KR20180003354A - Thermosetting epoxy resin composition having fast-curing property, low-viscosity and high thermal-resistance - Google Patents

Abstract

The present invention relates to an epoxy resin composition satisfying fast curing properties, low viscosity and high thermal resistance. The epoxy resin composition according to the present invention has rapid curing speed, low viscosity and excellent thermal resistance. Accordingly, the epoxy resin composition can be applied in fields needing to secure production speed and requiring molding availability and thermal properties.

Description

TECHNICAL FIELD [0001] The present invention relates to an epoxy resin composition having a fast curability, a low viscosity, and a high heat resistance,

The present invention relates to an epoxy resin composition which satisfies both fast curability, low viscosity and high heat resistance.

The epoxy resin composition has excellent workability and is excellent in electrical characteristics, heat resistance, adhesiveness, and moisture resistance of cured products and is widely used in the fields of electric and electronic parts, structural materials, adhesives, paints and the like.

Such an epoxy resin composition is required to improve various properties such as fast curability, low viscosity, flame retardancy, and heat resistance according to its use. The epoxy resin composition is composed of a resin having two or more epoxy bonds in the molecule and a curing agent which reacts with the resin, and the physical properties of the epoxy resin composition vary depending on the resin and curing agent used. Accordingly, efforts have been made to obtain an epoxy resin composition having desired properties by controlling the kinds of the resin and the curing agent.

For example, Japanese Laid-Open Patent Application No. 2014-214169 discloses a resin composition comprising an epoxy resin, an acid anhydride, a compound having a hydroxyphenyl structure having an acid dissociation constant of 10.2 or more and 13 or less and an organic phosphorus compound or an imidazole derivative Based epoxy resin composition. However, the composition has a low glass transition temperature of about 115 to 130 占 폚, which is insufficient in heat resistance.

In the case of an epoxy resin composition used for automobile parts and interior and exterior materials, excellent heat resistance is required so that the material properties do not vary depending on molding conditions. Further, in the case of a curved surface shape or a large-sized structural material, a low viscosity property is required in order to ensure ease of molding. Finally, fast curability is essential to improve productivity.

However, an epoxy resin composition satisfying three properties of fast curability, low viscosity and high heat resistance has not yet been developed.

Japanese Laid-Open Patent Application No. 2014-214169, a two-component epoxy resin composition for a fiber-reinforced composite material, and a fiber-

The present inventors have found that a base epoxy resin; Low viscosity epoxy resin; And a polyfunctional or multifunctional epoxy resin; and an epoxy resin composition comprising an amine-based curing agent containing two or more primary amines as a curing agent and containing a boron-based curing accelerator as a curing accelerator And that the composition had a fast curing rate and a low viscosity and exhibited a high glass transition temperature, thereby completing the present invention.

Accordingly, an object of the present invention is to provide an epoxy resin composition that simultaneously satisfies fast curability, low viscosity, and high heat resistance.

In order to accomplish the above object, the present invention provides an epoxy resin composition comprising an epoxy resin, a reactive diluent, an amine curing agent, and a boron curing accelerator, wherein the epoxy resin comprises a basic epoxy resin; Low viscosity epoxy resin; And a multi-functional or multi-functional epoxy resin.

Wherein the epoxy resin composition comprises 5 to 25% by weight of a basic epoxy resin, 5 to 25% by weight of a low viscosity epoxy resin, 20 to 60% by weight of a polyfunctional or multifunctional epoxy resin, 1 to 15% by weight of a diluent, %, And 0.1 to 5 wt% of a curing accelerator.

The epoxy resin composition according to the present invention exhibits a high curing rate, low viscosity, and excellent heat resistance. Therefore, the present invention can be applied to a field where a production speed is required, ease of molding and heat resistance are required.

The epoxy resin composition proposed in the present invention is characterized by having a fast curing property, low viscosity and high heat resistance at the same time, including various compositions, and having a long pot life.

That is, the present invention provides an epoxy resin composition comprising (i) an epoxy resin, (ii) a reactive diluent, (iii) an amine curing agent, and (iv) a boron curing accelerator. Low viscosity epoxy; Resin and a polyfunctional or multifunctional epoxy resin.

The "fast curing property" property of the epoxy resin composition referred to in the present specification means that a rapid curing speed, that is, a short time curing occurs, usually means that the gel time is short. The gelling time means the time taken for the resin to have a fluidity and gradually harden, and the shorter the gelling time, the faster the curing. The epoxy resin composition proposed in the present invention achieves excellent fast curability at 80 DEG C with a gelation time of 50 seconds or less, preferably 40 seconds or less.

The "low viscosity" properties of the epoxy resin compositions referred to herein are related to the handling characteristics and use of the resin, and the lower the viscosity is, the more advantageous it is for application in mass production processes. The viscosity is a value measured at room temperature of 25 占 폚. The epoxy resin composition of the present invention has a viscosity of 3000 cps, preferably 2700 cps or less, and exhibits a low viscosity.

The "high heat resistance" property of the epoxy resin composition referred to in this specification relates to the heat resistance characteristic of the cured product obtained after curing, which means the strength to withstand at high temperatures. The heat resistance of the resin composition can be confirmed by measuring the glass transition temperature, and when the glass transition temperature is high, it means that the heat resistance is high. The epoxy resin composition of the present invention has a glass transition temperature (Tg) of 150 DEG C or more and high heat resistance.

