KR101193137B1 - Non halogen-free flame retardant epoxy resin composition for reinforcing environmentally conservative seismic - Google Patents

Abstract

PURPOSE: A halogen-free frame retardant resin composition is provided to not generate toxic carcinogenic substances such as dioxins at combustion while having flame retardance by using environment-friendly phosphorous-based flame retardant. CONSTITUTION: A halogen-free frame retardant resin composition consists of 100.0 parts by weight of a first composition of resin components and 100.0 parts by weight of a second composition. The first composition comprises 60-70 weight% of epoxy base resin and 30-40 weight% of phosphorous-based flame retardant. The second composition comprises 55-65 weight% of modified cycloaliphatic amine, 15-25 weight% of polyoxypropylene diamine, 5-10 weight% of tackifier comprising 3-glycidoxypropyltrimethoxysilane and phosphate acid, and 5-10 weight% of dimethylaminomethyl phenolics-based curing accelerator.

Description

Non-halogen-free flame retardant epoxy resin composition for reinforcing environmentally conservative seismic

The present invention relates to a flame-retardant epoxy resin composition for non-halogen-free environment-friendly seismic repair reinforcement.

In particular, it minimizes the content of halogen to minimize the generation of toxic gases, and it is suitable for RoHs by including a phosphorus (P) -based flame retardant, it is flame-retardant (UL-94 Vo) to impart a fire to block the combustion by the self-extinguishing action at the beginning of combustion. Non-halogen-free, eco-friendly earthquake-resistant repair and reinforcement flame retardant epoxy resin composition which can improve adhesion with cement building structure and steel structure by using 3-glycidoxypropyltrimethoxysilane and phosphoric acid, which have excellent heat resistance and dimensional stability. It is about.

Recently, there has been a growing interest in environmental issues around the world, and regulations on the generation of toxic substances in the disposal of electrical and electronic products have been tightened. Conventional epoxy resin compositions generally use amine-based curing agents and curing accelerators in addition to brominated bifunctional epoxy resins and polyfunctional epoxy resins as main materials, and epoxy resins satisfying UL (Underwriters Laboratory) 94V-O. The composition contains 15-20 wt% bromine. However, the halogen compound containing bromine has excellent flame retardancy, but generates a toxic gas upon combustion, and is likely to generate dioxins and frans which are carcinogens. For this reason, the use of brominated epoxy resin is restrict | limited.

Accordingly, British Patent No. 1,112,139 and Japanese Patent Laid-Open No. 2-269730 disclose various epoxy resin compositions in which nitrogen compounds, phosphorus compounds, organic compounds and the like are blended. However, the compounds described in these publications not only adversely affect the curing of the epoxy resin, but also have problems such as deterioration in moisture resistance and heat resistance of the cured composition.

The present invention has been made to solve the conventional problems as described above, the main object of the present invention by using a phosphorus-based flame retardant that is an environmentally friendly material instead of halogen-based flame retardant while having a flame retardant and generates toxic carcinogens such as dioxin during combustion The present invention provides a non-halogen-free, flame-retardant epoxy resin composition for environmentally friendly earthquake-resistant repair.

Another object of the present invention is a non-halogen-free which can improve adhesion to cement building structures and steel structures by forming a curing agent composed of a modified alicyclic amine having good heat resistance and dimensional stability and a modified polyoxypropylene diamine having excellent durability and elasticity. It is to provide a flame-retardant epoxy resin composition for environmentally friendly earthquake-resistant repair.

According to the first aspect of the present invention for achieving the above object,
100 parts by weight of the first composition of the resin component containing 60 to 70% by weight of the epoxy base resin and 30 to 40% by weight of the phosphorus flame retardant; And adhesion promoters 5 to 10, including 55 to 65% by weight of modified alicyclic amine, 15 to 25% by weight of polyoxypropylenediamine, 3-glycidoxypropyltrimethoxysilane, and phosphoric acid. It provides a non-halogen-free environmentally friendly earthquake-resistant maintenance-retardant flame-retardant epoxy resin composition consisting of; 100 parts by weight of the second composition comprising 5% by weight to 10% by weight of the curing accelerator of dimethylaminomethyl phenols.

