KR100383253B1 - Vinyl ester resin for F.R.P insulation rod pultrusion and manufacturing method of pultrusion molded product using the same - Google Patents

Abstract

PURPOSE: A vinyl ester resin for pultrusion of FRP insulation rod, its preparation method and a method for preparing a pultrusion molded product by using the resin are provided, to improve moldability, workability, heat resistance, corrosion resistance and thermal expansion stability of a resin. CONSTITUTION: The vinyl ester resin is prepared by reacting an epoxy resin and an acrylic acid or methacrylic acid in the ratio of 1-1.5 by equivalence in the presence of a catalyst by dropping-reaction to prepare a vinyl ester resin binder of an acid value of 20 or less; adding a styrene monomer and an acryl monomer to the vinyl ester resin binder to react them; and adding a thermoplastic resin and an additive to prepare a vinyl ester resin. Preferably the epoxy resin is bisphenol A or phenol-formaldehyde novolac-type epoxy resin having an epoxy equivalence of 100-500 and has a fluidity by increasing the temperature to 80-120 deg.C.

Description

F.R.P Insulation Rod Pultruded Vinyl Ester Resin and Manufacturing Method of Pultruded Molded Product Using the Same

The present invention relates to a vinyl ester resin for FRP insulating rod pultrusion and a method for producing a pultruded molded article using the same, and more particularly for the pultrusion by reacting a novolak-type epoxy resin, bisphenol A-type epoxy resin and (meth) acrylic acid After preparing the vinyl ester binder, a styrene monomer and an acrylic monomer, a thermoplastic resin, an antifoaming agent, and the like are added to prepare a vinyl ester resin for drawing molding having excellent physical properties such as excellent moldability, workability and heat resistance, corrosion resistance, and thermal expansion stability. The present invention relates to a method for producing a molded article for FRP insulating rods having excellent physical properties by mixing a vinyl ester resin prepared above with a filler, an internal mold release agent, a curing agent, a strength reinforcing agent, and impregnating the glass fiber and passing the mold. .

Porcelain, which is the predominant insulator of existing insulators, has the disadvantages of weak impact strength, difficulty in manufacturing, weakness of flashover due to fouling, and difficulty in handling due to heavy weight.

In manufacturing an insulating molded article, an inorganic composite insulator such as silicone rubber has recently been developed and widely used as a material that has improved such a problem.

Such silicone rubber composite insulators require FRP insulation rods made of resin for cores, unlike iron bars used as cores in insulators such as insulators. That is, in the inorganic composite insulator, the F.R.P insulation rod is used for the core of the silicone rubber composite insulator which is used for the purpose of maximizing insulation, improving strength such as impact resistance and reducing weight.

Known FRP insulation rods are FRP insulation rods manufactured using unsaturated polyester resins, epoxy resins, EPDM, etc., and these conventional insulation rods have problems with heat resistance, corrosion resistance, thermal expansion stability, and the like. Improvement is urgently needed.

According to these demands, the use of epoxy resins is increasing, and in particular, conventional FRP insulation rods used for cores are manufactured by drawing molding method. Epoxy resins take a lot of drawing loads during drawing and have low pot life. It is pointed out as a big problem, and the economic problem is also a serious problem because the price is higher than other balances.

Therefore, in the present invention, in order to solve the problems appearing in the FRP insulation rod pull-out resin, which is a raw material of the FRP insulation rods made of the conventional epoxy resin as described above, a series of compositions such as the composition of the resin and the additive composition is renewed, and The present invention has been completed by knowing that a suitable result can be obtained by preparing a molded article while appropriately adjusting the manufacturing process.

The present invention is superior in strength and heat resistance, thermal expansion stability and corrosion resistance compared to FRP insulated rods molded with conventional unsaturated polyester resin, and excellent in workability and price compared to FRP insulated rods molded with epoxy resin, In addition, the purpose of the present invention is to provide a method for producing a novolak-type vinyl ester resin and a FRP insulation rod molded product using the resin to manufacture an FRP insulation rod having excellent properties in terms of workability and strength when compared with EPDM. .

In the present invention, in preparing a drawn resin for FRP insulation rods, the reaction is performed by adding acrylic acid or methacrylic acid to the epoxy resin, adding an equivalent ratio of (meth) acrylic acid / epoxy resin to 1 to 1.5 with a catalyst and dropping the reaction. Preparing a vinyl ester resin binder having an acid value of 20 or less, adding a styrene monomer and an acrylic monomer to the vinyl ester resin binder and reacting the same, and adding a thermoplastic resin and an additive thereto to prepare a vinyl ester resin for preparing a molded article. Characterized in that it comprises a step to.

