KR102402019B1 - Non-flame epoxy resin with thermal shock resistance in water and composition and Sensor filler containing the same - Google Patents

Abstract

The present invention relates to a flame-retardant epoxy resin having excellent adhesion to inorganic materials such as metal, non-ferrous metal, plastic material, and glass, and excellent resistance to thermal shock and/or thermal shock in water, and a sensor filler using the same.

Description

Non-flame epoxy resin with thermal shock resistance in water and composition and Sensor filler containing the same}

The present invention relates to a flame-retardant epoxy resin having excellent resistance to thermal shock and/or thermal shock in water and a sensor filler using the same.

Temperature sensors are used to obtain temperature information necessary for operation and operation of refrigerators for home or business use, cooling devices for testing, industrial refrigeration warehouses, and plastic houses that require proper temperature maintenance.

Looking at the structure of the temperature sensing unit 100 of the temperature sensor shown in FIG. 1 , the temperature sensing unit 100 is provided with a temperature sensing sensor 130 in a protective tube 110 made of metal or plastic, and the temperature sensing unit 100 A wire wrapped in a heat-resistant coating is connected to the sensor 130 . In addition, the inside of the protective tube 110 in which the temperature sensor 130 is embedded is filled with a resin as a heat-resistant sealing member 150 to fix the temperature sensor 130 and at the same time prevent moisture from flowing into the inside. prevent.

As a filling resin, it is generally used by adding a curing agent such as polyamine to an epoxy resin. Such an epoxy resin has advantages of excellent adhesion, heat resistance, chemical resistance, electrical properties and mechanical properties. However, the epoxy resin has a disadvantage in that it has a low adhesion to inorganic materials such as alumina used as a filler. This occurred. In addition, there is a problem in that a gap is generated between the protective tube 110 and the epoxy resin due to insufficient adhesive force, and moisture is introduced.

In addition, since the temperature sensor is used in a wide temperature range of -20°C to +80°C, resistance to thermal shock in water is an important factor. There was a problem in that the protective tube and the epoxy resin were separated during the underwater thermal shock test.

Republic of Korea Patent Publication No. 10-2013-0016533 (published on February 18, 2013) Republic of Korea Patent Publication No. 10-1665596 (published on October 13, 2016)

The present invention relates to an invention that was completed by knowing the optimum composition and composition ratio of an epoxy resin having excellent flame retardancy, hardness, elongation and adhesive strength, as well as excellent resistance to thermal shock in water, while minimizing the use of a reactive diluent, that is, the present invention is a flame-retardant epoxy resin with excellent resistance to thermal shock in water, and relates to an invention suitable for applying it as a sensor filling resin (filler) for temperature sensors and automobile sensors.

The present invention for solving the above problems is a flame-retardant epoxy resin with excellent resistance to thermal shock in water, and includes a two-component epoxy resin including a main agent and a curing agent, wherein the main subject is an alkoxysilane-modified epoxy resin, a phosphorus-based flame retardant, a melamine-based flame retardant, It includes a silane-based additive and a filler, and the curing agent includes aliphatic amine and polyoxy (C ₁ to C ₅ alkylene)diamine.

In addition, another object of the present invention relates to a sensor filler, including the flame-retardant epoxy resin.

The flame-retardant epoxy resin of the present invention has excellent adhesion to metals, non-ferrous metals, plastic materials, and inorganic materials such as glass, Cl- content is 200 ppm or less, and is a flame ^- retardant type with excellent underwater thermal shock and/or thermal shock, a temperature sensor, Suitable for use as a sensor filling resin (filler) for automobile sensors and the like.

1 is a cross-sectional view illustrating a temperature sensing unit of a temperature sensor.

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

The flame-retardant epoxy resin of the present invention is a two-component epoxy resin containing a main agent and a curing agent, and when applied as a sensor filling resin (filler) such as a temperature sensor or automobile sensor, mix the main agent and the curing agent and then apply as a filler.