Furthermore, according to the second aspect of the present invention,
45 to 54 wt% epoxy base resin and 10 to 18 wt% phosphorus flame retardant, 15 to 23 wt% aluminum hydroxide, 3-glycidoxypropyltrimethoxysilane and phosphate acid 100 parts by weight of the first composition of the resin component comprising 1 to 5% by weight of an adhesion promoter comprising 5 to 10% by weight of a silica-based anti-settling agent and 15 to 24% by weight of an aluminum metal powder; And adhesion promoters 1 to 20 to 15% by weight of modified alicyclic amine, 25 to 35% by weight of modified polyamido amine, 3-glycidoxypropyltrimethoxysilane, and phosphoric acid. Non-halogen-free eco-friendly earthquake-proof consisting of; 5 parts by weight, 1 to 5% by weight of the silica-based anti-settling agent, 25 to 35% by weight of aluminum hydroxide and 15 to 25% by weight of aluminum metal powder; A flame retardant epoxy resin composition for repair reinforcement is provided.

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Furthermore, according to the third aspect of the present invention,
100 parts by weight of the first composition of the resin component comprising 60 to 68% by weight of epoxy base resin and 30 to 38% by weight of phosphorus flame retardant, and 1 to 5% by weight of an additive including a flame retardant or an antifoaming agent; And 40 to 50% by weight of modified alicyclic amine as first curing agent, 40 to 50% by weight of polyether amine as second curing agent, 3-glycidoxypropyltrimethoxysilane and phosphoric acid The non-halogen-free environmentally friendly earthquake-resistant repair reinforcement flame retardant epoxy resin composition consisting of; 100 parts by weight of the second composition comprising an adhesion promoter of 1 to 5% by weight and a curing accelerator of 5 to 10% by weight of dimethylaminomethyl phenols.

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The flame retardant epoxy resin composition for non-halogen free eco-friendly earthquake-resistant repair reinforcement according to the present invention is environmentally friendly because it can suppress the generation of harmful substances such as dioxins by replacing the halogen-based flame retardant with phosphorus-based flame retardant.

Moreover, it is excellent in heat resistance, dimensional stability, durability, and elasticity by making a modified alicyclic amine hardening | curing agent and polyoxypropylene diamine the main component as a hardening | curing agent.

In addition, by using 3-glycidoxypropyltrimethoxysilane as an adhesion promoter, excellent adhesion is imparted, thereby enabling firm adhesion with the adherend (cement building structure and steel structure).

Hereinafter, embodiments according to the present invention are disclosed.

In describing the embodiments, the same reference numerals refer to the same configuration, and additional descriptions that may overlap or limit the meaning of the invention may be omitted in describing the embodiments of the present invention.

Prior to the detailed description, the concept of the invention, in spite of the singular form of the present disclosure, in the light of the circumstances in which the singular / plural is not clearly distinguished in the use of Korean and in the ordinary terminology used in the art. It is used in the sense that it includes plural expressions unless otherwise contradictory or clearly different from each other. In addition, the words "include", "have", "include", "comprise", or the like described or described in this specification may indicate in advance the possibility of the presence or addition of one or more other features or components, or a combination thereof. It should be understood that it does not exclude.

In addition, in the present invention, 'composition' is a term that includes the meaning of the original mixture and the compound, in the present invention 'composition' of the 'binder composition' is a 'mixture', unless otherwise stated or contrary to the overall content of the invention It is used to mean '.

The non-halogen-free, eco-friendly earthquake-resistant repair reinforcement epoxy resin composition for the present invention is largely provided by three embodiments.

1st Example  Explain.

The flame-retardant epoxy resin composition for non-halogen-free environment-friendly earthquake-resistant repair of a 1st Example mixes 100 weight part of 1st compositions which comprise a resin component, and 100 weight part of 2nd compositions which comprise a hardening | curing agent component.