In addition, the present invention includes a vinyl ester resin for producing a molded article manufactured as described above.

In addition, the present invention is 1 to 10 parts by weight of filler, 0.5 to 2 parts by weight of internal mold release agent, 0.1 to 3 parts by weight of hardener, 0.2 to 1 parts by weight of strength enhancer 80 to 100 parts by weight of the vinyl ester resin for producing a molded product manufactured as described above Containing pultruded molding compositions.

In addition, the present invention by adding a filler, a releasing agent, a curing agent and a strength enhancer to the vinyl ester resin for producing a pultruded molded article prepared as described above to prepare a pultruded molded article composition, and impregnated it with glass fibers to pass through the mold and cured molded article It includes a method for producing a molded article comprising the step of pulling and cutting.

Hereinafter, the present invention will be described in more detail.

In the present invention, in the production of vinyl ester resin for FRP insulation rod drawing molding, acrylic acid or methacrylic acid is added to a novolak epoxy resin and a bisphenol A epoxy resin to react with each other, and the equivalent ratio of (meth) acrylic acid / epoxy resin is 1-. 1.5 and preparing a vinyl ester resin binder having an acid value of 20 or less by mixing and dropping the catalyst with acrylic acid or methacrylic acid, and adding and mixing styrene monomer, acrylic monomer, thermoplastic resin and additives to the vinyl ester resin binder. In the manufacturing method of the resin comprising the step of making, and in preparing the FRP insulating rod molded article composition using the resin thus prepared, the step of preparing by adding a filler, a releasing agent, a curing agent, a strength enhancer to the vinyl ester resin prepared above, and the glass Impregnated in fiber and passed through mold to cure Pulling out the molded article out at a constant temperature and speed characterized by a molded article production method of the composition step of cutting.

The above manufacturing method will be described in more detail as an example as follows.

First, the manufacturing process of the drawing molding resin for F.R.P insulation

1) adding 30 to 60 parts by weight of an epoxy equivalent of 100 to 500 epoxy resin and raising the temperature to 80 to 120 ° C. to allow flow;

2) adding a polymerization inhibitor and a color stabilizer at the temperature of step 1),

3) dropping the mixed solution of acrylic acid or methacrylic acid and the catalyst so that the equivalent ratio of (meth) acrylic acid / epoxy resin is 1 to 1.5 within 5 minutes after adding the polymerization inhibitor and the color stabilizer;

4) preparing a vinyl ester resin binder having an acid value of 20 or less by isothermal reaction by raising the temperature at 90 to 150 ℃ after the dropping reaction,

5) reacting 50 to 80 parts by weight of the vinyl ester resin binder with 20 to 50 parts by weight of a styrene monomer or an acryl-based reactive monomer to react;

6) to 80 to 90 parts by weight of the prepared vinyl ester resin 10 to 20 parts by weight of the thermoplastic resin and the antifoaming agent 0.05 to 0.5 parts by weight of the reaction step

It may be made, including.

In addition, the process for producing a molded article composition for F.R.P insulation from the prepared resin

7) mixing the filler, the internal mold release agent, the curing agent and the strength reinforcing agent into the vinyl ester resin prepared in step 6),

8) impregnating the glass fiber in the step 7) so that the glass fiber is 50 to 85% by weight into a mold,

9) Cutting the molded product by pulling the molded product of step 8) from 5 to 80 cm / min from the mold by increasing the temperature at the inlet side and the outlet side while adding coolant to the mold inlet.

It consists of.

When described in detail each step as a preferred embodiment by separating the resin manufacturing step and the molded article composition manufacturing step of the present invention as follows.

1) Resin Preparation Step 1: Fluidization Step of Epoxy Resin

In order to produce a vinyl ester resin binder, an epoxy resin having an epoxy equivalent of 100 to 500 in a novolak-type epoxy and bisphenol-A type is placed in a reactor provided with a stirrer, a thermometer, a cooler (total condenser), a dropping device, and the like. Then heat and raise the temperature to 80 ~ 120 ℃ when the flow is confirmed.