Among the flame-retardant epoxy resin components, the subject has an alkoxy group, so it has excellent adhesion to inorganic materials such as aluminum and glass, and has an organic functional group that chemically bonds with organic materials, so it plays a role in bonding organic materials and inorganic materials and reduces the surface energy of organic materials to reduce inorganic materials A silane-modified epoxy resin that can improve the adhesion between copper and nickel by improving wetting on the surface of

In addition, phosphorus-based flame retardants and melanin-based flame retardants were introduced to improve thermal shock resistance by securing flame retardancy of the epoxy resin.

In addition, by introducing an alumina-based filler with excellent adhesion and thermal conductivity, the thermal shock in water when filling the sensor is superior to other epoxy resins, and the elongation is 300% or more, which is excellent in cold-temperature stability.

More specifically, the subject includes an alkoxysilane-modified epoxy resin, a phosphorus-based flame retardant, a melamine-based flame retardant, a silane-based additive, and a filler.

Among the main components, the alkoxysilane-modified epoxy resin may be an alkoxysilane-modified epoxy resin having an alkoxysilane group represented by the following formula (1).

[Formula 1]

In Formula 1, R ¹ is a linear alkyl group having 1 to 20 carbon atoms or a pulverized alkyl group having 3 to 20 carbon atoms, preferably a straight chain alkyl group having 1 to 15 carbon atoms, more preferably a straight chain alkyl group having 1 to 10 carbon atoms. It is a chain-type alkyl group.

In addition, R ² in Formula 1 is a linear alkyl group having 1 to 4 carbon atoms having an organic functional group of a vinyl group, a glycidoxy group, an acryl group or a mercapto group, preferably having a glycidoxy group or a mercapto group having 1 carbon number to 4 straight-chain alkyl groups. In a preferred embodiment of R ² , examples of R ² include a glycidoxymethyl group, α-glycidoxyethyl group, β-glycidoxyethyl group, α-glycidoxypropyl group, β-glycidoxypropyl group, α-glycidoxypropyl group, mercaptomethyl group, α-mercaptoethyl group, β-mercaptoethyl group, α-mercaptopropyl group, β-mercaptopropyl group, γ-mercaptopropyl group, etc. are mentioned. .

This alkoxysilane group has both an alkoxy group having excellent affinity with an inorganic material and an organic functional group having excellent affinity with an organic material, so that it can be easily combined with an epoxy resin, and also improves wettability by reducing surface energy with a protective tube to improve adhesion this is increased

In this case, the alkoxysilane-modified epoxy resin may be obtained by reacting an alkoxysilane having an organic functional group represented by the following Chemical Formula 2 with an epoxy resin. Specifically, it can be prepared by esterifying an epoxy resin and a compound containing a carboxyl group (eg, dimer acid), followed by de-alcoholization of an organic functional group-containing alkoxysilane.

[Formula 2]

In Formula 2, R ¹ and R ² are the same as R ¹ and R ² in Formula 1 above.

Examples of such alkoxysilane compounds include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycy Doxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane , β-glycidoxypropyl-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyl and triethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

On the other hand, as the epoxy resin reacted with the alkoxysilane, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, cresol novolac (Kresol novolac) )-type epoxy resin, phenol novolac-type epoxy resin, brominated epoxy resin, phenoxy resin, urethane-modified epoxy resin, NBR-modified epoxy resin, or a mixture thereof.

The content of the alkoxysilane-modified epoxy resin in the main component may be included in an amount of 10 wt% to 20 wt%, preferably 12 wt% to 20 wt%, more preferably 13 to 19 wt%. At this time, when the amount of the alkoxysilane-modified epoxy resin is less than 10% by weight, sufficient adhesion cannot be obtained or a problem of low hardness may occur, and when it exceeds 20% by weight, it is difficult to process the epoxy resin composition, and elongation and storage stability It is better to use it within the above range because it may fall rather.