The resin component constituting the first composition comprises an epoxy base resin and a phosphorus flame retardant.

Preferably 60 to 70% by weight epoxy base resin, may be included 30 to 40% by weight phosphorus flame retardant. If the phosphorus-based flame retardant is less than the weight percent composition, the flame retardancy is lowered, and if the composition is more than the weight percent, the flame retardancy is not economical because only the cost increases without significant change.

The epoxy base resin may be used without limitation, and specifically, a general epoxy resin, an epoxy resin containing chlorine, a noblock resin or a mixture thereof may be used. In addition, it is also possible to use a mixture of one or more materials commonly used in the field of the present invention, such as acrylic, urethane, fiber-reinforced plastics (FRP), latex resin. Specific examples of the epoxy resins may include R1475, KEM-128M, KEM-128-70, KEM-134-60, etc., which can be purchased from Kukdo Chemical, and one or more selected from the above types may be used and mixed. It is not.

In addition, the phosphorus flame retardant chemical name APP (Ammonium Polyphosphate), CG-P (Red Phousphours), TCEP (Tris (2-chloroethyl) Phosphate), IPPP (Isopropylphenyl Diphenyl Phosphate), TPP (Tripheyl Phosphate), TEP (Triethyl Phosphate) ), Resorcinol di phosphate (RDP), Trisyl Phosphate (TCP), TCPP, Reofos-65, and Phosflex-31L. Phosphorus-based flame retardant of the present invention may be a mixture of one or more of these.

Some polymers of the phosphorus-based flame retardant form carbonaceous char when pyrolyzed. The production of this char reduces the combustible fuel and turns off the fire by blocking heat by creating a thick barrier on the surface of the burning molecule. This action takes place in the condensation phase and phosphorus is an important condensation flame retardant. Phosphorus is pyrolyzed to produce phosphoric acid, which increases the amount of char by acting as a dehydration catalyst in the burning material. The mechanism for forming char is very complex, but phosphorus compounds contain oxygen atoms in polymer structures such as PC and PPO, and are very effective flame retardants for polymers that form char during combustion.

In particular, unlike the conventional halogen flame retardant, phosphorus (P) -based flame retardant is an environmentally friendly material that does not generate dioxin, a carcinogen when fired, and exhibits flame retardancy comparable to halogen flame retardant.

On the other hand, the cured component constituting the second composition is made of a mixture of modified alicyclic amine, polyoxypropylenediamine (Polyoxypropylenediamine), adhesion promoter and curing accelerator.

Preferably, the curing component may include 55 to 65% by weight of modified alicyclic amine, 15 to 25% by weight of polyoxypropylene diamine, 5 to 10% by weight of adhesion promoter, and 5 to 10% by weight of curing accelerator.

Here, the modified cycloaliphatic amine is an element that affects the heat resistance and dimensional stability improvement, if the composition is lower than the stomach weight%, the heat resistance and dimensional stability is lowered, if the composition is higher than the stomach weight%, the heat resistance and dimensional stability is increased but proportional to The price will rise. The modified alicyclic amine is preferably selected to a viscosity of about 1,000 to 2,500 cps in order to improve heat resistance and dimensional stability based on the composition ratio of the above range, the amine value is preferably between 300 and 360. Such product is KH-817 from Kukdo Chemical. As the modified alicyclic amine, for example, triethylenetriamine or triethyltetramine may be used, and xylene may be used as a non-reactive diluent, and methylphenol such as dimethylaminomethylphenyl may be further used as a catalyst.

Polyoxypropylenediamine is included for the improvement of durability and elasticity. Here, if the polyoxypropylene diamine is lower than the weight percent by weight, durability and elasticity is lowered, and when the polyoxypropylene diamine is higher than the weight percent, durability and elasticity is not greatly improved, but cost is unnecessarily increased, which is inefficient.