2) Resin Preparation Step 2: Polymerization Agent and Color Stabilizer Input Step

After confirming that the epoxy resin was completely melted, 0.001 to 0.15 parts by weight of the polymerization inhibitor was added to the total amount, and 0.001 to 0.1 part by weight of the color stabilizer was added.

3) Resin Preparation Step 3: Dropping Reaction Step

1.5 to 4.0% by weight of acrylic acid or methacrylic acid and its (meth) acrylic acid at an equivalent ratio of (meth) acrylic acid / epoxy within 5 minutes after the addition of the polymerization inhibitor and the color stabilizer at the temperature of 80 to 120 ° C. The mixed solution mixed with the catalyst is dropped and the ring-opening reaction of the epoxy resin and the acid is performed. In this case, if the equivalent ratio is less than 1, an excessive amount of unreacted epoxy resin is present, which causes a problem in storage stability. If the equivalent ratio is greater than 1.5, an excessive amount of unreacted acrylic monomer is present, affecting mechanical properties and the like.

4) Resin manufacturing step 4: ring opening maintenance reaction step

After the three-step reaction, the reaction temperature is increased to 90 to 150 ° C., and the retention reaction is carried out at an acid value of 20 or less until the dilution viscosity of the styrene monomer or the acrylic monomer is 3 to 20 poise, and the number average molecular weight is 500 to 5,000. While manufacturing a vinyl ester resin binder.

5) Resin Preparation Step 5: Dilution Step

0.001 to 0.1 parts by weight of the same color stabilizer as used in the binder manufacturing process is added to the vinyl ester resin binder obtained in the four-step reaction, and cooled to 80 to 120 ℃ by styrene monomer and acrylic monomer, polymerization inhibitor and curing A vinyl ester resin is prepared by diluting with a mixed solution prepared by mixing 0.00005 to 0.005 parts by weight of a metal soap salt as an accelerator. In particular, the reactive monomers added here are added to provide a good appearance through the strength impartment required in the pultrusion and the good surface hardness of the resin molding. Such monomers are preferably added to the polymerization inhibitor and color stabilizer and added within 5 minutes to prevent polymerization by cooling the dilution effect and the temperature of the reaction system.

6) Resin Preparation Step 6: Additive Addition Step

After cooling the vinyl ester resin prepared in step 5 to 30 to 50 ℃ 10 to 20 parts by weight of a thermoplastic resin, 0.05 to 0.5 parts by weight of a defoaming agent is mixed to prepare a final resin. Here, the thermoplastic resin is added to prevent curing shrinkage during the pultrusion.

7) Molded article manufacturing step 1: blending and additives

1 to 10 parts by weight of the filler, 0.5 to 2 parts by weight of the internal mold release agent, 0.1 to 3 parts by weight of the curing agent, and 0.2 to 1 part by weight of the strength enhancer are added to 80 to 100 parts by weight of the vinyl ester resin prepared in step 6 of preparing the resin.

8) Step 2 of the molded article: impregnated glass fiber

The glass fiber having a diameter of 10 to 30 μm of the monofilament is impregnated into the compound of the first step of manufacturing the molded article so that the glass fiber is 50 to 85% by weight and placed in a mold.

9) Molded article manufacturing step 3: Curing and pulling out the molded product

Molded product is cut into 5 ~ 80 cm per minute in the temperature range of 150 ~ 230 ℃ at the inlet side and 150 ~ 230 ℃ at the outlet side while cutting water is inserted into the mold inlet to obtain the finished product.

As the epoxy resin used in the production method of the present invention as described above, epoxy resins having an epoxy equivalent of 100 to 500 are preferably used as bisphenol A type epoxy resins and phenol-formaldehyde novolac type epoxy resins.

As the reaction catalyst, triethylamine, ethyltrimethyl ammonium bromide, dimethylbenzylamine, di-n-butylamine, dimethylphenylbenzyl ammonium chloride, chromium acetylacetate, triphenylstyrene, tetramethyl amnonium chloride, and triphenylphosphate Fins and the like, and as a polymerization inhibitor, hydroquinone, toluhydroquinone, hydroquinone methyl ether, p -benzoquinone, dimethyl- p -benzoquinone, p -tertiarybutylcatechol and the like can be used.

Phosphorus compounds such as phosphoric acid and phosphorous acid may be used as color stabilizers, and triphenylantimony, triphenyl phosphate, Doverforce 8 (trade name of Dover Chemical, Japan), naphthobin KX-405 (Metelgegelshaft, Germany) Agasa trade name) may be used.

