KR20020048653A - Diffcult Combustibility Hi-Intensity Epoxy Composition For Insulator - Google Patents

Abstract

PURPOSE: Provided are fire retardant high strength epoxy resin compositions which can provide fire retardancy for an insulator while not reducing flexural strength of the insulator. CONSTITUTION: The fire retardant high strength epoxy resin composition include an epoxy resin, dimeric acid modified epoxy resin as a plasticizer, brominated epoxy resin and antimony trioxide as a fire retarding agent, glass fiber, silica, aluminum hydroxide as an inorganic filler, Me-THPA and propylene glycol modified Me-THPA as a curing agent and tertiary amine compound as a curing promoter. The epoxy resin is a compound having at least two epoxy groups in one molecule and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, epoxy resins obtainable by epoxidation of polycarbonic acid glycidylether, cyclohexane derivatives, liquid mono epoxy or mixtures of two or more thereof.

Description

Diffcult Combustibility Hi-Intensity Epoxy Composition For Insulator

The present invention relates to a flame-retardant high-strength epoxy resin composition, and more particularly to a high-strength epoxy resin composition that has a flame retardancy while maintaining electrical and mechanical properties.

Conventional epoxy resin composition is used for the electrical insulation treatment of electrical components such as high-voltage transformer and insulator, CT (Current Transformer), PT (Potential Transformer), bushing (Bushing) of electronic components such as automobiles, TVs. The epoxy resin composition for such a use requires crack resistance, plasticity, flame retardancy, volume resistivity at high temperature, partial discharge resistance, adhesiveness, moisture resistance, heat shock resistance, and the like. In particular, in the case of insulators, mechanical strength is very important in addition to the above characteristics.

In addition, insulators currently used in Korea are not flame retardant, causing fire and property damage in the event of fire. In recent years, the characteristics of insulators having flame retardancy are urgently required in terms of safety.

Conventional flame retardant techniques for epoxy resin compositions include a method of imparting flame retardancy to molded articles using organic compounds such as halogen-based, phosphorus-based, nitrogen-based, and inorganic compounds such as antimony trioxide, aluminum hydroxide powder, and magnesium hydroxide powder.

However, the epoxy resin composition to which the flame retardant is added, while the flame retardancy is imparted due to the shape of the particles and the characteristics of the raw material, significantly lowers the bending strength of the molded product, and when a large amount of use, the electrical properties are deteriorated.

An object of the present invention is to solve the above-mentioned drawbacks, to impart flame retardancy to insulators that are not flame retardant, and to solve the problem that the flexural strength of insulators decreases due to imparting flame retardancy while maintaining the characteristics of existing insulators. It is providing the flame-retardant high strength insulator epoxy resin composition which gave flame retardancy.

In order to achieve the above object, as a result of examining various kinds of epoxy resin composition, epoxy bromide resin, antimony trioxide, aluminum hydroxide was added to impart flame retardancy, and glass fiber ( Fiber glass), dimer acid modified epoxy resin was used.

When the raw material used in the epoxy molding and the characteristics thereof are described in detail, the epoxy resin used is a compound having two or more epoxy groups in one molecule, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, Epoxy resins obtained by epoxidation of polycarboxylic acid glycidyl ethers and cyclohexane derivatives can be used, and these can be used alone or in combination of two or more thereof. In addition to this, liquid monoepoxy etc. can also be used as needed.

A dimer acid-modified epoxy resin is used as the plasticizer, and it is a glycidyl ether type of high molecular compound having an equivalent weight of 200 to 900 g / eq and an acid value of dimer acid of 100 to 300 mg KOH / g. For example, YD-171, YD-172 (trade name of Kukdo Chemical Co., Ltd.), or E-871, E-872 (trade name of epoxy product of SHELL Corporation) can be used. Since the dimer acid modified epoxy resin has a high molecular weight and a long molecular chain, it increases the flexibility of the molding to significantly reduce the hardening shrinkage and internal stress generated during molding, thereby improving the impact strength, flexural strength and thermal shock resistance. The blending amount of the dimer acid-modified epoxy resin is 3 to 20 wt% based on 100 wt% of the main ingredient. If the blending amount is less than 3 wt%, the plasticity is insufficient. On the contrary, if the blending amount is more than 20 wt%, the electrical properties are significantly lowered. Therefore, it is important to select an appropriate blending amount.

