content or adding inorganic filler Among these, (1) water-solubilization is the VOC content in the resin composition for electrical insulation. If it is attempted to decrease, the resin composition becomes cloudy due to standing over time, and therefore it is necessary to use a part of an organic solvent having good compatibility with the resin. As a result, the VOC content in the resin composition can be reduced only to 10% by weight (Patent Document 1, Patent Document 2).
In the powdering of (2), VOC is hardly generated at the time of electrical insulation treatment, but since the resin composition for electrical insulation is powdery, it can diffuse into the atmosphere and cause various problems as dust. Due to the nature, handling was not easy. Furthermore, when the melting temperature of the composition is high or when the viscosity at the time of melting is high, there is a concern that impregnation into the coil may be reduced.
The high solidification of (3) is that, in the conventional method, if the VOC content in the resin composition for electrical insulation is to be reduced, the viscosity becomes high and the impregnation property to the coil of the electrical equipment is reduced. Therefore, there is not much effect in reducing the VOC content in the resin composition for electrical insulation.
As a countermeasure for this, unsaturated polyester resins having a structural unit of dicyclopentadiene (= DCPD) have been the subject of numerous patents and have been utilized.

  According to Patent Document 3, it is achieved by newly introducing a dicyclopentadiene structure in the production of polyester, has good storage stability, is a liquid composition even at room temperature, or has a softening point that can be easily processed. It has been found that a composition which is low and can be stably stored in a universal form for a very long time can be obtained without containing monomers having vinylic unsaturation. However, in this method, the air drying property and the characteristics after heat deterioration are remarkably worse than those of the general-purpose resin composition, and cannot be actually used in the conventional manufacturing method by thermosetting, and UV light and heat are combined. Suitable for curing only.

  As a method for maintaining the characteristics after thermal deterioration, there are a polyimide wire, a polyamideimide wire, and a polyesterimide wire, which have been conventionally used for insulated wires having heat resistance. Among these, for example, polyester imide in which an imide bond and an isocyanurate ring are introduced into a molecular chain using tris (2-hydroxyethyl) isocyanurate (hereinafter abbreviated as THEIC) from the viewpoint of balance between characteristics and price. Resin is often used. However, the adhesion of the polyesterimide varnish using the conventional THEIC was insufficient for the requirements.

  As means for improving the adhesion between the polyesterimide varnish and the conductor using THEIC, Patent Document 4 and Patent Document 5 disclose that a thiol compound is blended in the polyesterimide varnish. However, when this method is used, the adhesion between the conductor and the film is improved, but the air drying property is deteriorated, and the obtained resin has a high molecular weight, and there is no organic solvent having a good compatibility. Then, problems such as poor workability occur. Furthermore, there has been a problem that the adhesion between the conductor and the film after heat deterioration is extremely reduced.

  In addition, as a technique for improving air drying properties, as in the method described in Patent Document 6, a reaction of dicyclopentadienyl monomaleate with a fatty acid, unsaturated dibasic acid, saturated acid and alcohol component of a dry or semi-dry vegetable oil. A technique is described in which an unsaturated polyester obtained by adding a xylene-formaldehyde resin and a polymerization initiator is contained.

Further, in Patent Document 7, 25 to 50% by weight of a polyester (meth) acrylate containing a structural unit derived from tetrahydrophthalic acids in a skeleton, 15 to 55% by weight of an epoxy (meth) acrylate, and a monofunctional (meth) acrylate monomer And a method of using a curable resin composition containing 15 to 45% by weight of a monomer having a boiling point of 90 ° C. or higher at 6.7 × 10 ³ Pa, containing 50 to 100% by weight of a bifunctional (meth) acrylate monomer However, as a method of using this, only a material for covering concrete, mortar, steel plate, glass, wood, etc., in particular, a top coat material for FRP waterproof lining is specified, and a resin composition for electrical insulation. Not applied as.

Japanese Patent Laid-Open No. 2001-243838 JP 2002-235296 A JP 2000-515565 A JP-A-2-58567 JP 7-316425 A JP-A-10-139994 JP 2001-151832 A Japanese Patent Publication No.51-40113

  In view of such problems, the present invention has been heretofore aimed at reducing the VOC contained in a resin composition in a resin composition for electrical insulation and a method for producing an electrical device using the same for the purpose of launching an environmentally friendly product. It exhibits a cured product characteristic such as good electrical insulation and good stability equivalent to or better than the liquid type resin composition, and is generated during electrical insulation treatment of electrical equipment from the viewpoint of safety improvement and work environment. The present invention provides a resin composition capable of reducing VOC, and further provides a method for producing an electrical equipment insulator using the electrical insulation resin composition.