Adhesion enhancers are included to improve adhesion to cement building structures and steel structures. Here, when the adhesion promoter is lower than the above weight%, the adhesion decreases, and when the adhesion enhancer is higher than the above weight%, the increase in adhesion is slowed and unnecessary costs are added.

The adhesion promoter may include 3-glycidoxypropyltrimethoxysilane and phosphate acid in order to obtain greater adhesion within the above composition range, and their optimum combination ratio is 3 Preference is given to 46 to 59% by weight of 3-glycidoxypropyltrimethoxysilane and 41 to 54% by weight of phosphate acid. Its combination ratio is the optimal ratio for maximizing adhesion. Therefore, when the combination ratio of 3-glycidoxypropyltrimethoxysilane and phosphoric acid is out of the above range, a phenomenon occurs that the adhesion is weakened.

The curing accelerator should be a material from which the side reactants can be extracted through an exchange reaction with the amine (modified alicyclic amine, polyoxypropylene diamine). Therefore, the curing accelerator may be a material of dimetalaminomethyl phenols. The substances of the above-mentioned dimetalaminomethylphenols are specifically di- (2,6-dimethylaminomethyl) -phenol, tris- (2,4,6-dimethylaminomethyl) -phenol and ortho- (dimethylaminomethyl) -phenol Etc. can be mentioned. These can be used individually or in mixture of 1 or more types.

Second Example  Explain.

The flame retardant epoxy resin composition for non-halogen-free environment-friendly seismic repair reinforcement of the second embodiment is mixed with 100 parts by weight of the first composition constituting the resin component and 100 parts by weight of the second composition constituting the curing agent component as in the first embodiment. Is done.

The resin component constituting the first composition comprises an epoxy base resin, a phosphorus flame retardant, aluminum hydroxide, an adhesion promoter, an antisettling agent, and an aluminum metal powder.

Preferably 45 to 54% by weight of epoxy base resin, 10 to 18% by weight of phosphorus flame retardant, 15 to 23% by weight of aluminum hydroxide, 1 to 5% by weight of adhesion promoter, 5 to 10% by weight of anti-settling agent and aluminum metal powder It may comprise 15 to 24% by weight.

The epoxy base resin may be used without limitation, and specifically, a general epoxy resin, an epoxy resin containing chlorine, a noblock resin or a mixture thereof may be used. In addition, it is also possible to use a mixture of one or more materials commonly used in the field of the present invention, such as acrylic, urethane, fiber-reinforced plastics (FRP), latex resin. Specific examples of the epoxy resins may include R1475, KEM-128M, KEM-128-70, KEM-134-60, etc., which can be purchased from Kukdo Chemical, and one or more selected from the above types may be used and mixed. It is not.

In addition, the phosphorus flame retardant chemical name APP (Ammonium Polyphosphate), CG-P (Red Phousphours), TCEP (Tris (2-chloroethyl) Phosphate), IPPP (Isopropylphenyl Diphenyl Phosphate), TPP (Tripheyl Phosphate), TEP (Triethyl Phosphate) ), Resorcinol di phosphate (RDP), Trisyl Phosphate (TCP), TCPP, Reofos-65, and Phosflex-31L. Phosphorus-based flame retardant of the present invention may be a mixture of one or more of these.

Some polymers of the phosphorus-based flame retardant form carbonaceous char when pyrolyzed. The production of this char reduces the combustible fuel and turns off the fire by blocking heat by creating a thick barrier on the surface of the burning molecule. This action takes place in the condensation phase and phosphorus is an important condensation flame retardant. Phosphorus is pyrolyzed to produce phosphoric acid, which increases the amount of char by acting as a dehydration catalyst in the burning material. The mechanism for forming char is very complex, but phosphorus compounds contain oxygen atoms in polymer structures such as PC and PPO, and are very effective flame retardants for polymers that form char during combustion.

In particular, unlike the conventional halogen flame retardant, phosphorus (P) -based flame retardant is an environmentally friendly material that does not generate dioxin, a carcinogen when fired, and exhibits flame retardancy comparable to halogen flame retardant.