As flame retardant, antimony trioxide should be used mixed with epoxy bromide. In the case of powder-type brominated flame retardants, for example, organic compounds such as DBDPE (Decabromodiphenylether) have the highest bromine content (over 83%), so they are excellent in terms of flame retardancy. Flame retardant epoxy resins containing bromine are used. Epoxy bromide resins having a equivalent weight of 150 to 700 g / eq and a bromine content of about 5 to 80 wt% are obtained by reacting TBBA (Tetrabromobisphenol A) with ECH (Epichlorohydrin). The blending amount of brominated epoxy resin is 3-20 wt% based on the main 100 wt%, and if the blending amount is less than 3 wt%, there is no flame retardant effect. Do. In addition, antimony trioxide is used in combination with bromine-based flame retardant because it acts to increase the flame retardant effect by radical reaction with bromine when used in combination with bromine-based flame retardant rather than inorganic flame retardant with average particle size of 0.5 ~ 20㎛. Antimony trioxide is used in the amount of 3 to 20 wt% based on 100 wt% of the main ingredient. If the amount is less than 3 wt%, the flame retardant effect is not. .

Inorganic fillers are used by mixing silica powder, glass fiber and aluminum hydroxide powder. Aluminum hydroxide has an average particle size of 1 to 50㎛ and a flame retardant effect is exhibited by a dehydration reaction in which 2Al (OH) ₃ is decomposed into Al ₂ O ₃ and 3H ₂ O during thermal decomposition. Bromine-based flame retardants are thermally decomposed at about 300 ° C. to be self-extinguishing, while aluminum hydroxide has a flame retardant effect at about 200 ° C., which is lower than that of bromine-based flame retardants. The compounding quantity of aluminum hydroxide is 3-37 wt% with respect to 100 wt% of main materials. If the blending amount is less than 3wt%, there is no flame retardant effect, and if the blending amount is more than 37wt%, the bending strength is significantly lowered, so it is important to select an appropriate blending amount. The said aluminum hydroxide can also use aluminum hydroxide of the type which surface-treated the particle | grains with a silane coupling agent, etc., These can be used individually or in mixture.

Glass fiber has an average fiber particle size of 1 ~ 50㎛, and it is a fibrous particle, and has excellent electrical insulation, heat resistance, moisture resistance, durability, especially flexural strength characteristics. Therefore, it is possible to reduce the bending strength of aluminum hydroxide added to impart flame retardancy. It is used to supplement and improve flexural strength by using fiber. The blending amount of glass fiber is 3 to 59 wt% based on 100 wt% of the main ingredient. If the blending amount is less than 3 wt%, there is no effect of improving the flexural strength, and if the blending amount is more than 59 wt%, the viscosity of the composition increases and workability is lowered, so the selection of an appropriate blending amount is important.

Silica powder has an average particle size of 1 to 50㎛ and is used because it has a needle shape and excellent electrical insulation, heat resistance, moisture resistance, durability, crack resistance and flexural strength characteristics. The blending amount of silica is used in the range of 3 to 57 wt% based on the main 100 wt%. If the blending amount is less than 3 wt%, there is no flexural strength effect, and if the blending amount is more than 57 wt%, the viscosity of the composition increases and workability is lowered, so the selection of an appropriate blending amount is important. The silica may also be used a type of silica surface-treated particles, such as a silane coupling agent, these may be used alone or mixed.

As a curing agent, a product obtained by modifying Me-THPA (Methyl-tetrahydrophthalic anhydride) or Me-THPA by esterification with propylene glycol (Propyleneglycol) is used. When Me-THPA is modified with propylene glycol, the crack resistance of moldings is increased and hardening shrinkage and internal stress generated during molding are reduced. The mixing ratio of propylene glycol uses Me-THPA and propylene glycol at a ratio of 2: 1 or less, and when the mixing ratio exceeds 2: 1, the viscosity of the composition increases and workability is lowered, and electrical characteristics are also lowered. It is important to choose the right amount. When Me-THPA is modified, propylene glycol is used to denature, but in addition, polyhydric alcohols such as ethylene glycol (EG), polyethylene glycol (DEG), polyethylene glycol (PEG), polypropylene glycol (PPG) and neopentyl glycol (NPG) are used. May be used to denature Me-THPA. In addition to the hardener, Me-HHPA (Methyl-hexahydrophthalic anhydride), THPA (Tetrahydrophthalic anhydride), HHPA (Hexahydrophthalic anhydride), MHAC (methyl anhydride anhydride), MNA (methyl anhydride anhydride), DDSA (Dodecenyl sussinic anhydride), etc. Acid anhydride hardeners may be used, and these may be used alone or in combination of two or more.