The present invention includes [1] (A) a polyesterimide resin, (B) an α, β-unsaturated polybasic acid or an anhydride thereof and trimethylolpropane, or a derivative thereof as essential components. A resin composition comprising an unsaturated polyester resin obtained by reacting a monohydric alcohol as a synthetic raw material as an essential material.
The present invention also provides [2] (A) a polyesterimide resin, (B1) an epoxy compound having one or more epoxy groups in the molecule and an α, β-unsaturated monobasic acid. It becomes a saturated epoxy ester resin, and a modified unsaturated epoxy ester resin obtained by reacting 1 to 20 mol% of an unsaturated acid anhydride with respect to the hydroxyl group of the obtained unsaturated epoxy ester resin is an essential material. It is a resin composition.
Moreover, this invention is a resin composition as described in said [1] or said [2] whose molecular weight of [3] polyesterimide resin (A) is the range of 400-10000.
Moreover, this invention is a resin composition as described in said [1] whose molecular weight of [4] unsaturated polyester resin (B) is 200-10000.
Moreover, this invention is a resin composition as described in said [2] whose molecular weight of [5] modified | denatured unsaturated epoxy ester resin (B1) is 200-10000.
Moreover, this invention is [6] polyesterimide resin (A) 100 weight part of unsaturated polyester resin (B) containing 10-100 weight part of said [1], [3], [4] The resin composition according to any one of the above.
[7] The present invention [2], [3] or [5] contains 10 to 300 parts by weight of the modified unsaturated epoxy ester resin (B1) with respect to 100 parts by weight of [7] polyesterimide resin (A). ] The resin composition in any one of.
The present invention also provides [8] an electrically insulating resin composition comprising a polymerization initiator and a stabilizer in the resin composition according to any one of [1] to [7].
Moreover, this invention is a manufacturing method of the electrical equipment insulator characterized by coating [9] electrical equipment with the resin composition for electrical insulation as described in said [8], and hardening | curing.

  The resin composition for insulating electrical equipment according to the present invention significantly reduces VOC generated during electrical insulation treatment of electrical equipment from the viewpoint of improving safety and working environment, compared to conventional resin compositions. In addition, the present invention can provide a highly reliable electric device that exhibits cured product characteristics such as air drying properties and electrical insulation properties that are equal to or higher than those of conventional liquid type resin compositions, and good stability.

  The polyesterimide resin (A) in the present invention is represented by the general formula (1) as a part of the acid component.

〔式中、Ｒ^１はトリカルボン酸残基等の３価の有機基、Ｒ^２はジアミン残基等の２価の有機基を意味する〕で表されるイミドカルボン酸を用いるものが好ましい。

It is preferable to use an imidocarboxylic acid represented by the formula [wherein R ¹ represents a trivalent organic group such as a tricarboxylic acid residue, and R ² represents a divalent organic group such as a diamine residue].

  Examples of the imide carboxylic acid represented by the general formula (1) include imide carboxylic acid obtained by reacting 2 mol of tricarboxylic anhydride with 1 mol of diamine (see Patent Document 8). In addition, diamine and tricarboxylic acid anhydride may not be used as imide carboxylic acid by reacting in advance, and diamine and tricarboxylic acid anhydride may be added during the production of polyesterimide resin to form an imide dicarboxylic acid residue. .

Examples of the tricarboxylic acid anhydride include trimellitic acid anhydride, 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyltricarboxylic acid anhydride, and trimellitic acid anhydride is preferable.
As the diamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 1,4-diaminonaphthalene, hexamethylenediamine, diaminodiphenylsulfone and the like are used.

  The amount of imide dicarboxylic acid used is preferably in the range of 5 to 50 equivalent%, more preferably in the range of 20 to 45 equivalent% of the total acid component. If the amount of imidodicarboxylic acid used is too small, the heat resistance tends to be inferior, while if too large, the flexibility may be lowered.

  As an acid component other than the above-mentioned imide dicarboxylic acid, terephthalic acid or a lower alkyl ester thereof, for example, terephthalic acid diesters such as monomethyl terephthalate, lower alkyl diesters of terephthalic acid, for example, dimethyl terephthalate, and the like are used. Further, isophthalic acid, adipic acid, phthalic acid, sebacic acid and the like can also be used.

  Examples of the alcohol component to be esterified by reacting with the imide carboxylic acid to form a polyesterimide resin include, for example, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,3-butanediol, and 1,4-butanediol. Diols such as glycerol, triols such as glycerin, trimethylolpropane and hexanetriol are used. These acid components and alcohol components may be used alone or in combination of two or more.

  The blending ratio of the alcohol component and the acid component is low / solvent-free and has a low molecular weight with good workability, and from the viewpoint of flexibility and heat resistance, the equivalent ratio of hydroxyl group to carboxyl group is 1.3 to 30 is preferable, and 1.5 to 10 is more preferable. If the equivalent ratio of the hydroxyl group to the carboxyl group is larger than 30, the flexibility tends to decrease, and if it is less than 1.3, the heat resistance tends to decrease.

  The synthesis of the polyesterimide resin used in the present invention is performed, for example, by combining the acid component and the alcohol component in the presence of an esterification catalyst at a temperature of 160 to 250 ° C, preferably 170 to 250 ° C for 3 to 15 hours, preferably Is carried out by heating for 5 to 10 hours. In this case, examples of the esterification catalyst used include tetrabutyl titanate, lead acetate, dibutyltin laurate, and zinc naphthenate. The reaction is preferably performed in an inert atmosphere such as nitrogen gas. The above-mentioned imide dicarboxylic acid may be synthesized in advance, or imidation and esterification by mixing and heating components that become imide and imide acid of trimellitic anhydride simultaneously with other acid components and alcohol components. May be performed simultaneously. At this time, the blending amount of diamine and trimellitic anhydride is preferably set to an amount corresponding to the blending amount of the imide dicarboxylic acid. Moreover, since the viscosity at the time of synthesis is high, synthesis can also be performed in the presence of a phenol solvent such as phenol, cresol, xylenol, and the like.

  The number average molecular weight of the polyesterimide resin used in the present invention (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve, the same shall apply hereinafter) is preferably 400 to 10,000. More preferably, it is 500-3000. If it is less than 400, the curability of the resin and the properties of the cured resin are extremely inferior. If it exceeds 10,000, the viscosity is too high and the workability deteriorates.