Acrylic reactive monomers include vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, and dodecyl (meth) Acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (iso) bonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) acrylic Latex, methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, biphenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, diallyl telephthalate, diallyl Tallylate, diallyl carbonate, divinylbenzene, trimethylol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. can be used.

As the metal soap salt, one or more soap salts selected from salts of Co, Cu, Ca, K, Zn, Ir, and Mn may be used.

As the thermoplastic resin, saturated polyester resin, polystyrene, polyethylene and copolymer, polymethacrylic acid and copolymer, polyvinyl acetate and copolymer, vinyl chloride, polycaprolactone, cellulose acetate butylate, modified polyurethane, and the like can be used. have.

A non-silicone type can be used as an antifoamer.

As the filler, one or more selected from calcium carbonate, alumina hydroxide and aluminum silicate may be used.

For internal mold release agents, PS-125 (Axle, USA) and XLUB S-125 (Samsung Oil, Korea) can be used.

The curing agent may be selected from benzoyl peroxide, t-butyl peroxy benzoate and bis (4-t-butylcyclohexyl) peroxy dicarbonate.

This invention will be described in more detail based on the examples. However, the examples do not limit the present invention. Unless otherwise specified in the following examples, parts means parts by weight.

Next, Examples 1-3 and Comparative Examples 1-4 are manufacture examples of resin, and Examples 4-6 and Comparative Examples 5-8 are manufacture examples of a molded article.

Example 1

1) Epoxy resin: 30 parts by weight of a no-block type resin (Dow Chemical USA, DEN438)

2) Epoxy resin: 13 parts by weight of bisphenol A resin (Korea Chemical, R8834)

3) Color stabilizer: Triphenyl antimony 0.05 parts by weight

4) 0.05 parts by weight of hydroquinone monomethyl ether

5) toluhydroquinone 0.05 part by weight

6) 20.3 parts by weight of (meth) acrylic acid

7) dimethylbenzylamine 0.5 parts by weight

8) Color stabilizer: Triphenylantimony 0.02 parts by weight

9) 0.025 parts by weight of hydroquinone monomethyl ether

10) toluhydroquinone 0.01 parts by weight

11) 27.03 parts by weight of styrene monomer

12) p -tertiary butyl catechol 0.004 parts by weight

13) 0.00005 parts by weight of copper naphthenate

14) 10.48 parts by weight of thermoplastic resin (saturated polyester resin)

15) 0.1 part by weight of antifoaming agent

After the above 1) and 2) are put into a reactor equipped with a stirrer, a thermometer, a dropping device, a charge cooler, and the like, and heated to check the flow, the temperature is increased while stirring at a temperature of 80 to 120 ° C.

Then add 3), 4) and 5) above. After closing the lid of the reactor after the reaction 6), 7) the pre-prepared solution in a dropping device for 1 hour in a dropping device within 5 minutes and then continue to react by raising the reaction temperature to 90 ~ 150 ℃ using exothermic After the acid value is 20 or less, the reaction is carried out until the styrene monomer dilution viscosity becomes 3 to 20 poise, and then 8), 9) and 10) are added thereto to prepare a vinyl ester binder. The vinyl ester resin binder was cooled to 90-120 ° C., diluted with 11), 12) and 13) mixed solution, cooled to 30-50 ° C., and then 14), 15) were added to prepare 101.619 parts by weight of resin.

Example 2

1) Epoxy resin: 30.5 parts by weight of a no-block type resin (Dow Chemical USA, DEN431)

2) Epoxy resin: 15 parts by weight of bisphenol A resin (Korea Chemical, R8834)

3) Color stabilizer: Triphenyl antimony 0.05 parts by weight

4) 0.05 parts by weight of hydroquinone monomethyl ether

5) toluhydroquinone 0.05 part by weight

6) 20.3 parts by weight of (meth) acrylic acid

7) dimethylbenzylamine 0.5 parts by weight

8) Color stabilizer: Triphenylantimony 0.02 parts by weight

9) 0.025 parts by weight of hydroquinone monomethyl ether

10) toluhydroquinone 0.01 parts by weight

11) 30.03 parts by weight of styrene monomer

12) p -tertiary butyl catechol 0.004 parts by weight

13) 0.00005 parts by weight of copper naphthenate

14) 9.5 parts by weight of thermoplastic resin (polyvinyl acetate)

15) 0.1 part by weight of antifoaming agent

The manufacturing process is the same as that of the said resin manufacture example 1.