Next, among the main ingredients, the phosphorus-based flame retardant may use a general phosphorus-based flame retardant used in the art, but preferably TCP (Tricresyl phosphate), TPP (Triphenyl phosphate), TXP (Trixylenyl phosphate) and trade name Reofos R-65 ( (Triphenyl Phosphates Isopropylated) may include at least one selected from the group consisting of. And, the content of the phosphorus-based flame retardant is 1.0 to 5.0 wt%, preferably 1.0 to 4.5 wt%, more preferably 1.5 to 4.0 wt%, based on the total weight of the main ingredient At this time, if the phosphorus-based flame retardant content is less than 1.0% by weight, there may be a problem of reducing the flame retardancy, and if it exceeds 5.0% by weight, there may be a problem of reducing thermal shock and/or thermal shock in water. It is recommended to use it within the range.

Next, among the main components, the melamine-based flame retardant serves to increase the flame retardancy of the epoxy resin together with the phosphorus-based flame retardant, and a general melamine-based flame retardant used in the art may be used, but preferably MCA (melamine cyanurate), MPP (melamine pyrophosphate) and APP (ammonium polyphosphate) may include one or more selected from. And, the content of the melamine-based flame retardant may include 5.0 to 15.0% by weight, preferably 5.0 to 14.0% by weight, more preferably 7.5 to 12.0% by weight based on the total weight of the main agent. At this time, if the content of the melamine-based flame retardant is less than 5.0% by weight, there may be a problem of reduced flame retardancy, and if it exceeds 15.0% by weight, there may be a problem of reduced workability due to an increase in viscosity, so it is recommended to use it within the above range.

Next, among the main components, the silane-based additive serves to improve adhesion, and may include glycidoxyalkyl trialkoxy silane, preferably r-glycidoxypropyl trimethoxy silane, glycidoxypropyl tri It may include at least one selected from ethoxy silane, glycidoxypropyl tripropoxy silane, glycidoxyethyl trimethoxy silane, glycidoxyethyl triethoxy silane, and glycidoxyethyl tripropoxy silane. Further, the content of the silane-based additive may be 0.5 to 5.0 wt%, preferably 0.5 to 4.0 wt%, more preferably 1.0 to 3.0 wt%, based on the total weight of the main agent. In this case, if the content of the silane-based additive is less than 0.5% by weight, there may be a problem of insufficient adhesion, and if it exceeds 5.0% by weight, there may be a problem in that thermal shock is reduced, so it is preferable to use it within the above range.

Next, among the main ingredients, the filler uses silane-coated alumina to increase thermal conductivity, and the shape of the filler is spherical and angular, respectively, mixed and used to enhance workability, flowability, and durability. The particle size is D ₅₀ 4-50 μm, preferably D ₅₀ 40-50 μm, so that the overall particle size is evened to improve workability during filling. And, by using such a silane-coated alumina, it is possible to improve the adhesion to improve the thermal shock in water (-5 ℃ ~ +95 ℃) from 10,000 cycles of the existing product to 15,000 cycles (cycle).

The silane as the alumina coating material is methyltriethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltri Ethoxysilane, bis-(triethoxysilylpropyl)tetrasulfide, bis-(triethoxysilylpropyl)disulfide, gamma-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltri Ethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-phenyl-gamma-amino Propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane , 3-mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, Octyltriethoxysilane, 3-chloropropyltriethoxysilane, vinyl-tris-(2-methoxyethoxy)silane, 3-mercaptopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane, 3 It may include at least one selected from -chloropropylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, and n-octadecyltrimethoxysilane.

And, the content of the filler in the main agent is the remaining amount excluding the alkoxysilane-modified epoxy resin, phosphorus-based flame retardant, melamine-based flame retardant, and silane-based additive in the total weight of the main agent.

In addition, the filler further includes inorganic fillers such as silica, diatomaceous earth, zinc oxide, iron oxide, tin oxide, titanium oxide, silicon nitride, rubber particles, and organic fillers such as polyester particles in addition to silane-coated alumina in addition to silane-coated alumina. You may.

In addition, the epoxy resin of the present invention may further include an adhesion promoter to improve adhesion as a main component. As the adhesion promoter, methacryloxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, epoxy ester phosphate acid, or the like may be used. In the case of the methacrylooxypropyl trimethoxy silane adhesion promoter, there is no shrinkage or expansion due to curing of the epoxy resin composition.