  In addition, the α, β-unsaturated polybasic acid or an anhydride thereof, which is an essential synthetic raw material for the unsaturated polyester resin (B) in the present invention, is, for example, an α, β-unsaturated dibasic acid or an anhydride thereof. Examples thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides thereof such as maleic anhydride. Two or more of these may be used in combination.

  Further, as trimethylolpropane, which is another essential component of the unsaturated polyester resin (B) in the present invention, or a derivative thereof, other than trimethylolpropane, polyoxyethylene trimethylolpropane ether or trimethylolpropane diallyl ether To be elected. Two or more of these may be used in combination. These contents are blended so as to be 10/100 to 100/100, more preferably 50/100 to 85/100, when the total amount of all polyvalent glycols is 100 parts. When it is less than 10, the air drying property of the resulting resin tends to deteriorate.

  As the polybasic acid used in the present invention, an α, β-unsaturated polybasic acid or its anhydride is used to adjust the concentration of the unsaturated group, and to impart characteristics such as flexibility and heat resistance. In addition, a saturated polybasic acid or an anhydride thereof is used in combination. At this time, as α, β-unsaturated polybasic acid or anhydride a thereof and saturated polybasic acid b, a / (a + b) = 0.2 / 1 to 0.95 / 1, more preferably It mix | blends so that it may become 3/1-0.8 / 1. When the α, β-unsaturated polybasic acid or anhydride thereof is less than 0.2 / 1, the strength of the obtained molded product gradually decreases, and the strength of the obtained molded product tends to decrease. Therefore, the α, β-unsaturated polybasic acid or the anhydride a thereof is more preferably a / (a + b) = 0.3 / 1 to 0.75 / 1, and 0.4 / 1 to Particularly preferred is 0.7 / 1.

  Saturated polybasic acids or anhydrides used in combination include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexahydrophthalic acid Examples thereof include acid, hexahydrophthalic anhydride, glutaric acid, adipic acid, sebacic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, dimer acid, succinic acid, azelaic acid, and rosin-maleic acid adduct. Two or more of these may be used in combination. If necessary, a saturated polybasic acid ester can also be used.

  Saturated polybasic acid esters include ethylene glycol, propylene glycol, butylene glycol and other alkylene glycols, especially linear alkylene glycol and adipic acid, sebacic acid, terephthalic acid, naphthalic acid Dibasic acids such as linear alkylene groups, or low molecular weight esters or high molecular weight esters (ie saturated polyesters) of a dibasic acid in which a paraphenyl group and a carboxyl group are bonded. (Ethylene terephthalate), di (butylene terephthalate), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, di (ethylene adipate), di (butylene adipate) G), polyethylene adipate, polybutylene adipate, etc.These can also use 2 or more types together.

  Polyhydric alcohols, which are another synthetic raw material for unsaturated polyester resins, include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol 1,3-butanediol, and 1,6-hexanediol. And dihydric alcohols such as neopentyl glycol, 1,4-cyclohexanediol and hydrogenated bisphenol A, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol. Two or more of these may be used in combination.

  The polybasic acid and the polyhydric alcohol are equivalent ratios, and when the polybasic acid is 1, it is preferable to use the polyhydric alcohol in the range of 1 to 5, and in the range of 1.005 to 2.0. More preferably. When the polyhydric alcohol decreases, the molecular weight of the unsaturated polyester resin obtained tends to increase or gelation tends to occur when the polyester resin is produced. When the polyhydric alcohol increases, the acid value decreases and the curability of the resin is poor. Tend to occur.

  As a manufacturing method of unsaturated polyester resin, it can be based on a conventionally well-known method. For example, the polybasic acid and the polyhydric alcohol are subjected to a condensation reaction, and the condensation water generated when both components react is removed from the system. Removal of the condensed water out of the system is preferably carried out by natural distillation or reduced pressure distillation through an inert gas. In order to promote the distillation of the condensed water, a solvent such as toluene or xylene can be added to the system as an azeotropic component. The progress of the reaction can be generally known by measuring the amount of distillate produced by the reaction, quantifying the functional group at the end, and measuring the viscosity of the reaction system.

  The temperature of the reaction is preferably 150 ° C. or higher, and the reaction is carried out while ventilating an inert gas such as nitrogen or carbon dioxide in order to prevent side reactions such as coloring and gelation of the unsaturated polyester resin due to oxidation. It is preferable. For this reason, a glass, stainless steel or the like is selected as the reaction apparatus, and a stirring apparatus, a fractionation apparatus for preventing distillation of alcohol components due to azeotropy of water and alcohol components, and raising the temperature of the reaction system. It is preferable to use a reactor equipped with a heating device, a temperature control device for this heating device, a blowing device for inert gas such as nitrogen, and the like.

  Although depolymerization is possible at high temperatures even in the absence of a reaction catalyst, for example, by using a catalyst such as t-butyl titanate, the temperature for depolymerization such as cracking and polycondensation reaction is lowered. be able to. The blending amount is preferably 0.01 to 1% by weight, more preferably 0.1 to 0.5% by weight, based on the total amount of all acid components. When the blending amount of the reaction catalyst exceeds 1% by weight, not only the time required for depolymerization such as cracking is not shortened, but also the weather resistance and hot water resistance of the resulting cured resin are lowered.

  The reaction temperature for carrying out the synthesis reaction is preferably in the range of 150 to 300 ° C, more preferably in the range of 160 to 280 ° C. When this temperature exceeds 300 ° C., boiling and evaporation of the polyhydric alcohol become intense. The reaction temperature can be conveniently selected and set according to the boiling point of the polyhydric alcohol used. The pressure inside the reactor adjusted to carry out the polycondensation reaction in the synthesis can proceed without any problem even at normal pressure, but the reaction is accelerated by increasing the boiling point of the polyhydric alcohol by pressurization. be able to. In this case, it is preferable to carry out in the range of normal pressure to 0.1 MPa.