In addition, the aluminum hydroxide has an average particle size of 1 ~ 50㎛, a flame retardant effect is shown by the dehydration reaction that 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 15 to 23%. If the blending amount is less than 15% by weight, there is no flame retardant effect. If the blending amount is more than 23% by weight, the flexural strength is significantly lowered, so the selection of an appropriate blending amount is important. The aluminum hydroxide may also be used aluminum hydroxide of the type surface-treated with a silane coupling agent, these may be used alone or in combination.

Adhesion enhancers are included to improve adhesion to cement building structures and steel structures. Here, when the adhesion promoter is lower than the above weight%, the adhesion decreases, and when the adhesion enhancer is higher than the above weight%, the increase in adhesion is slowed and unnecessary costs are added.

The adhesion promoter may include 3-glycidoxypropyltrimethoxysilane and phosphate acid in order to obtain greater adhesion within the above composition range, and their optimum combination ratio is 3 Preference is given to 46 to 59% by weight of 3-glycidoxypropyltrimethoxysilane and 41 to 54% by weight of phosphate acid. Its combination ratio is the optimal ratio for maximizing adhesion. Therefore, when the combination ratio of 3-glycidoxypropyltrimethoxysilane and phosphoric acid is out of the above range, a phenomenon occurs that the adhesion is weakened.

The antisettling agent is added for the purpose of imparting and preventing the sedimentation, and may be a silica type, such as silicon oxide (SiO ₂ ), and if the antisettling agent is less than 5% by weight, its role is negligible. If it is not more than 10% by weight, it becomes an excess, resulting in poor fluidity during operation and lowering of surface leveling.

In addition to inorganic fillers, the aluminum metal powder is crystalline silica, fused silica, alumina, magnesia, talc, mica, kaolin, clay, diatomaceous earth, calcium silicate, titanium oxide, glass fiber, calcium fluoride, calcium sulfate, barium sulfate, calcium phosphate, carbon Fibers, carbon nanotubes, potassium titanate fibers and the like, and any one or a plurality of these may be mixed and used. The inorganic filler is 15 to 24% by weight, but less than 15% by weight stiffness or flame retardancy is lowered, when more than 24% by weight is the problem that the fluidity is lowered or mechanical strength is lowered.

On the other hand, the cured component constituting the second composition is modified aliphatic amine (Modified aliphatic amine), modified polyamidoamine (Modified Polyamidoamine), adhesion promoter, sedimentation inhibitor, aluminum hydroxide (aluminium hydroxide) and aluminum metal powder is mixed.

Preferably, the curing component is modified aliphatic amine (Modified aliphatic amine) 15-20% by weight, modified polyamidoamine (Modified Polyamidoamine) 25-35% by weight, adhesion promoter 1-5% by weight, sedimentation inhibitor 1-5% %, 25% to 35% by weight of aluminum hydroxide and 15 to 25% by weight of aluminum metal powder.

Here, the modified cycloaliphatic amine is an element that affects the heat resistance and dimensional stability improvement, if the composition is lower than the stomach weight%, the heat resistance and dimensional stability is lowered, if the composition is higher than the stomach weight%, the heat resistance and dimensional stability is increased but proportional to The price will rise. The modified alicyclic amine is preferably selected to a viscosity of about 1,000 to 2,500 cps in order to improve heat resistance and dimensional stability based on the composition ratio of the above range, the amine value is preferably between 300 and 360. Such product is KH-817 from Kukdo Chemical. For example, triethylenetriamine or triethyltetramine may be used as the modified alicyclic amine, and xylene may be used as a non-reactive diluent, and methylphenol such as dimethylaminomethylphenyl may be further used as a catalyst.

The modified polyamidoamine, like the modified alicyclic amine, also affects the heat resistance and dimensional stability improvement. If the composition is lower than the weight%, the heat resistance and the dimensional stability are lowered. Increases but the price rises in proportion.