Benzyldimethylamine, a tertiary amine, is used as a curing accelerator, and the blending amount of benzyldimethylamine is 0.05 to 1 wt% based on 20 wt% of the curing agent. If the blending amount is less than 0.05wt%, there is no hardening effect, so the curing speed is slowed down, and workability is lowered. If it exceeds 1wt%, the curing speed is too fast. It is important to choose the right amount. In addition to this, DMP-10 (2- (Dimethylaminomethyl) phenol), DMP-30 (2,4,6-Tris (Dimethylam inomethyl) phenol), DBU (1,8-Diazabiscyclo (5,4,0) undecan), K Tertiary amines such as -61B (Tri-2-ethylhexyl acid salt of DMP-30), Pyrrolidine, Pyridine, Piperidine, Triethanolamine, N, N'-Dimethylpyperazine, imidazoles and derivatives thereof, Lewis acid and Bronsted acid salt, A quaternary ammonium salt etc. can be used as a hardening accelerator, These can also be used individually or in mixture of 2 or more.

As a coupling agent, the silane coupling agent whose organic functional group is an epoxy group is used. The compounding quantity of a silane coupling agent uses 3 weight% or less with respect to 100 weight% of main materials. When the blending amount is more than 3wt%, the flexural strength is not improved any more, and the silane coupling agent may be hydrolyzed to degrade the electrical properties, so it is important to select an appropriate blending amount. In addition to these, organic functional groups such as Amino, Mercapto, Methacryloxy, and Vinyl type silane coupling agents can also be used. In addition, an antifoamer, a pigment, etc. can be used within the range which does not affect the characteristic of a molded object.

Hereinafter, a more preferable embodiment of the flame retardant high strength insulator epoxy resin composition according to the present invention will be described in detail. Table 1 shows a compounding example for each of the following compositions. In the following examples, "%" means "wt%".

Example 1

10% epoxy resin, 20% brominated epoxy resin, 3% dimer acid modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 3%, aluminum hydroxide 3%, glass fiber 3%, silica 57%, Me- A mixture of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded in an insulator mold for 10 to 20 minutes at a temperature of 120 to 140 ° C, and then for 8 hours at a temperature of 160 to 180 ° C. Cured to form insulators.

Example 2

Epoxy resin 8%, Brominated epoxy resin 23%, Dimer acid modified epoxy resin 3%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 3%, Aluminum hydroxide 3%, Glass fiber 10%, Silica 49%, Me- The mixture composed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyl dimethylamine was molded under the same conditions as in <Example 1>.

Example 3

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Defoamer 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- The mixture composed of 19.8% of methyltetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 4

Epoxy resin 16%, Brominated epoxy resin 2%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Defoamer 0.3%, Antimony trioxide 20%, Aluminum hydroxide 10%, Glass fiber 15%, Silica 26%, Me- The mixture composed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 5

10% epoxy resin, 15% brominated epoxy resin, 5% dimer acid-modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 5%, aluminum hydroxide 10%, glass fiber 5%, silica 49%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 6

Epoxy Resin 11%, Brominated Epoxy Resin 20%, Dimer Acid Modified Epoxy Resin 2%, Silane Coupling Agent 0.7%, Antifoaming Agent 0.3%, Antimony Trioxide 3%, Aluminum Hydroxide 3%, Glass Fiber 3%, Silica 57%, Me- A mixture of 19.8% methyl tetrahydrophthalic anhydride (THPA) and 0.2% benzyldimethyl amine was formed under the same conditions as in <Example 1>.

Example 7

10% epoxy resin, 3% brominated epoxy resin, 20% dimer acid-modified epoxy resin, 0.7% silane coupling agent, 0.7% antifoaming agent, 0.3% antimony trioxide, 10% aluminum hydroxide, 15% glass fiber, 21% silica, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 8

Epoxy resin 7%, Brominated epoxy resin 3%, Dimer acid modified epoxy resin 23%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 10%, Aluminum hydroxide 20%, Glass fiber 12%, Silica 24%, Me- The mixture composed of 19.8% of methyltetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 9

Epoxy resin 13%, Brominated epoxy resin 5%, Dimer acid modified epoxy resin 12%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 7%, Aluminum hydroxide 30%, Glass fiber 23%, Silica 9%, Me- The mixture composed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 10

10% epoxy resin, 20% brominated epoxy resin, 3% dimer acid modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 2%, aluminum hydroxide 8%, glass fiber 3%, silica 53%, Me- A mixture of 19.8% methyl tetrahydrophthalic anhydride (THPA) and 0.2% benzyldimethyl amine was formed under the same conditions as in <Example 1>.