  The number average molecular weight of the unsaturated polyester resin of the present invention (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve, the same shall apply hereinafter) is preferably from 200 to 10,000. More preferably, it is 500-2000. If it is less than 200, the curability of the resin and the properties of the cured resin are extremely inferior. If it exceeds 10,000, the viscosity is too high and the workability deteriorates.

  Examples of the polymerizable monomer used in a small amount according to the present invention include aromatic vinyl units such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, and tert-butylstyrene. , Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, Methacrylic acid esters of polyhydric alcohols such as dipentaerythritol tetramethacrylate, pentaerythritol hexamethacrylate, pentaerythritol hexaacrylate, diallyl phthalate, triallyl Cyanurate, acrylonitrile, and the like. Two or more of these may be used in combination. Among them, styrene is preferable from the viewpoint of compatibility with the unsaturated polyester resin and cost.

  An unsaturated polyester resin and a polymerizable monomer (reactive diluent) are blended, and a polymerization inhibitor is added as necessary to obtain an unsaturated polyester resin composition. The blending ratio of the resin composition and the polymerizable monomer at this time is such that when the total amount of both is 100 parts by weight, the resin is 60 to 100 parts by weight and the polymerizable monomer is 40 to 0 parts by weight. It is preferable to do this. If it is 40 parts by weight or more, the viscosity of the unsaturated polyester resin composition is too low, the workability is poor, the properties of the coating film at the time of curing are lowered, and the amount of VOC generation is increased.

  Examples of the polymerization initiator used in the present invention include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters, alkylperesters. And the like. The amount of the polymerization initiator is determined according to each of the curing conditions and the aspects such as the appearance and characteristics of the cured resin product. From the viewpoint of storage stability of the material and molding cycle, the content is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total amount of the unsaturated polyester resin and the polymerizable monomer.

  Stabilizers used as necessary in the present invention include p-benzoquinone, hydroquinone, naphthoquinone, p-toluquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p-benzoquinone, p-tert-butyl. Catechol, 2,5-di-tert-butylhydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol and the like can be mentioned. The blending amount is conveniently determined depending on the storage stability of the resin composition, the curing temperature and the curing time during actual machine processing, and the blending amount is usually 0.00 with respect to 100 parts by weight of the total amount of the resin composition. The amount is preferably 01 to 5.0 parts by weight, more preferably 0.01 to 3 parts by weight, and particularly preferably 0.01 to 0.1 parts by weight.

In the present invention, as a compound containing one or more epoxy groups in one molecule, which is an essential synthetic raw material of the modified unsaturated epoxy ester resin (B1), for example, glycidyl polyether of polyhydric alcohol or polyhydric phenol, epoxidation Examples include fatty acids, epoxidized drying oil acids, epoxidized diolefins, esters of epoxidized diunsaturated acids, epoxidized saturated polyesters, and the like, which can be used alone or in combination. Examples of commercially available products include, for example, Epon825, Epon828, Epon1001, Epon1002, Epon1004, Epon1007, or Epon1009 manufactured by Shell Sekiyu KK, Epicoat 815, Epicoat 827, Epicoat 828, Epicoat 834, Epicoat manufactured by Yuka Shell Epoxy Co., Ltd. 1055, Epicoat 827-X-75, Epicoat 1001-B-80, Epicoat 1001-X-70, Epicoat 1001-X-75, Epicoat 1001, Epicoat 1002, Epicoat 1004, Epicoat 1007 or Epicoat 1009, manufactured by Asahi Kasei Epoxy Corporation AER334, AER330, AER331, AER337, AER661, AER664, AER667 or AER669, Asahi Denka Kogyo Adeka Resin EP-4200, Adeka Resin EP-4300, Adeka Resin EP-4100, Adeka Resin EP-4340, Adeka Resin EP-5100, Adeka Resin EP-5200, Adeka Resin EP-5400, Adeka Resin EP-5700 or Adeka Resin EP-5900, Sumitomo SUMI Epoxy ELA-115, SUMI Epoxy ELA-127, SUMI Epoxy ELA-128, SUMI Epoxy ELA-134, SUMI Epoxy ESA-012, SUMI Epoxy ESA-014, SUMI Epoxy ESA-017 or SUMI Epoxy ESA-019 manufactured by Chemical Industries, Ltd. Manufactured by Dainippon Ink & Chemicals, Inc., Epicron 855, Epicron 840, Epicron 860, Epicron 1050, Epicron 205 , Epicron 4050, Epicron 7050 or Epicron 9050, DER330, DER331, DER661, DER662, DER664, DER667, or DER669 manufactured by Dow Chemical (Japan), Pre-Epo PE-10, Pre-Epo PE-25 manufactured by Dainippon Colors Co., Ltd. , Pre-Epo PE-70, Pre-Epo PE-80, Pre-Epo PE-100, Pre-Epo PE-120 or Pre-Epo PE-150, Etototo YD-115, Etototo YD-127, Etototo YD-128, Etototo YD-134 Epototo YD-011, Epototo YD-012, Epototo YD-014, Epototo YD-017 or Epototo YD-019, Araldite GY-250 manufactured by Ciba Geigy Japan, Aral Daito GY-261, Araldite GY-30, Araldite 6071, Araldite 6084, Araldite 6097 or Araldite 6099, Epomic R-130, Epomic R-139, Epomic R-140, Epomic R-144, Epomic R-144 manufactured by Mitsui Chemicals, Inc. 301, Epomic R-302, Epomic R-304, Epomic R-307 or Epomic R-309.
Among these, a compound having two or more epoxy groups in one molecule is preferable, and a compound having only one epoxy group in one molecule is preferably used in the range of 0 to 10% by weight. .