Example 3

1) Epoxy resin: 30.5 parts by weight of a no-block type resin (Dow Chemical USA, DEN431)

2) Epoxy resin: 15 parts by weight of bisphenol A resin (Kukdo Chemical, YD-134)

3) Color stabilizer: Triphenyl antimony 0.05 parts by weight

4) 0.05 parts by weight of hydroquinone monomethyl ether

5) toluhydroquinone 0.05 part by weight

6) 20.3 parts by weight of (meth) acrylic acid

7) dimethylbenzylamine 0.5 parts by weight

8) Color stabilizer: Triphenylantimony 0.02 parts by weight

9) 0.025 parts by weight of hydroquinone monomethyl ether

10) toluhydroquinone 0.01 parts by weight

11) 30.03 parts by weight of styrene monomer

12) p -tertiary butyl catechol 0.004 parts by weight

13) 0.005 parts by weight of copper naphthenate

14) 9.5 parts by weight of thermoplastic resin (polystyrene)

15) 0.1 part by weight of antifoaming agent

The manufacturing process is the same as that of the said resin manufacture example 1.

Comparative Example 1

Except that the unsaturated polyester resin (R3732N, Korea Chemical Products) was the same as in Example 1.

Comparative Example 2

Except for using an unsaturated polyester resin (AROPOL 2036L, Ashland Chemical, USA) is the same as in Example 1.

Comparative Example 3

Except that the vinyl ester resin (R3792N, Korea Chemical) was the same as in Example 1.

Comparative Example 4

Except for using an epoxy resin (EPON RESIN 9310, Shell Chemical, USA) is the same as in Example 1.

Experimental Example 1

Only the resins of Examples 1 to 3 and Comparative Examples 1 to 4 were measured for tensile strength, tensile modulus, flexural strength, flexural modulus and elongation, and the results are shown in Table 1 below.

Here, the tensile strength (kg / ㎠) and tensile modulus (kg / ㎠) was measured by ASTM D638, flexural strength (kg / ㎠) and flexural modulus (kg / ㎠) was measured by ASTM D790, elongation (%) Was measured using ISO R527.

Examples 4-6 and Comparative Examples 3-4

F.R.P insulation rods were prepared by mixing the resins prepared according to the resin preparation examples 1 to 3 and the commercialized resin comparative examples 1 to 4 with the compositions as shown in the following Table 2.

1) Example 4: Resin Preparation Noble vinyl vinyl ester resin prepared according to Example 1

Example 5 Resin Preparation Noblock Vinyl Ester Resin Prepared According to Example 2

Example 6 Resin Preparation Noblock vinyl ester resin prepared according to Example 3

Comparative Example 5: Unsaturated Polyester Resin (R3732N, Korea Chemicals)

Comparative Example 6: Unsaturated Polyester Resin (AROPOL2036L, Ashland Chemical, USA)

Comparative Example 7: Vinyl Ester Resin (R3792N, Korea Chemical)

Comparative Example 8: Epoxy Resin (EPON RESIN 9310, Shell Chemical, USA)

2) Examples 4-6 and Comparative Examples 5-7: Alumina Hydroxide (SB-432, Solem Corporation USA)

Comparative Example 8: Aluminum silicate (ASP 400P, made by Engelhard, USA)

3) Examples 4 to 6 and Comparative Examples 5 to 7: Bis (4-t-butylcyclohexyl) peroxydicarbonate (Pergadox 16, medicinal product, Japan)

Comparative Example 8: Epoxy Curing Agent (Epon Curing Agent 9360, manufactured by Shell Chemical, USA)

4) Examples 4 to 6 and Comparative Examples 5 to 7: t-butylperoxy benzoate (TBPB, medicinal product, Japan)

Comparative Example 8: Epoxy Curing Accelerator (Epon Curing Agent accelerator537, manufactured by Shell Chemical, USA)

5) Strength reinforcing material: RA9709 (Korea Chemical Products)

6) Examples 4-6 and Comparative Examples 5-7: PS-125 (Axle, USA)

Comparative Example 8: MOLD WIZ INT1846 (Axle, USA)

7) Low-shrinkants include thermoplastics, polyethylene (Microcin FN510, Quantum, USA), Polystyrene (MR63004, Aristec, USA), Polyvinyl acetate and copolymers (LP-90, Union Carbide, USA) ), Modified urethane (Q8000, manufactured by Ashland, USA) saturated polyester resin (R3703, Korea Chemical)

Experimental Example 2

Physical properties of the molded article having a diameter of 10 to 50 mm of the FRP insulating rods prepared according to Examples 4 to 6 and Comparative Examples 5 to 8, and pot life (hr) and glass fiber content of the molded article after the preparation (% By weight), drawing workability (forming), tensile strength (kgf), torsional strength (kg · mm), appearance (visual observation) were measured, and the results are shown in Table 3 below.