Example 11

15% epoxy resin, 3% brominated epoxy resin, 10% dimer acid-modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 25%, aluminum hydroxide 3%, glass fiber 10%, silica 33%, Me- A mixture of 19.8% methyl tetrahydrophthalic anhydride (THPA) and 0.2% benzyldimethyl amine was formed under the same conditions as in <Example 1>.

Example 12

Epoxy resin 10%, Brominated epoxy resin 5%, Dimer acid-modified epoxy resin 13%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 3%, Aluminum hydroxide 37%, Glass fiber 28%, Silica 3%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 13

10% epoxy resin, 20% brominated epoxy resin, 3% dimer acid-modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 5%, aluminum hydroxide 2%, glass fiber 3%, silica 56%, Me- A mixture of 19.8% Methyltetrahydrophthalic anhydride (THPA) and 0.2% benzyldimethyl amine was formed under the same conditions as in <Example 1>.

Example 14

10% epoxy resin, 5% epoxy brominated resin, 13% dimer acid modified epoxy resin, 0.7% silane coupling agent, 0.7% antifoaming agent, 0.3% antimony trioxide, 3% aluminum hydroxide, 23% glass fiber, 3% silica, Me- A mixture of 19.8% methyl tetrahydrophthalic anhydride (THPA) and 0.2% benzyldimethyl amine was formed under the same conditions as in <Example 1>.

Example 15

13% epoxy resin, 15% brominated epoxy resin, 3% dimer acid-modified epoxy resin, 0.7% silane coupling agent, 0.7% antifoaming agent, 0.3% antimony trioxide, 3% aluminum hydroxide, 59% glass fiber, 3% silica, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 16

10% epoxy resin, 20% brominated epoxy resin, 3% dimer acid-modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 4%, aluminum hydroxide 3%, glass fiber 2%, silica 57%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 17

13% epoxy resin, 13% brominated epoxy resin, 5% dimer acid-modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 3%, aluminum hydroxide 5%, glass fiber 47%, silica 13%, Me- The mixture composed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 18

12% epoxy resin, 13% brominated epoxy resin, 3% dimer acid-modified epoxy resin, 0.7% silane coupling agent, 0.7% antifoaming agent, 0.3% antimony trioxide, 3% aluminum hydroxide, 62% glass fiber, 3% silica, Me- The mixture composed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 19

Epoxy Resin 13%, Brominated Epoxy Resin 15%, Dimer Acid Modified Epoxy Resin 4%, Silane Coupling Agent 0.7%, Antifoaming Agent 0.3%, Antimony Trioxide 3%, Aluminum Hydroxide 3%, Glass Fiber 59%, Silica 2%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 20

Epoxy resin 8%, Brominated epoxy resin 17%, Dimer acid modified epoxy resin 3%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 3%, Aluminum hydroxide 3%, Glass fiber 3%, Silica 62%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 21

15% epoxy resin, 3% brominated epoxy resin, 10% dimer acid modified epoxy resin, silane coupling agent 0.7%, antifoaming agent 0.3%, antimony trioxide 20%, aluminum hydroxide 5%, glass fiber 10%, silica 36%, Me- The mixture formed of 14.8% of methyl tetrahydrophthalic anhydride (THPA), 5.0% of propylene glycol, and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 22

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- The mixture formed of 13.2% of methyl tetrahydrophthalic anhydride (THPA), 6.6% of propylene glycol, and 0.2% of benzyldimethylamine was formed under the same conditions as in <Example 1>.

Example 23

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- The mixture formed of 9.9% of methyl tetrahydrophthalic anhydride (THPA), 9.9% of propylene glycol, and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 24

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- The mixture composed of 19.97% of methyl tetrahydrophthalic anhydride (THPA) and 0.03% of benzyldimethylamine was formed under the same conditions as in <Example 1>.