When the adhesion enhancer is used, its appropriate content is 0.01 to 3.0% by weight, preferably 0.1 to 2.0% by weight, based on the total weight of the main agent.

Next, among the epoxy resin components, the curing agent is for crosslinking the epoxy with each other, and increases the adhesion of the resin composition. In this case, aliphatic amine and polyoxy (C ₁ to C ₅ alkylene) diamine may be used as the curing agent.

The aliphatic amine can improve physical properties such as thermal shock in water, stability at high and low temperatures, and durability, and aliphatic amine is isophorone diamine, 1,3-cyclohexanebis(methylamine), 4,4'-methylene Bis(cyclohexylamine), 1,2-diaminocyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-dianinodicyclohexylmethane, bis(amino Cyclohexyl)methane, 1,4-cyclohexanediamine, bis(aminomethyl)norbornane, piperazine, aminoethylpiperazine (AEP) and 4,4′-methylenebis-(2-methyl-cyclohexanamine) may include at least one selected from among, preferably 4,4'-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane, 3,3'-dimethyl-4,4'-diamino It may include at least one selected from dicyclohexylmethane, 4,4'-dianinodicyclohexylmethane, and 4,4'-methylenebis-(2-methyl-cyclohexanamine).

And, the content of aliphatic amine in the curing agent may include 10 to 20% by weight, preferably 12 to 18% by weight, more preferably 13 to 17% by weight of the total weight of the curing agent. At this time, if the content of aliphatic amine is less than 10% by weight, the durability of the epoxy resin may be poor, and if it exceeds 20% by weight, the thermal shock resistance in water may be deteriorated, so it is recommended to use it within the above range.

And, the polyoxy (C ₁ ~ C ₅ alkylene) diamine reduces the thermal expansibility at high temperature of the epoxy resin, increases water resistance and viscosity to increase thermal shock resistance in water, and has a large molecular weight and thus plasticity It improves the flexibility of the epoxy resin by being rich in it, and improves the flexibility of the epoxy resin at cold and temperature. In addition, there is almost no shrinkage by suppressing the exothermic reaction during the reaction (mixing of the epoxy base material and the curing agent), and the workability can be improved because the curing time is long. The content of polyoxy (C ₁ to C ₅ alkylene) diamine in the curing agent may be the remaining amount other than the aliphatic amine.

In addition, the curing agent may further include a curing catalyst. The curing catalyst is for increasing the curing rate and curing degree of the resin composition, and a phosphorus-based catalyst, an amine-based catalyst, or the like may be used. At this time, the phosphorus-based catalyst includes triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate, and the like, and the amine-based catalyst includes dicyandiamide, 2-methylimidazole, and 2-ethyl-4. Imidazole derivatives such as -methylimidazole, 1-cyanoethyl-2-methylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole can be used. These curing catalysts may be used alone or in mixture of two or more.

The epoxy resin of the present invention includes the main agent and the curing agent in a weight ratio of 1: 0.1 to 0.3, preferably, the main agent and the curing agent in a weight ratio of 1: 0.12 to 0.25, more preferably, the main agent and the curing agent in a weight ratio of 1: 0.12 It may be included in a weight ratio of ~ 0.20. At this time, if the amount of the curing agent used is less than 0.1 weight ratio, the curing rate of the epoxy resin is too slow, the adhesive strength may not be sufficient, and even if used in excess of 0.3 weight ratio, there is no effect of improving physical properties, which is uneconomical.

In addition, the epoxy resin of the present invention may further include a reactive diluent in addition to the main agent and curing agent. The reactive diluent is for controlling the viscosity of the epoxy resin, and glycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, and the like may be used. The reactive diluent may be used in an amount of 5 parts by weight or less based on 100 parts by weight of the main agent.

In addition, the epoxy resin according to the present invention may further include one or more additives selected from the group consisting of pigments, defoaming agents, dispersants and surfactants. The pigment may be added in an amount of 5 parts by weight or less based on 100 parts by weight of the main agent. Other additives may also be added in an amount of 5 parts by weight or less based on 100 parts by weight of the main mixture.