Note 3) Table 3 below shows the molding diameters based on 16 mm.

When comparing Examples 4 to 6 and Comparative Examples 3 to 4 of the present invention from the results of Tables 1 and 3 above, as shown in Table 1 of Experimental Example 1, the resin alone had some inferior physical properties, but the Experimental Example In 2, the pot life which can be known for molding operation time is equivalent to Comparative Examples 5-7 and is superior to Comparative Example 8. The glass fiber content is difficult to increase from 65% of Comparative Examples 5 to 6, while Examples 4 to 6 can be raised to 79% and have the same glass fiber content as Comparative Examples 7, 8. The drawing workability (formability) shows that the drawing load is significantly lower than that of Comparative Examples 5, 6 and 8, and thus the moldability is excellent. In the molded article, the tensile failure load and the torsional load value are superior to Comparative Examples 5, 6 and 7. The appearance state shows very superior to Comparative Example 8. In all the items of workability and physical properties compared with the comparative example, the results show that each item is remarkably superior without thirteen items.

Therefore, the drawable noblock vinyl ester resin of the present invention has excellent moldability than conventional resins, and when the F.R.P insulation rod is manufactured using the same, it is possible to manufacture an F.R.P insulation rod having excellent physical properties of the molded article.

As described above, the present invention, unlike the prior art in the production of vinyl ester resin for FRP insulating rod pultrusion molding, a novolak-type epoxy resin, bisphenol A-type epoxy resin and (meth) acrylic acid by reacting the pulsion molding vinyl ester After preparing a binder, a styrene monomer, an acrylic monomer, a thermoplastic resin, an antifoaming agent, etc. may be added to prepare a pultruded vinyl ester resin having excellent physical properties such as excellent moldability, workability and heat resistance, corrosion resistance, and thermal expansion stability. In addition, the filler, the internal mold release agent, the curing agent, the strength reinforcing agent, etc. are mixed with the vinyl ester resin prepared above, and impregnated in the glass fiber to pass through the mold, thereby having the effect of producing a pulled molded article for excellent FRP insulating rods. will be. As a result, it is possible to provide a product that is more economical and of superior quality than conventional insulation.

Claims (26)