Example 25

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- A mixture formed of 19.95% of methyl tetrahydrophthalic anhydride (THPA) and 0.05% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 26

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- The mixture composed of 19.0% of methyl tetrahydrophthalic anhydride (THPA) and 1.0% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 27

Epoxy resin 15%, Brominated epoxy resin 3%, Dimer acid-modified epoxy resin 10%, Silane coupling agent 0.7%, Antifoaming agent 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me- The mixture composed of 18.5% of methyl tetrahydrophthalic anhydride (THPA) and 1.5% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 28

Epoxy resin 15.7%, Brominated epoxy resin 3%, Dimer acid modified epoxy resin 10%, Antifoam 0.3%, Antimony trioxide 20%, Aluminum hydroxide 5%, Glass fiber 10%, Silica 36%, Me-THPA (Methyl tetrahydrophthalic anhydride) The mixture composed of 19.8% and benzyldimethylamine 0.2% was molded under the same conditions as in <Example 1>.

Example 29

Epoxy resin 15.7%, brominated epoxy resin 3%, dimer acid-modified epoxy resin 10%, silane coupling agent 1%, antifoaming agent 0.3%, antimony trioxide 20%, aluminum hydroxide 5%, glass fiber 10%, silica 35%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 30

Epoxy resin 15.7%, brominated epoxy resin 3%, dimer acid modified epoxy resin 10%, silane coupling agent 3%, antifoaming agent 0.3%, antimony trioxide 20%, aluminum hydroxide 5%, glass fiber 10%, silica 38%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

Example 31

Epoxy resin 15.7%, brominated epoxy resin 3%, dimer acid modified epoxy resin 10%, silane coupling agent 5%, antifoaming agent 0.3%, antimony trioxide 20%, aluminum hydroxide 5%, glass fiber 10%, silica 31%, Me- The mixture formed of 19.8% of methyl tetrahydrophthalic anhydride (THPA) and 0.2% of benzyldimethylamine was molded under the same conditions as in <Example 1>.

<Unit: wt%> Example Example One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 subject Epoxy resin 10 8 15 16 10 11 10 7 13 10 15 10 10 10 13 Brominated epoxy resin 20 23 3 2 15 20 3 3 5 20 3 5 20 5 15 Dimer Acid Modified Epoxy Resin 3 3 10 10 5 2 20 23 12 3 10 13 3 13 3 Silane coupling agent 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Antifoam 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Antimony trioxide 3 3 20 20 5 3 10 10 7 2 25 3 5 3 3 Aluminum hydroxide 3 3 5 10 10 3 20 20 30 8 3 37 2 42 3 Fiberglass 3 10 10 15 5 3 15 12 23 3 10 28 3 23 59 Silica 57 49 36 26 49 57 21 24 9 53 33 3 56 3 3 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Hardener Me-THPA 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 19.8 Propylene glycol - - - - - - - - - - - - - - - Benzyldimethylamine 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sum 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20

<Unit: wt%> Example Example 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 subject Epoxy resin 10 13 12 13 8 15 15 15 15 15 15 15 15.7 15.7 15.7 15.7 Brominated epoxy resin 20 13 13 15 17 3 3 3 3 3 3 3 3 3 3 3 Dimer Acid Modified Epoxy Resin 3 5 3 4 3 10 10 10 10 10 10 10 10 10 10 10 Silane coupling agent 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 - One 3 5 Antifoam 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Antimony trioxide 4 3 3 3 3 20 20 20 20 20 20 20 20 20 20 20 Aluminum hydroxide 3 5 3 3 3 5 5 5 5 5 5 5 5 5 5 5 Fiberglass 2 47 62 59 3 10 10 10 10 10 10 10 10 10 10 10 Silica 57 13 3 2 62 36 36 36 36 36 36 36 36 35 33 31 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Hardener Me-THPA 19.8 19.8 19.8 19.8 19.8 14.8 13.2 9.9 19.97 19.95 19.0 18.5 19.8 19.8 19.8 19.8 Propylene glycol - - - - - 5.0 6.6 9.9 - - - - - - - - Benzyldimethylamine 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.03 0.05 1.0 1.5 0.2 0.2 0.2 0.2 Sum 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20

Next, a comparative example for comparing the product characteristics of each composition described in the above embodiment was described in detail below, and the compounding examples for each composition are shown in Table 2. "%" In the following comparative example means "wt%".

Comparative Example 1

A mixture of epoxy resin 24.2%, mono epoxy resin 5%, silane coupling agent 0.5%, antifoaming agent 0.3%, silica powder 70%, Me-THPA (Methyl-tetrahydrophthalic anhydride) 19.8%, and benzyldimethylamine 0.2% 10 to 20 minutes at 120-140 ℃

After molding for a while, the insulator was formed by curing for 8 hours at a temperature of 160 ~ 180 ℃.