As the α, β-unsaturated monobasic acid, methacrylic acid, acrylic acid, crotonic acid, cinnamic acid, sorbic acid and the like can be used, and these can be used in combination. In general, methacrylic acid is preferably used from the viewpoint of corrosion resistance. The α, β-unsaturated monobasic acid is blended so that the equivalent ratio of epoxy group / carboxyl group is preferably 1.6 to 0.6, more preferably 1.2 to 0.9. The
As the unsaturated acid anhydride to be reacted with the hydroxyl group of the unsaturated epoxy ester resin, maleic anhydride, itaconic anhydride, citraconic anhydride, or the like can be used.
The unsaturated acid anhydride is preferably used in a proportion corresponding to 1 to 20 mol% with respect to the hydroxyl group of the unsaturated epoxy ester resin, and preferably used in a proportion corresponding to 2 to 10 mol%. Is more preferable. If the amount of the unsaturated acid anhydride used is outside this range, the storage stability of the modified unsaturated epoxy ester resin is poor and gelation tends to occur.

  For the reaction of unsaturated epoxy ester resin with unsaturated acid anhydride, as an addition catalyst, halides such as zinc chloride and lithium chloride, sulfides such as dimethyl sulfide and methylphenyl sulfide, dimethyl sulfoxide, methyl sulfoxide, methyl ethyl Sulfoxides such as sulfoxide, tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine, hexamethylenediamine, and hydrochlorides or bromoacids thereof, tetramethylammonium chloride, trimethyldodecylbenzylammonium chloride, etc. Examples include quaternary ammonium salts, sulfonic acids such as p-toluenesulfonic acid, and mercaptans such as ethyl mercaptan and propyl mercaptan. 0.05-2 weight part is preferable with respect to 100 weight part of unsaturated epoxy ester resins, and, as for the compounding quantity of an addition catalyst, 0.1-1.0 weight part is further more preferable.

  An unsaturated monomer may be blended as one component of the modified unsaturated epoxy ester resin. Unsaturated monomers to be blended include halogens such as styrene, vinyl toluene, ethyl vinyl benzene, isopropyl styrene, tertiary butyl styrene, α-methyl styrene, sec-butyl styrene, divinyl benzene, chlorostyrene, dichlorostyrene, etc. Aromatic vinyl monomers such as modified styrene, diallyl phthalate, triallyl cyanurate, acrylic acid, methacrylic acid, vinyl acetate, methyl acrylate, ethyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate Methacrylic acid alkyl ester, neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol hexamethacrylate , Methacrylic acid esters of polyhydric alcohols such as pentaerythritol hexaacrylate, diallyl phthalate, triallyl cyanurate, acrylonitrile. Two or more of these may be used in combination. Among these, styrene is preferable from the viewpoint of compatibility with the modified unsaturated epoxy ester resin and cost. The unsaturated monomer is preferably added in an amount of 30 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the modified unsaturated epoxy ester resin.

As a method for producing the modified unsaturated epoxy ester resin, a conventionally known method can be used. For example, the polybasic acid component and the polyhydric alcohol component are subjected to a condensation reaction, and the condensation water generated when both components react is removed from the system. Removal of the condensed water out of the system is preferably carried out by natural distillation or reduced pressure distillation through an inert gas. In order to promote the distillation of the condensed water, a solvent such as toluene or xylene can be added to the system as an azeotropic component. The progress of the reaction can be generally known by measuring the amount of distillate produced by the reaction, quantifying the functional group at the end, and measuring the viscosity of the reaction system.
The reaction temperature is preferably 90 ° C. or higher. For this reason, a glass, stainless steel or the like is selected as the reaction apparatus, and a stirring apparatus, a fractionation apparatus for preventing distillation of alcohol components due to azeotropy of water and alcohol components, and raising the temperature of the reaction system. It is preferable to use a reactor equipped with a heating device, a temperature control device for the heating device, and the like.
The reaction temperature for carrying out the synthesis reaction is preferably in the range of 80 ° C to 120 ° C, more preferably in the range of 90 ° C to 110 ° C. When this temperature exceeds 120 ° C., there is a possibility that a problem occurs that the reaction is vigorously gelled. The reaction temperature can be selected and set conveniently depending on the polyhydric alcohol used.
The pressure inside the reactor adjusted to carry out the polycondensation reaction in the synthesis can proceed without any problem even at normal pressure, but the reaction can be promoted by increasing the boiling point of the polyhydric alcohol by pressurization. Can do. In this case, it is preferable to carry out in the range of normal pressure to 0.1 MPa.
The number average molecular weight of the modified unsaturated epoxy ester resin used in the present invention (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve, the same applies hereinafter) is preferably 200 to 10,000. More preferably, it is 500-2000. If it is less than 200, the curability of the resin and the properties of the cured resin are extremely inferior. If it exceeds 10,000, the viscosity is too high and the workability deteriorates.