The epoxy resin of the present invention described above may have thermal shock in water of 12,000 cycles or more, preferably 12,000 to 20,000 cycles. In addition, the elongation may be 300% or more, preferably 300 to 500%.

In addition, the epoxy resin of the present invention may have a hardness (Shore A) of 55 or more, preferably 55 to 85, more preferably 65 to 85.

In addition, the epoxy resin of the present invention may have a Cl ⁻ content of 200 ppm or less, preferably 170 ppm or less.

In addition, the epoxy resin of the present invention may have a pot life (25 ℃, 3KG) of 5 hours or more.

The epoxy resin of the present invention is suitable for use as a filling resin (filler) of a sensor, for example, a temperature sensor such as an air conditioner, a refrigerator, a water purifier, and a sensor filling resin (filler) such as a car sensor suitable for In addition, the epoxy resin of the present invention is a paint or adhesive for concrete, cement mortar, leather, glass, rubber, plastic, wood, cloth, paper, etc. in addition to the sensor filling resin; adhesive tapes for packaging, adhesive labels, frozen food labels, rim-bal labels, POS labels, adhesive wallpaper, adhesives for adhesive flooring; processed paper such as art paper, lightweight court paper, cast coat, and impregnated paper; fiber treatment agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers, and metal fibers; It can be used for a wide range of applications such as sealing materials, cement admixtures, and building materials such as waterproofing materials.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are not intended to limit the scope of the present invention, which should be construed to aid understanding of the present invention.

[Example]

Example 1: Preparation of flame-retardant epoxy resin for bonding and molding

(1) 15 wt% of an alkoxysilane-modified epoxy resin having an alkoxysilane group represented by the following formula (1), 2.5 wt% of TCP (Tricrecyl phosphate), a phosphorus-based flame retardant, 10 wt% of a melamine-based flame retardant, MCA (melamine cyanurate), a silane-based additive Phosphorus r-Glycidoxypropyl trimethoxy silane A base was prepared by mixing and stirring 2% by weight and the remaining amount of silane coated alumina (filler).

The alkoxysilane-modified epoxy resin is prepared through the following process.

745 g of bisphenol F-type epoxy resin (Kukdo Chemical Co., Ltd., trade name: YDF-170) and 180 g of dimer acid (Fujian Liancheng baixin Science & Technology, trade name BX-18) were added and dissolved at 100°C. Next, 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at a temperature of 120° C. for 3 hours. 75 g of mercaptopropyltrimethoxysilane (Dow Corning, trade name Z-6062) was added thereto, followed by de-methanol reaction at 130° C. for 4 hours to obtain an alkoxysilane-modified epoxy resin.

(2) 15 wt% of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, which is an aliphatic amine, separately from the subject, and 85 wt% of polyoxypropylenediamine was mixed and stirred to prepare a curing agent.

(3) Next, the main agent and the curing agent were mixed in a weight ratio of 1: 0.17 (=6: 1) to prepare an eco-friendly flame-retardant adhesive and molding resin.

[Formula 1-1]

In the above formula, R ¹ is a methyl group, and R ² is an α-mercaptopropyl group.

Examples 2 to 9 and Comparative Examples 1 to 9

In the same manner as in Example 1, the production of an eco-friendly flame-retardant adhesive and molding resin was prepared, but as shown in Table 1 below, the composition ratio of the main agent and the curing agent was changed to prepare the resin, respectively.