In the production of the FRP insulating rod drawing resin, the reaction is performed by adding acrylic acid or methacrylic acid to the epoxy resin, but adding an equivalent ratio of (meth) acrylic acid / epoxy resin to the catalyst at 1 to 1.5 with a catalyst and dropping the acid to 20 or less. Preparing a vinyl ester resin binder; and adding and reacting a styrene monomer and an acrylic monomer to the vinyl ester resin binder; and adding a thermoplastic resin and an additive thereto. Method for producing vinyl ester resin for drawing molded article. According to claim 1, wherein the epoxy resin is bisphenol A and phenol-formaldehyde novolak-type epoxy resin of 100 to 500 epoxy resin of the equivalent weight is drawn up to 80 to 120 ℃ to allow a flow Method for producing vinyl ester resin for use. The method of claim 1, wherein the acrylic acid or methacrylic acid is added to the polymerization inhibitor and the color stabilizer at 80 to 120 ° C and the acrylic acid or methacrylic acid is added within 5 minutes of the draw molding vinyl ester of the resin Manufacturing method. The method of claim 3, wherein the polymerization inhibitor is one or two or more selected from hydroquinone, toluhydroquinone, hydroquinone monomethyl ether, p -benzoquinone, dimethyl- p -benzoquinone and p -tertiarybutylcatechol. Method for producing a vinyl ester resin for drawing molding, characterized in that it is used. The said polymerization inhibitor uses 0.001-0.15 weight part with respect to 30-60 weight part of epoxy resins, The manufacturing method of the vinyl ester resin for drawing molding of Claim 3 or 4 characterized by the above-mentioned. The method of claim 3 or 4, wherein the color stabilizer and the polymerization inhibitor are added at two stages before the dropping reaction and after the production of the vinyl ester binder. The method of claim 6, wherein the color stabilizer is used in an amount of 0.001 to 0.1 parts by weight based on 30 to 60 parts by weight of the epoxy resin. The method of claim 1, wherein the catalyst is triethylaminecetyltrimethyl ammonium bromide, dimethylbenzylamine, di-n-butylamine, dimethylphenylbenzyl ammonium chloride, chromium acetylacetate, triphenylstibin, tetramethyl ammonium chloride and tri A process for producing a vinyl ester resin for drawing molding, using one or more selected from phenylphosphine. The method of claim 1 or 8, wherein the catalyst is added at 1.5 to 4.0% by weight based on the amount of acrylic acid or methacrylic acid added. The method of claim 1, wherein after the dropping reaction is completed, the temperature of the reaction system is raised to 105-150 ° C. for isothermal reaction. The method of claim 1, wherein the vinyl ester resin binder is prepared by having a styrene monomer dilution viscosity of 3 to 20 poises and a number average molecular weight of 500 to 5,000. The method of claim 1, wherein the styrene monomer or acryl monomer is vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or oxyl (meth). ) Acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (iso) bonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, chlorophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, biphenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Yate, diallyl terephthalate, diallyl phthalate, diallyl carbonate, divinylbenzene, trimethylol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate pentaerythritol A method for producing a vinyl ester resin for pultrusion molding, comprising one or two or more selected from tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. The method of claim 1 or 12, wherein the styrene monomer or acrylic monomer is used at 20 to 50 parts by weight based on 50 to 80 parts by weight of the vinyl ester resin binder. The method of claim 1, wherein when the styrene monomer or the acrylic monomer is added, the same color stabilizer as used in the vinyl ester resin binder manufacturing process is added and reacted. The pulmonary molding vinyl ester resin according to claim 1, wherein after the addition of the styrene monomer or the acrylic monomer, the metal soap salt is added and mixed at 0.00005 to 0.005 parts by weight with respect to 50 to 80 parts by weight of the vinyl ester resin binder. Manufacturing method. The method of claim 15, wherein as the metal soap salt, one or more soap salts selected from the salts of Co, Cu, Ca, K, Zn, Mn and Ir is used for the production of pultruded vinyl ester resin, characterized in that Way. The method of claim 1, wherein the vinyl ester resin as a thermoplastic resin, saturated polyester resin, polystyrene, polyethylene and copolymers, polymethacrylic acid and copolymers, polyvinyl acetate and copolymers, vinyl chloride, polycaprolactone, cellulose acetate Method for producing pulmonary molding vinyl ester, characterized in that one or more selected from butyrate, modified polyurethane. 18. The process for producing a vinyl ester resin for pultrusion molding according to claim 17, wherein 0.05 to 0.5 parts by weight of a non-silicone system, which is an antifoaming agent, is further used. Vinyl ester resin for the production of F.R.P insulation rod pultruded molded article prepared according to claim 1. Adding a filler, a releasing agent, a curing agent, and a strength modifier to the vinyl ester resin for preparing a molded article manufactured according to claim 1 to prepare a molded article, and impregnating it with glass fiber to pass through the mold and cured the molded article. Method for producing a molded article comprising the step of pulling and cutting. 21. The method of claim 20, wherein the glass fiber is placed in a mold such that the glass fiber having a diameter of 10 to 30 µm of the monofilament is 50 to 85% by weight of the glass fiber. The method of claim 20, wherein the step of cutting the molded product by pulling it out of the mold is carried out at 5 to 80 cm per minute at a temperature of 150 to 230 ° C at the inlet side at a temperature range of 150 to 230 ° C at the inlet side while putting the coolant into the inlet of the mold. A method for producing a molded article, characterized in that the molded article is cut. 1 to 10 parts by weight of filler, 0.5 to 2 parts by weight of internal mold release agent, 0.1 to 3 parts by weight of curing agent and 0.2 to 1 part by weight of strength modifier Containing molded articles. The pultruded molded article according to claim 23, wherein the filler is one or more selected from alumina hydroxide, aluminum silicate and calcium carbonate. 24. The molded article of claim 23 wherein the curing agent is selected from benzoyl peroxide, t-butyl peroxy benzoate and bis (4-t-butylcyclohexyl) peroxy dicarbonate. 24. The molded product according to claim 23, wherein the strength enhancer is a silane coupling agent.