Comparative Example 2

Epoxy resin 19.2%, Mono epoxy resin 5%, Brominated epoxy 5%, Silane coupling agent 0.5%, Antifoaming agent 0.3%, Antimony trioxide 5%, Aluminum hydroxide 25%, Silica 40%, Me-THPA 19.8%, Benzyldimethylamine 0.2 The mixture composed of% was molded under the same conditions as in <Comparative Example 1>.

<Unit: wt%> Comparative Raw Material Name Comparative Example 1 Comparative Example 2 subject Epoxy resin 24.2 19.2 Mono epoxy resin 5 5 Brominated Epoxy - 5 Silane coupling agent 0.5 0.5 Antifoam 0.3 0.3 Antimony trioxide - 5 Aluminum hydroxide - 25 Silica 70 40 Sum 100 100 Hardener Me-THPA 19.8 19.8 Benzyldimethylamine 0.2 0.2 Sum 20 20

Table 3 shows the results of flame retardancy, flexural strength, partial discharge extinction voltage, and workability test of the insulators formed by the compositions of Examples and Comparative Examples.

The tested insulator is a insulator product embedded in a switchboard for a nuclear power plant. The diameter is Φ 91 mm, the height H is 95 mm, the rated voltage is 7.2 kV, and the bending strength is not less than 1,071 kg / cm ^2. International standard of IEC (International Electrical Commission) of IEC Standard type JO16-75 with 91mm in diameter (Φ), 130mm in height (H), rated voltage 12kV, flexural strength over 1,183kg / cm2 Species were molded and tested.

The test methods of inflammability, flexural strength, and partial discharge extinction voltage, which are insulator evaluation items, are as follows.

-Flame retardant: According to IEC 60660 24 inflammability test method.

-Flexural strength: Based on the test method of flexural strength of IEC 60660 19 insulator.

-Partial discharge extinction voltage: Based on the test method of partial discharge extinction voltage of IEC 60660 17 insulator.

According to the test results of Examples and Comparative Examples, the compositions of Examples 1, 3, 5, 7, 9, 12, 15, and 17 showed good flame retardancy by appropriate use of epoxy bromide, antimony trioxide, and aluminum hydroxide. The bending strength was also excellent by using dimer acid-modified epoxy resin, glass fiber, and silica properly. In addition, good results were obtained for both partial discharge extinction voltage and workability.

However, in the case of the composition of Examples 4, 10, 13, the flame retardancy was reduced. This resulted in no flame retardant effect by using too small amount of epoxy bromide, antimony trioxide and aluminum hydroxide used to impart flame retardancy.

In addition, in the case of the compositions of Examples 6, 14, 16, and 19, the bending strength was lowered. In Example 6, too small amount of the dimer acid-modified epoxy resin used to impart plasticity was found to have no effect of improving flexural strength due to plasticity, and in Example 14, aluminum hydroxide was used to impart flame retardancy. Too much excess was used, and in Examples 16 and 19, it was found that the flexural strength was reduced due to the too small amount of glass fiber and silica.

In the case of the compositions of Examples 2, 8 and 11, it was shown that the partial discharge extinction voltage is lowered. It was found that the electrical properties were deteriorated due to the excessive use of epoxy bromide resin, antimony trioxide and dimer acid modified epoxy resin used to impart flame retardancy.

In the case of the compositions of Examples 18 and 20, workability was decreased during insulator molding. This is because the excessive use of the glass fiber and silica used to improve the flexural strength, the viscosity is increased, the defoaming property is lowered and the injection speed is slowed when the mold injection, the workability is shown to be lowered.

Example 3,21,22,23 Comparing the physical properties of the composition when using Me-THPA alone as in Example 3 and Me-THPA and propylene glycol as in Example 21,22 3: 1 or 2: 1 In the case of using at the compounding ratio of, the flame retardancy, flexural strength, partial discharge extinction voltage and workability were all good.However, as in Example 23, Me-THPA and propylene glycol were modified at the ratio of 1: 1. In the case of increasing viscosity, workability was lowered and partial discharge extinction voltage was also lowered.