division
(weight%) topic hardener topic:
hardener
weight ratio Modified Epoxy Resin taking over
flame retardant melamine
flame retardant silane
additive filler Aliphatic
amine polyoxy
propylene
diamine Example 1 15 2.5 10 2 remaining amount 15 85 1: 0.17 Example 2 19 2.5 10 2 remaining amount 15 85 1: 0.17 Example 3 12 2.5 10 2 remaining amount 15 85 1: 0.17 Example 4 15 1.0 10 2 remaining amount 15 85 1: 0.17 Example 5 15 4.5 10 2 remaining amount 15 85 1: 0.17 Example 6 15 2.5 5 2 remaining amount 15 85 1: 0.17 Example 7 15 2.5 14 2 remaining amount 15 85 1: 0.17 Example 8 15 2.5 10 0.5 remaining amount 15 85 1: 0.17 Example 9 15 2.5 10 4 remaining amount 15 85 1: 0.17 Comparative Example 1 22 2.5 10 2 remaining amount 15 85 1: 0.17 Comparative Example 2 8 2.5 10 2 remaining amount 15 85 1: 0.17 Comparative Example 3 15 - 10 2 remaining amount 15 85 1: 0.17 Comparative Example 4 15 6.0 10 2 remaining amount 15 85 1: 0.17 Comparative Example 5 15 4.0 2 2 remaining amount 15 85 1: 0.17 Comparative Example 6 15 2.5 17 2 remaining amount 15 85 1: 0.17 Comparative Example 7 15 2.5 10 - remaining amount 15 85 1: 0.17 Comparative Example 8 15 2.5 10 6.5 remaining amount 15 85 1: 0.17 Comparative Example 9 15 2.5 10 2 remaining amount 15 85 1: 0.05

Experimental Example 1: Physical property measurement experiment

The hardness, elongation, pot life, flame retardancy and Cl- content of the flame-retardant epoxy resin for bonding and molding prepared in Examples and Comparative Examples were measured, and the results are shown in Table 2 below.

At this time, hardness was measured based on ASTM D2240, elongation was measured based on ASTM D638, and flame retardancy was measured based on UL-94.

division Hardness
(shore A) elongation
(%) housekeeping time
(25℃, 3KG) flame retardant Comparative Example 11
(control group) 43 370% 6 hours 30 minutes non-play Example 1 70 345 6 hours 25 minutes V1 Example 2 72 323 6 hours 05 minutes V1 Example 3 61 356 6 hours 35 minutes V1 Example 4 70 348% 6 hours 20 minutes V1 Example 5 69 339% 6 hours 25 minutes Vo Example 6 70 352% 6 hours 30 minutes V1 Example 7 68 332% 6 hours 30 minutes Vo Comparative Example 1 75 287% 6 hours 00 minutes V1 Comparative Example 2 48 363% 6 hours 45 minutes V1 Comparative Example 3 72 352% 6 hours 10 minutes V2 Comparative Example 4 65 330% 6 hours 30 minutes Vo Comparative Example 5 71 355% 6 hours 30 minutes V2 Comparative Example 6 67 307% 6 hours 30 minutes Vo

In the case of Comparative Example 1 containing the alkoxysilane-modified epoxy resin in an amount of more than 20% by weight of 22% by weight, when compared with Example 2 (19% by weight), the hardness is excellent, but the elongation is rapidly reduced to less than 300% There was a problem, in the case of Comparative Example 2 containing the alkoxysilane-modified epoxy resin at 10% by weight of mimine and 8% by weight, when compared with Examples 1 and 3 (12% by weight), there was a problem that the hardness was too low .

In the case of Comparative Example 3 in which the phosphorus-based flame retardant was not used, when compared with Example 4, the flame retardancy was not good, and in Comparative Example 4, in which the phosphorus-based flame retardant content exceeded 6 wt%, the flame retardancy was excellent However, compared to Example 5 (4.5 wt%), the effect of improving physical properties was insignificant.

And, in the case of Comparative Example 5, in which the content of the melamine-based flame retardant is less than 5.0% by weight of 2% by weight, compared with Example 6 (5% by weight), there is a problem that the flame retardancy is inferior, and the content of the melamine-based flame retardant is 15% by weight In the case of Comparative Example 6 using 17% by weight in excess of %, compared with Example 7 (14% by weight), the effect of improving physical properties was insignificant and the viscosity of the epoxy resin increased rapidly, resulting in poor workability and elongation. There was a problem with a sharp decline.