If necessary, blend a polyesterimide resin and a modified unsaturated epoxy ester resin with an unsaturated monomer (reactive diluent), which is a polymerizable monomer, and if necessary, add stabilizers and polymerization initiators for electrical insulation. The resin composition is used. 10 to 300 parts by weight of the modified unsaturated epoxy ester resin (B1) is contained with respect to 100 parts by weight of the polyesterimide resin (A). The modified unsaturated epoxy ester resin is preferably 10 to 100 or 100 to 300 parts by weight.
The blending ratio of the resin composition and the reactive diluent at this time is 70 to 100 parts by weight of the resin composition and 30 to 0 parts by weight of the reactive diluent when the total amount of both is 100 parts by weight. It is preferable to do this. If it exceeds 30 parts by weight, the viscosity of the resin composition is too low, resulting in poor workability and an increase in the amount of VOC generated.

  Stabilizers that can be used as necessary in the present invention include p-benzoquinone, hydroquinone, naphthoquinone, p-toluquinone, 2,5-diphenyl-p-benzoquinone, 2,5 diacetoxy-p-benzoquinone, p-tert- Examples include butyl catechol, 2,5-di-tert-butylhydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol. The blending amount is conveniently determined by the curability of the resulting resin composition, but the blending amount is preferably 0.01 to 5.0 parts by weight, more preferably 0 to 100 parts by weight of the resin composition. 0.01 to 3 parts by weight, particularly preferably 0.01 to 0.1 parts by weight.

  Examples of the polymerization initiator used in the present invention include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters, alkylperesters. And the like. The amount of the polymerization initiator is determined according to each of the curing conditions and the aspects such as the appearance and characteristics of the cured resin product. From the viewpoint of the storage stability of the material and the molding cycle, it is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total amount of the polyesterimide resin, the modified unsaturated epoxy ester resin and the polymerizable monomer. It is.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to these. In the examples, “parts” means “parts by weight” unless otherwise specified.

Synthesis of polyesterimide resin (A) 1386 parts of 2-methyl-1,3-propanediol, 4,4 ′ were added to a 3 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirring device. -Add 138.6 parts of diaminophenyl ethane, 268.8 parts of trimellitic anhydride, 581 parts of isophthalic acid, and 0.7 parts of tetrabutyl titanate in a nitrogen stream from room temperature (25 ° C) in 1 hour. The temperature was raised to 175 ° C. and reacted for 2 hours. Next, the obtained solution was heated to 200 ° C. in 5 hours and reacted for 3 hours to obtain a resin having a resin acid value of 19. 411.6 parts of maleic anhydride was added to the resulting solution, the temperature was raised again to 215 ° C., and the mixture was reacted for 6 hours to obtain a polyesterimide resin (A) having an acid value of 12. The viscosity of the polyesterimide resin (A) was 2.3 Pa · s at 25 ° C.

Synthesis of polyesterimide resin (B) Into a 3 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirrer, 882 parts of 2-methyl-1,3-propanediol, 4,4 ′ -138.6 parts of diaminophenyl ethane, 268.8 parts of trimellitic anhydride, 581 parts of isophthalic acid, and 0.7 parts of tetrabutyl titanate were added, and the temperature was raised to 175 ° C from room temperature in 1 hour in a nitrogen stream. The reaction was allowed to warm for 2 hours. Next, the obtained solution was heated to 200 ° C. in 5 hours and reacted for 3 hours to obtain a resin having a resin acid value of 22. 411.6 parts of maleic anhydride was added to the resulting solution, the temperature was raised again to 215 ° C., and the mixture was reacted for 6 hours to obtain a polyesterimide resin (A) having an acid value of 12. 40 parts of styrene was added to 60 parts of this polyesterimide resin to synthesize polyesterimide resin (B). The viscosity of the polyesterimide resin (B) is 1.2 Pa. At 25 ° C. s.

Synthesis of unsaturated polyester resin (A) In a 2 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirrer, 884.4 parts of trimethylolpropane, α, β-unsaturated polybasic acid or The anhydride and polybasic acid, 1610.4 parts of benzoic acid and 323.4 parts of maleic anhydride, were added, heated from room temperature to 160 ° C in 1 hour in a nitrogen stream, and then raised to 215 ° C in 5 hours. And reacted for 6 hours. The unsaturated polyester resin (A) obtained has a resin acid value of 9 and a viscosity of 1.5 Pa. At 25 ° C. s.

Synthesis of Unsaturated Polyester Resin (B) In a 2 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirrer, 1438.1 parts of trimethylolpropane diallyl ether and maleic anhydride 313. 6 parts and 3.5 parts of tetrabutyl titanate were added, the temperature was raised from room temperature to 160 ° C. in 1 hour in a nitrogen stream, and then the temperature was raised to 200 ° C. in 5 hours and reacted for 6 hours. The unsaturated polyester resin (B) obtained has a resin acid value of 13 and a viscosity of 3.9 Pa. At 25 ° C. s.

Synthesis of unsaturated polyester resin (C) 245.15 parts of maleic anhydride and 1859.00 parts of TP200 (5.5 molar equivalents of OH, TP200 is ethoxylation of 1 mole of trimethylolpropane and 20 moles of ethylene oxide) Product), 3.00 parts dibutyltin dilaurate (DBTL) and 0.30 parts hydroquinone were added. The mixture was rapidly heated to 120 ° C. under a gentle stream of nitrogen. The temperature was then gradually increased to 190 ° C. over 6 hours and the water obtained from the condensation was removed by distillation. A highly viscous liquid resin is obtained and has an acid value of 26 and a viscosity at 25 ° C. of 25.6 Pa.s. s.