Example 3,24,25,26,27 Comparing the physical properties of the compositions, Examples 3,25,26 showed good results in terms of flame retardancy, flexural strength, partial discharge extinction voltage, and workability. When the compounding amount of benzyl dimethylamine was 0.03%, the curing was incomplete and the density of the cured product was lowered, resulting in the decrease in flexural strength, the partial discharge extinction voltage and the workability. In the case of%, the curing rate is fast, and the bending stress, partial discharge extinction voltage and workability are decreased due to internal stress during curing.

Example 3,28,29,30,31 Comparing the physical properties of the compositions Example 3,28,29,30 In this case, all of the flame retardancy, flexural strength, partial discharge extinction voltage and workability showed good results, As shown in Fig. 31, when the blending amount of the silane coupling agent was 5%, the partial discharge extinction voltage was decreased due to the addition of the silane coupling agent.

On the other hand, in the case of the comparative example, the composition of Comparative Example 1 was found to be good in flexural strength, partial discharge extinction voltage and workability, but the flame retardancy was lowered. It was found that there is no flame retardance because no brominated epoxy resin, antimony trioxide and aluminum hydroxide are used to impart flame retardancy.

In the case of the composition of Comparative Example 2, unlike the composition of Comparative Example 1, since the epoxy bromide, antimony trioxide, and aluminum hydroxide were used to impart flame retardancy, the silica content was relatively decreased and the flexural strength was lowered.

Examples and Comparative Test Items Example One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 JO16-60 * Flame retardant *** ○ ○ ○ × ○ ○ ○ ○ ○ × ○ ○ × ○ ○ ○ Flexural Strength **** ○ ○ ○ ○ ○ × ○ ○ ○ ○ ○ ○ ○ × ○ × Partial discharge extinction voltage ***** ○ × ○ ○ ○ ○ ○ × ○ ○ × ○ ○ ○ ○ ○ Workability****** ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ JO16-75 ** Flame retardant ○ ○ ○ × ○ ○ ○ ○ ○ × ○ ○ × ○ ○ ○ Flexural strength ○ ○ ○ ○ ○ × ○ ○ ○ ○ ○ ○ ○ × ○ × Partial discharge extinction voltage ○ × ○ ○ ○ ○ ○ × ○ ○ × ○ ○ ○ ○ ○ Workability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Examples and Comparative Test Items Example Comparative example 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 One 2 JO16-60 Flame retardant ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ Flexural strength ○ ○ × ○ ○ ○ ○ × ○ ○ × ○ ○ ○ ○ ○ × Partial discharge extinction voltage ○ ○ ○ ○ ○ ○ × × ○ ○ × ○ ○ ○ × ○ ○ Workability ○ × ○ × ○ ○ × × ○ ○ × ○ ○ ○ ○ ○ ○ JO16-75 Flame retardant ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ Flexural strength ○ ○ × ○ ○ ○ ○ × ○ ○ × ○ ○ ○ ○ ○ × Partial discharge extinction voltage ○ ○ ○ ○ ○ ○ × × ○ ○ × ○ ○ ○ × ○ ○ Workability ○ × ○ × ○ ○ × × ○ ○ × ○ ○ ○ ○ ○ ○

* JO16-60: IEC (International Electrical Commission) international standard product, diameter (Φ) 91mm, height (H) 95mm, rated voltage 7.2kV

** JO16-75: IEC international standard product, diameter (Φ) 91mm, height (H) 130mm, rated voltage 12kV

*** Flame retardant: IEC 60660 24, ○: Burning time within 60 seconds, ×: Burning time exceeding 60 seconds

**** Flexural Strength: IEC 60660 19, JO16-60 type, ○: 1,071kg / cm2 or more, ×: less than 1,071kg / cm2,

JO16-75 type ○: 1,183kg / cm2 or more, ×: 1,183kg / cm2,

***** Partial discharge extinction voltage: IEC 60660 17, JO16-60 type, ○: 4.57 kV or more, ×: Less than 4.57 kV

JO16-75 type, ○: 7.62 kV or more, ×: 7.62 kV or less

****** Workability: Injection state and defoaming state during insulator molding, ○: Good, ×: Poor

As described above, according to the present invention, there is an effect of maintaining the characteristics of the insulator as it is, without the problem that the flexural strength of the insulator is significantly reduced when imparting flame retardancy, and also being used in switchboards such as nuclear power plants and substations. By providing flame resistance to insulators, it is effective to secure product safety in using insulators, such as reducing damages to property and humans in case of fire.