Such modified polyamidoamine is preferably prepared by condensation reaction of amines such as aliphatic amines, aromatic amines, and cycloaliphatic amines with dimeric acid or monomeric fatty acid such that the amine number is about 200 to 500. Various amines usable for their preparation include ethylenediamine, diethylenetriamine, triethylenetetraamine, pentaethylene hexaamine, N- (3-aminopropyl) -1, 2-ethanediamine, N, N'-bis -(3-aminopropyl) -1,2-ethanediamine, bis- (3-aminopropyl) amine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,3- Pentanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, aminoethylpiperazine, meta-xylenediamine, phenylenediamine, 4 , 4'-diaminodiphenylmethane, toluene diamine, isophoronediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminocyclohexylmethane, and the like. .

The other compositions of the second composition, the adhesion promoter, the anti-settling agent, the aluminum hydrated aluminum and the aluminum metal powder, differ only in the mixing ratio from the previous first composition, and thus the detailed description thereof will be omitted.

Third Example  Explain.

The flame retardant epoxy resin composition for non-halogen-free environment-friendly seismic repair reinforcement of the third embodiment is the same as the first and second embodiments, 100 parts by weight of the first composition constituting the resin component and 100 parts by weight of the second composition constituting the curing agent component. It is made by mixing.

The resin component constituting the first composition comprises an epoxy base resin, a phosphorus flame retardant, an additive, and an adhesion promoter.

Preferably, the epoxy base resin may include 60 to 70% by weight, phosphorus flame retardant 30 to 40% by weight, additives 1 to 5% by weight and adhesion promoter 1 to 5% by weight.

The epoxy base resin may be used without limitation, and specifically, a general epoxy resin, an epoxy resin containing chlorine, a noblock resin or a mixture thereof may be used. In addition, it is also possible to use a mixture of one or more materials commonly used in the field of the present invention, such as acrylic, urethane, fiber-reinforced plastics (FRP), latex resin. Specific examples of the epoxy resins may include R1475, KEM-128M, KEM-128-70, KEM-134-60, etc., which can be purchased from Kukdo Chemical, and one or more selected from the above types may be used and mixed. It is not.

In addition, the phosphorus flame retardant chemical name APP (Ammonium Polyphosphate), CG-P (Red Phousphours), TCEP (Tris (2-chloroethyl) Phosphate), IPPP (Isopropylphenyl Diphenyl Phosphate), TPP (Tripheyl Phosphate), TEP (Triethyl Phosphate) ), Resorcinol di phosphate (RDP), Trisyl Phosphate (TCP), TCPP, Reofos-65, and Phosflex-31L. Some polymers form carbonaceous char when thermally decomposed. The production of this char reduces the combustible fuel and turns off the fire by blocking heat by creating a thick barrier on the surface of the burning molecule. This action takes place in the condensation phase and phosphorus is an important condensation flame retardant. Phosphorus is pyrolyzed to produce phosphoric acid, which increases the amount of char by acting as a dehydration catalyst in the burning material. The mechanism for forming char is very complex, but phosphorus compounds contain oxygen atoms in polymer structures such as PC and PPO, and are very effective flame retardants for polymers that form char during combustion.

In particular, unlike the conventional halogen flame retardant, phosphorus (P) -based flame retardant is an environmentally friendly material that does not generate dioxin, a carcinogen when fired, and exhibits flame retardancy comparable to halogen flame retardant.

Additives may be added, for example, a flame retardant, there is no limitation as long as the epoxy resin has an effect that can be maintained above the ignition temperature, conventionally known zinc oxide (molybdenum oxide) and ferrocene (molrocdenum oxide) and ferrocene (ferrocene) Etc. may be selectively used alone or in combination of two or more kinds thereof. Alternatively, the antifoaming agent may be further included in the additive. Antifoaming agent is not limited as long as it has the effect of removing harmful bubbles, and optionally, octyl alcohol, cyclohexanol, cyclohexane, higher alcohol, ethylene glycol You may use it.