Experimental Example 2: Underwater Thermal Shock Test

The underwater thermal shock test of the eco-friendly flame-retardant adhesive and molding resins prepared in Examples 1 to 3, Examples 8 to 9 and Comparative Examples 7 to 9 were measured in the following manner, and the results are shown in Table 2 below. it was

(1) Underwater thermal shock test method

After bonding the copper-nickel case with the eco-friendly flame-retardant bonding and molding resin, it was immersed in water at 5° C. for 1 minute, and after 6 seconds, it was immersed in water at 95° C. for 1 minute, and then again in water at 5° C. for 6 seconds. immersed This was measured in 1 cycle. And, the occurrence of separation of the molded epoxy in the copper-nickel case and the occurrence of poor insulation resistance were measured.

In the evaluation of the underwater thermal shock test, if the separation of the epoxy and/or the insulation resistance did not occur on the basis of 1,000 cycles, it was passed, and if it did, it was indicated as fail.

division Whether there is a gap or poor insulation Example 1 pass Example 2 pass Example 3 pass Example 8 pass Example 9 pass Comparative Example 7 fail Comparative Example 8 fail Comparative Example 9 fail

In the case of Comparative Example 7 in which the silane-based additive was not used, there was a problem that the separation occurred due to insufficient adhesive strength, and in Comparative Example 8 using 6.5 wt% in excess of 5 wt% of the silane-based additive, Example 9 ( 4% by weight), there was a problem in that thermal shock properties in water were rather reduced.

In addition, in the case of Comparative Example 9 in which the curing agent was used too little for the main material, the curing rate of the epoxy resin was slow, and there was a problem in that the thermal shock property in water was not good.

Claims (6)

As a two-component epoxy resin comprising a main agent and a curing agent in a weight ratio of 1: 0.1 to 0.3,
The subject is 10 to 20% by weight of an alkoxysilane-modified epoxy resin having an alkoxysilane group represented by the following Chemical Formula 1, 1.0 to 5.0% by weight of a phosphorus-based flame retardant, 5 to 15% by weight of a melamine-based flame retardant, 0.5 to 5.0% by weight of a silane-based additive, and containing the remaining amount of filler,
The curing agent includes 13 to 17% by weight of aliphatic amine and the remaining amount of polyoxy (C ₁ to C ₅ alkylene) diamine,
The filler includes a silane-coated alumina having a D ₅₀ of 40-50 μm,
Flame-retardant epoxy resin for sensor filler with excellent water thermal shock resistance, characterized in that the thermal shock in water is 12,000 cycles or more, and the hardness (Shore A) is 55 to 85;
[Formula 1]

In Formula 1, R ¹ is a linear alkyl group having 1 to 20 carbon atoms or a pulverized alkyl group having 3 to 20 carbon atoms, and R ² is a vinyl group, a glycidoxy group, an acryl group, or a mercapto group having an organic functional group having 1 carbon number. to 4 straight-chain alkyl groups.
According to claim 1, wherein the silane of the silane coated alumina,
Methyltriethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, bis-(tri Ethoxysilylpropyl)tetrasulfide, bis-(triethoxysilylpropyl)disulfide, gamma-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, beta-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldime Toxysilane, mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, octyltriethoxysilane, 3- Chloropropyltriethoxysilane, vinyl-tris-(2-methoxyethoxy)silane, 3-mercaptopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, A flame-retardant epoxy resin for a sensor filler having excellent resistance to thermal shock in water, comprising at least one selected from vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, and n-octadecyltrimethoxysilane.
The method of claim 1, wherein the aliphatic amine is isophorone diamine, 1,3-cyclohexanebis(methylamine), 4,4'-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane, 3 ,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-dianinodicyclohexylmethane, bis(aminocyclohexyl)methane, 1,4-cyclohexanediamine, bis(aminomethyl ) Norbornane, piperazine, aminoethylpiperazine (AEP), 4,4'-methylenebis-(2-methyl-cyclohexanamine) water thermal shock resistance characterized in that it contains at least one selected from the group consisting of Excellent flame retardant epoxy resin for sensor fillers.
delete delete A sensor filler comprising the flame-retardant epoxy resin of any one of claims 1 to 3.

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