Example 1
(1) Preparation of resin mixture A Polyesterimide resin A and unsaturated polyester resin A were blended at 50 parts / 50 parts, and further 4 parts of t-butyl perbenzoate (Nippon Yushi Co., Ltd. perbutyl Z). Was added to obtain a resin composition A for electrical insulation. Using the resin composition A, the general characteristics were measured according to JIS C 2105.
Measurement of air drying property 3 g of the resin composition A was placed on a 90 mm × 90 mm tin plate so that the entire surface could be applied. This tin plate was set in a direction perpendicular to the ground and left in a 120 ° C. dryer. The surface state was confirmed with a finger, and the time when the stickiness disappeared was defined as the air drying time.
Measuring method of VOC generation amount Resin composition A is precisely weighed on a 1.5 g dish and allowed to stand in a dryer at 150 ° C. After 1 hour, it was taken out from the dryer, and the weight change rate of Composition A was measured.

(Example 2)
A resin composition B was prepared in the same manner as in Example 1 except that the unsaturated polyester resin A in Example 1 was changed to the unsaturated polyester resin B, and general characteristics and air drying properties were measured.

(Example 3)
Except having changed the unsaturated polyester resin A into the unsaturated polyester resin C in Example 1, the same operation as Example 1 was performed, the resin composition C was produced, and the general characteristic and air drying property were measured.

(Comparative Example 1)
A resin composition D was prepared in the same manner as in Example 1 except that only the polyesterimide resin A was used in Example 1, and general characteristics and air drying properties were measured.

(Comparative Example 2)
Except having used only unsaturated polyester resin A among Example 1, operation similar to Example 1 was performed, the resin composition E was produced, and the general characteristic and air drying property were measured.

(Comparative Example 3)
Except having used only unsaturated polyester resin B among Example 2, the same operation as Example 2 was performed, resin composition F was produced, and the general characteristic and air drying property were measured.

(Comparative Example 4)
Except having used only unsaturated polyester resin C among Example 3, operation similar to Example 3 was performed, resin composition G was produced, and the general characteristic and air drying property were measured.

(Comparative Example 5)
Except having used only the polyesterimide resin B among the comparative examples 1, the same operation as Example 1 was performed, the resin composition H was produced, and the general characteristic and air drying property were measured. The obtained results are shown in Table 1.

  (A) Polyesterimide resin, (B) α, β-unsaturated polybasic acid or anhydride thereof and trimethylolpropane, or a derivative thereof are included as essential components, and reaction is carried out using polybasic acid and polyhydric alcohol as synthetic raw materials. In Examples 1 to 3, which are resin compositions containing the unsaturated polyester resin obtained as an essential material, the air drying property is better than that of Comparative Example 1 using (A) the polyesterimide resin alone. Moreover, BDV before and behind heat deterioration becomes high compared with the comparative examples 2, 3, and 4 which used the unsaturated polyester resin independently, and it is favorable. In Comparative Example 5 using the polyesterimide resin B blended with styrene, the VOC generation amount is large.

Synthesis and composition of polyesterimide resin (C)
882 parts of 3-liter 1,3-propanediol, 138.6 parts of 4,4-diaminophenylethane, 268.8 trimellitic anhydride, equipped with thermometer, nitrogen blowing tube, rectification column and stirring device Parts, 581 parts of isophthalic acid, and 0.7 parts of tetrabutyl titanate were heated in a nitrogen stream from room temperature (25 ° C.) to 175 ° C. over 1 hour and reacted for 2 hours. Next, the obtained solution was heated to 200 ° C. in 5 hours and reacted for 3 hours to obtain a resin having a resin acid value of 22. 411.6 parts of maleic anhydride was added to the resulting solution, and the temperature was raised again to 215 ° C. and reacted for 6 hours to obtain a polyesterimide resin having an acid value of 28. 20 parts of styrene was added to 80 parts of this polyesterimide resin to obtain a polyesterimide resin composition (C). The viscosity of this composition was 2.8 Pa · s at 25 ° C.

Synthesis of modified unsaturated epoxy ester resin and composition thereof (B1)
As an epoxy compound having one or more epoxy groups in the molecule, 376 parts of diglycidyl ether of 4,4′-isopropylidenediphenol (manufactured by Ciel Petroleum Co., Ltd., Ep-828, epoxy equivalent 188), α, β-not As a saturated monobasic acid, 172 parts of methacrylic acid, 2 parts of benzyldimethylamine and 0.05 part of hydroquinone were charged in a reaction kettle and reacted at 11 ° C. When the acid value reached 5, 24 parts of maleic anhydride as an unsaturated acid anhydride was further added to the reaction kettle, and the reaction was stopped when the acid value reached 50. 85 parts of the reaction product of the obtained modified unsaturated epoxy ester resin was dissolved in 15 parts of styrene to obtain a modified unsaturated epoxy ester resin composition (B1). The viscosity of the modified unsaturated epoxy ester resin composition was 4.0 Pa · s at 25 ° C.

Example 4
(1) Preparation of Resin Composition A Polyesterimide resin composition C and modified unsaturated epoxy ester resin composition B1 were blended at 100 parts / 300 parts, and further 1 part of t-butyl perbenzoate (Nippon Yushi Co., Ltd.) A resin composition I was obtained by adding trade name Perbutyl Z). Using the resin composition I, the general characteristics were measured according to JIS C 2105.
Measurement of air drying property 3 g of the resin composition A was placed on a 90 mm × 90 mm tin plate so that the entire surface could be applied. This tin plate was set in a direction perpendicular to the ground and left in a 120 ° C. dryer. The surface state was confirmed with a finger, and the time when the stickiness disappeared was defined as the air drying time.