The first curing agent may apply a modified alicyclic amine as mentioned in another embodiment, and the second curing agent may apply a polyetheramine. Other components are already mentioned in the first and second embodiments, and thus detailed descriptions thereof will be omitted.

ingredient Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 Resin





Epoxy base resin 65 g 75 g 46 g 63 g 64 g 72 g Phosphorus Flame Retardant 35 g 25 g 13g 8 g 31 g 15 g Aluminum hydroxide - - 16 g 11 g - - Adhesion promoter - - 4 g 8 g 2 g 7g Sedimentation inhibitors - - 5g 2 g - - Aluminum metal powder - - 16 g 8 g - - additive - - - - 3g 6 g sub Total 100g 100g 100g 100g 100g 100g Curing Ingredient






Modified alicyclic amines 61 g 50 g 17g 12g 42 g 38 g Polyoxypropylenediamine 22 g 42 g - - - - Adhesion promoter 9g 4 g 3g 9g 3g 7g Hardening accelerator 8 g 4 g - - 7g 3g Modified polyamidoamine - - 26 g 42 g - - Sedimentation inhibitors - - 4 g 10g - - Aluminum hydroxide - - 29 g 18g - - Aluminum metal powder - - 21 g 9g - - Polyetheramine - - - - 48 g 52 g sub Total 100g 100g 100g 100g 100g 100g

As shown in Table 1, Examples 1, 2 and 3 were mixed with the composition constituting the halogen-free flame retardant epoxy resin in the present invention within the composition range of the claims, Comparative Examples 1, 2, 3 was formulated by mixing the composition outside the compositional scope of the claims. Mechanical properties according to this is shown in Table 2 below.

On the other hand, the epoxy base resin of Example 1 was used an epoxy resin containing chlorine, phosphorus-based flame retardant was used APP (Ammonium Polyphosphate), modified alicyclic amine was used triethylene triamine, adhesion promoter is 3-gly 47 wt% of 3-Glycidoxypropyltrimethoxysilane and 53 wt% of phosphoric acid were used, and a curing accelerator was di- (2,6-dimethylaminomethyl) -phenol.

In addition, the epoxy base resin and the phosphorus-based flame retardant of Example 2 were used the same components as in Example 1, the modified alicyclic amine was used triethylene triamine, and the anti-settling agent commonly included in the resin component and the curing component is silicon oxide (SiO ₂ ) was used, and adhesion promoters commonly included in the resin component and the curing component were used by 47% by weight of 3-glycidoxypropyltrimethoxysilane and 53% by weight of phosphoric acid. It became.

In the epoxy base resin and the phosphorus flame retardant of Example 3, the same components as in Example 1 were used, the additive was zinc oxide, and the modified alicyclic amine was triethylenetriamine, which is common to the resin component and the curing component. The adhesion promoter included as 47% by weight of 3-glycidoxypropyltrimethoxysilane and 53% by weight of phosphate acid, the curing accelerator was di- (2,6-dimethylaminomethyl ) -Phenol was used.

Item Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 The tensile strength
(N / mm ² ) 50 32 30 25 50 46 Flexural strength
(N / mm ² ) 70 57 50 44 60 55 Tensile shear
Adhesive strength
(N / mm ² ) 13 12 17 17 13 13 Compressive strength
(N / mm ² ) 120 101 80 76 100 97 Modulus of elasticity
(N / mm ² ) 1,100 1,059 1,000 890 900 887 Elongation (%) 13 12 1.5 1.2 12 11

As shown in Table 2, Examples 1, 2, and 3 can be seen that the mechanical properties are relatively superior to Comparative Examples 1, 2, and 3 corresponding thereto.

Although the present invention has been described in detail with respect to specific embodiments, it will be apparent to those skilled in the art that various modifications may be made without departing from the scope of the present invention.