Claims (15)

Epoxy resin, plasticizer, dimer acid-modified epoxy resin, flame retardant, brominated epoxy resin, antimony trioxide, inorganic filler, fiberglass, silica, aluminum hydroxide, hardener, Me-THPA, propylene glycol modified Me-THPA, hardening accelerator A flame retardant high strength epoxy resin composition comprising a tertiary amine compound. The method according to claim 1, wherein the epoxy resin is a compound having two or more epoxy groups in one molecule of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, polycarboxylic acid glycidyl ether, cyclohexane derivatives A flame retardant high strength epoxy resin composition comprising an epoxy resin obtained by epoxidation, a liquid monoepoxy, etc., and a mixture of two or more thereof. The dimer acid-modified epoxy resin has an equivalent weight of 200 to 900 g / eq, and an acid value of dimer acid of 100 to 300 mg KOH / g. Flame retardant high strength epoxy resin composition, characterized in that using 20 wt%. The method of claim 1, wherein the brominated epoxy resin is equivalent to 150 to 700 g / eq, bromine content is 5 to 80 wt%, the compounding amount is 3 to 20 wt% relative to the main 100 wt% of Table 1 Flame retardant high strength epoxy resin composition, characterized in that. The flame retardant high strength epoxy resin composition according to claim 1, wherein the antimony trioxide has an average particle size of 0.5 to 20 µm and a blending amount of 3 to 20 wt% based on the main 100 wt% of Table 1. The method of claim 1, wherein the aluminum hydroxide is aluminum hydroxide of the general type and the type surface-treated with a silane coupling agent, the average particle size of 1 to 50㎛, the compounding amount is 3 to 37 with respect to the 100 wt% of the main table Flame-retardant high strength epoxy resin composition, characterized in that using wt%. The flame-retardant high-strength epoxy resin composition according to claim 1, wherein the glass fiber has an average fiber particle size of 1 to 50 µm and a blending amount of 3 to 59 wt% is used based on 100 wt% of the main ingredient of Table 1. The method according to claim 1, wherein the silica is a silica of the general type and the type surface-treated with a silane coupling agent, etc., the average particle size of 1 to 50㎛, the compounding amount is 3 to 57 wt% relative to the main 100 wt% of Table 1 Flame retardant high strength epoxy resin composition, characterized in that the use. The flame-retardant high strength of claim 1, wherein the curing agent uses Me-THPA or propylene glycol-modified Me-THPA. Epoxy resin composition. The method of claim 9, wherein the Me-THPA denaturation is characterized by using polyhydric alcohols such as ethylene glycol (EG), diethylene glycol (DEG), polyethylene glycol (PEG), polypropylene glycol (PPG), neopentyl glycol (NPG), etc. Flame retardant high strength epoxy resin composition. The method of claim 9, wherein in addition to the hardening agent, methyl-hexahydrophthalic anhydride (Me-HHPA), tetrahydrophthalicanhydride (THPA), hexahydrophthalicanhydride (HHPA), methylhydric anhydride (MHAC), methylnahydride anhydride (MNA), and dodecenyl sussinic anhydri de Flame retardant high-strength epoxy resin composition characterized by using an acid anhydride curing agent such as a) or a mixture of two or more. The flame-retardant high strength epoxy resin composition according to claim 1, wherein the curing accelerator benzyldimethylamine is a tertiary amine and the compounding amount is 0.05 to 1 wt% based on 20 wt% of the curing agent of Table 1. The method according to claim 12, in addition to the curing accelerator DMP-10 (2- (Dimethylaminome thyl) phenol), DMP-30 (2,4,6-Tris (Dimethylam inomethyl) phenol), DBU (1,8-Diazabi scyclo (5) Tertiary amines and imidazoles such as (4,0) undecan), K-61B (tri-2-ethylhexyl acid salt of DMP-30), Pyrrolidine, Pyridine, Piperidine, Triethanolamine, N, N'-Dimethylpyperazine and A flame-retardant high strength epoxy resin composition comprising a derivative, Lewis acid, Bronsted acid salt, quaternary ammonium salt, or the like, or a mixture of two or more thereof. The flame-retardant high-strength epoxy resin composition according to claim 1, wherein the coupling agent is an epoxysilane coupling agent, and a compounding amount is 3 wt% or less based on the main 100 wt% of Table 1. The flame retardant high strength epoxy resin composition according to claim 14, wherein an organic functional group is used in addition to the coupling agent, and a silane coupling agent of Amino, Mercapto, Methacryloxy, or Vinyl type.