Method for measuring VOC generation amount Resin composition I is precisely weighed on a 1.5 g dish and allowed to stand in a dryer at 150 ° C. After 1 hour, the resin composition I was taken out from the dryer, and the weight change rate of the resin composition I was measured.
Measurement of Adhesive Force A helical coil was prepared using KMK-22A manufactured by Hitachi Magnet Wire and a magnet wire having a diameter of 1.0 mm. This was impregnated with resin composition I and cured at 150 ° C. for 30 minutes to prepare a test piece. Using this test piece, the distance between fulcrums was 50 mm, and a load was applied to the center of the test piece at a speed of 50 mm / min using an autograph manufactured by Shimadzu Corporation. The load at which the test piece breaks was defined as the fixing force.
Measurement of BDV (Insulation breakdown strength; Break Down Voltage)
Using a BDV measuring machine (Maywa Denki Co., Ltd.) in a 50 mm x 100 mm x 2 mm mold, set the test piece between a 20 mm diameter spherical electrode and a 20 mm diameter disk electrode in an oil bath. Then, the breakdown voltage was measured to determine the strength of the breakdown. The strength of dielectric breakdown after thermal degradation at 220 ° C. and 240 ° C. was also measured and shown in Table 2.

(Example 5)
In Example 4, the same operation as in Example 4 was carried out except that the polyesterimide resin composition C and the modified unsaturated epoxy ester resin composition were changed to 100 parts / 100 parts. J was prepared and measured for general properties, air drying properties, and adhesion.

(Example 6)
In Example 4, the same operation as in Example 4 was performed except that the composition of the polyesterimide resin composition C and the modified unsaturated epoxy ester resin B1 was changed to 100 parts / 50 parts to produce a resin composition K. General properties, air drying properties and adhesion were measured.

(Example 7)
In Example 4, polyester imide resin composition C and modified unsaturated epoxy ester resin B were changed to 100 parts / 400 parts, and the same operation as in Example 4 was performed to prepare resin composition L. General properties, air drying properties and adhesion were measured.

(Comparative Example 6)
A resin composition M was prepared in the same manner as in Example 4 except that only the polyesterimide resin composition C was used in Example 4, and the general characteristics, air drying properties, and adhesion strength were measured.

(Comparative Example 7)
A resin composition N was prepared in the same manner as in Example 4 except that only the modified unsaturated epoxy ester resin B was used in Example 4, and the general characteristics, air drying properties, and adhesion strength were measured.
The obtained results are shown in Table 2.

Although the comparative example 6 is an example which used only the polyesterimide resin composition C, it is inferior to adhering force. Comparative Example 7 is an example in which only the modified unsaturated epoxy ester resin B1 is used, and is inferior to the dryness and twisted pair BDV after heat degradation. On the other hand, in the resin composition using the polyesterimide resin composition C of Examples 4 to 7 and the modified unsaturated epoxy ester resin B1, the twisted pair BDV after Comparative Examples 6 and 7 was obtained. Is improved, and the amount of VOC generation becomes comparable. In particular, in Examples 4 and 5 containing 100 to 300 parts by weight of the modified unsaturated epoxy ester (B1) with respect to 100 parts by weight of the polyesterimide resin (A), VOC decreases.

Claims (12)

(A) Polyesterimide resin, (B) α, β-unsaturated polybasic acid or anhydride thereof and trimethylolpropane or derivative thereof are included as essential components, and polybasic acid or polyhydric alcohol is reacted as a synthetic raw material. A resin composition comprising an unsaturated polyester resin obtained as an essential material. The resin composition according to claim 1, wherein the α, β-unsaturated polybasic acid or anhydride thereof is α, β-unsaturated dibasic acid or anhydride thereof. The resin composition according to claim 2, wherein the α, β-unsaturated dibasic acid or an anhydride thereof is maleic acid, fumaric acid, itaconic acid, citraconic acid or maleic anhydride.
(A) A polyesterimide resin, (B1) an epoxy compound having one or more epoxy groups in the molecule and an α, β-unsaturated monobasic acid were reacted to obtain an unsaturated epoxy ester resin. A resin composition comprising, as an essential material, a modified unsaturated epoxy ester obtained by reacting an unsaturated acid anhydride corresponding to 1 to 20 mol% with respect to a hydroxyl group of an unsaturated epoxy ester resin. The resin composition according to claim 4, wherein the unsaturated acid anhydride is maleic anhydride, itaconic anhydride or citraconic anhydride. The resin composition according to any one of claims 1 to 5, wherein the molecular weight of the polyesterimide resin (A) is in the range of 400 to 10,000. The resin composition according to any one of claims 1 to 3, wherein the unsaturated polyester resin (B) has a molecular weight of 200 to 10,000. 6. The resin composition according to claim 4 , wherein the molecular weight of the modified unsaturated epoxy ester resin (B1) is 200 to 10,000. The resin composition in any one of Claims 1-3, 6 and 7 containing 10-100 weight part of unsaturated polyester resin (B) with respect to 100 weight part of polyesterimide resin (A). The resin composition according to any one of claims 4, 5, 6 and 8, comprising 10 to 300 parts by weight of the modified unsaturated epoxy ester resin (B1) with respect to 100 parts by weight of the polyesterimide resin (A). The resin composition for electrical insulation formed by containing a polymerization initiator and a stabilizer in the resin composition in any one of Claims 1-10 . A method for producing an electrical equipment insulator, comprising coating an electrical equipment with the resin composition for electrical insulation according to claim 11 and curing the electrical equipment.