Claims (13)

100 parts by weight of the first composition of the resin component containing 60 to 70% by weight of the epoxy base resin and 30 to 40% by weight of the phosphorus flame retardant; And
55-10% by weight of modified alicyclic amine, 15-25% by weight of polyoxypropylenediamine, 5-10% by weight of adhesion promoter including 3-glycidoxypropyltrimethoxysilane and phosphate acid 100 parts by weight of the second composition comprising% and 5 to 10% by weight of a curing accelerator of dimethylaminomethyl phenol;
Flame retardant epoxy resin composition for non-halogen-free eco-friendly earthquake-resistant repair made of.
The method of claim 1,
The viscosity of the modified alicyclic amine is 1,000 ~ 2,500 cps, the amine number is a non-halogen-free eco-friendly earthquake-resistant maintenance reinforcement flame retardant epoxy resin composition, characterized in that 300 to 360.
delete According to claim 1, wherein the curing accelerator,
One or more selected from the group consisting of di- (2,6-dimethylaminomethyl) -phenol, tris- (2,4,6-dimethylaminomethyl) -phenol and oso- (dimethylaminomethyl) -phenol Non-halogen-free eco-friendly earthquake-resistant repair reinforcement flame-retardant epoxy resin composition, characterized in that the mixed mixture.

45 to 54 wt% epoxy base resin and 10 to 18 wt% phosphorus flame retardant, 15 to 23 wt% aluminum hydroxide, 3-glycidoxypropyltrimethoxysilane and phosphate acid 100 parts by weight of the first composition of the resin component comprising 1 to 5% by weight of an adhesion promoter comprising 5 to 10% by weight of a silica-based anti-settling agent and 15 to 24% by weight of an aluminum metal powder; And
15 to 20% by weight of modified alicyclic amine, 25 to 35% by weight of modified polyamido amine, adhesion promoter 1 to 5 including 3-glycidoxypropyltrimethoxysilane and phosphoric acid 100 weight part of the 2nd composition of the hardening component containing 1 weight%, 1-5 weight% of anti-settling agents of a silica type | system | group, 25-35 weight% of aluminum hydroxide, and 15-25 weight% of aluminum metal powders;
Flame retardant epoxy resin composition for non-halogen-free environmentally friendly earthquake-resistant repair made of.
delete The method of claim 5,
The anti-settling agent is a non-halogen-free eco-friendly earthquake-resistant maintenance reinforcement flame retardant epoxy resin composition, characterized in that the silicon oxide (SiO ₂ ).
100 parts by weight of the first composition of the resin component comprising 60 to 68% by weight of epoxy base resin and 30 to 38% by weight of phosphorus flame retardant, and 1 to 5% by weight of an additive including a flame retardant or an antifoaming agent; And
40-50% by weight of modified alicyclic amine as first curing agent, 40-50% by weight of polyether amine as second curing agent, 3-glycidoxypropyltrimethoxysilane and phosphoric acid 100 parts by weight of the second composition comprising 1 to 5% by weight of an adhesion promoting agent and 5 to 10% by weight of a curing accelerator of dimethylaminomethyl phenol;
Flame retardant epoxy resin composition for non-halogen-free eco-friendly earthquake-resistant repair made of.
9. The method of claim 8,
The additive is a non-halogen-free, eco-friendly earthquake-resistant repair reinforcement, characterized in that a mixture of one or more selected from the group consisting of zinc oxide, molybdenum oxide and ferrocene as a flame retardant. Flame retardant epoxy resin composition.
delete delete 9. The method of claim 8,
The curing accelerator is one selected from the group consisting of di- (2,6-dimethylaminomethyl) -phenol, tris- (2,4,6-dimethylaminomethyl) -phenol, and oso- (dimethylaminomethyl) -phenol. Or non-halogen-free, eco-friendly earthquake-resistant repair reinforcement flame retardant epoxy resin composition, characterized in that the mixture is one or more kinds.
The method according to any one of claims 1, 5, and 8,
The halogen-free flame-retardant epoxy resin composition is a non-halogen-free eco-friendly earthquake-resistant repair reinforcement flame retardant epoxy resin composition, characterized in that used for repair reinforcement of civil engineering, building structures.