The "pot life" of the epoxy resin composition referred to in the present specification means a usable time after mixing or a usable time after opening, and means a working time based on a room temperature of 25 占 폚. That is, immediately after the raw materials are mixed, reaction occurs between the components, and the viscosity starts to increase and reaches a state that can not be used over time. In this case, the pot life refers to the time until the mixture can be used. Therefore, the longer the housekeeping time is, the better the work is. The epoxy resin composition of the present invention has a pot life of at least 30 minutes and a long pot life.

Each composition will be described in detail below.

(i) an epoxy resin

The epoxy resin composition according to the present invention is characterized by mixing three kinds of epoxy resins.

Specifically, the three kinds of epoxy resins include a first epoxy resin as a basic epoxy resin, a second epoxy resin as a low viscosity epoxy resin, and a third epoxy resin as a multifunctional or multifunctional epoxy resin.

The basic epoxy resin as the first epoxy resin is preferably a bisphenol-based epoxy resin containing a benzene structure and a hydrocarbon side chain, and having two epoxy groups in one molecule. The first epoxy resin that can be used is not particularly limited in the present invention and can be used conventionally in this field.

Preferably, the epoxy equivalent of the first epoxy resin may range from 150 to 400 g / eq, preferably from 150 to 250 g / eq. The weight average molecular weight (Mw) of the epoxy resin may be in the range of 300 to 5,000 g / mol, preferably 300 to 1,000 g / mol, and more preferably 300 to 500 g / mol.

Non-limiting examples of the first epoxy resin include bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol C2 type epoxy resin, bisphenol E type epoxy resin, bisphenol F type Epoxy resin, bisphenol G type epoxy resin, bisphenol S type epoxy resin, bisphenol P type epoxy resin, and bisphenol PH type epoxy resin. Preferably, bisphenol A type liquid epoxy resin or bisphenol F type liquid epoxy resin is used .

Examples of commercially available divalent epoxy resins include YD-128 (bisphenol A basic liquid epoxy resin) and YDF-170 (bisphenol F basic liquid epoxy resin) (manufactured by Kokudo Chemical Co., Ltd.).

The first epoxy resin is used in an amount of 5 to 25% by weight, preferably 7 to 15% by weight, based on 100% by weight of the total epoxy resin composition.

The second epoxy resin has a viscosity of 1,000 to 6,000 cps, preferably 1,000 to 4,000 cps. By including the resin, the epoxy resin composition of the present invention can exhibit low viscosity characteristics. That is, the viscosity of the first epoxy resin is 8000 cps or more, and when the epoxy resin is used alone, there is a problem that the viscosity of the final composition is high, so that impregnation can not be performed during product molding, but this can be solved through the use of the second epoxy resin .

The low viscosity epoxy resin as the second epoxy resin may have an equivalent weight in the range of 150 to 1,000 g / eq, preferably 150 to 250 g / eq. The weight average molecular weight (Mw) of the epoxy resin may be in the range of 300 to 10,000 g / mol, preferably 300 to 1,000 g / mol, and more preferably 300 to 500 g / mol.

The low-viscosity epoxy resin as the second epoxy resin may be a cycloaliphatic epoxy resin, a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a linear aliphatic epoxy resin, An epoxy resin, a heterocyclic ring-containing epoxy resin, a substituted epoxy resin, a naphthalene-based epoxy resin, and derivatives thereof.

The glycidyl ether type epoxy resin includes a glycidyl ether of a phenol and a glycidyl ether of an alcohol, and glycidyl ether of the phenol includes bisphenol A type, bisphenol B type, bisphenol AD type, bisphenol S type , Bisphenol-type epoxy resins such as bisphenol F type and resorcinol, and the like, which may be used alone or in combination of two or more.

The glycidylamine type epoxy resin may be at least one selected from the group consisting of diglycidyl aniline, tetraglycidyl diaminodiphenyl methane, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3 Triglycidyl-m-aminophenol, triglycidyl-p-aminophenol and the like having both a structure of bis (diglycidylaminomethyl) cyclohexane, glycidyl ether and glycidylamine, Two or more species can be used in combination.

The glycidyl ester type epoxy resin may be an epoxy resin made of a hydroxycarboxylic acid such as p-hydroxybenzoic acid or? -Hydroxynaphthoic acid and a polycarboxylic acid such as phthalic acid or terephthalic acid, and may be used alone or in combination of two or more can do.

The linear aliphatic epoxy resin may be a glycidyl ether such as trimethylol propane, pentaerythritol, dodecahydrobisphenol A, dodecahydrobisphenol F, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, They may be used alone or in combination of two or more.

The naphthalene-based epoxy resin may be at least one selected from the group consisting of 1,2-diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1,6-diglycidyl naphthalene, And epoxy resins having a naphthalene skeleton such as diglycidyl naphthalene, triglycidyl naphthalene and 1,2,5,6-tetraglycidyl naphthalene. These epoxy resins may be used alone or in combination of two or more.

An epoxy resin having an epoxycyclohexane ring in the molecule obtained by oxidizing triglycidylisocyanurate and a compound having a plurality of double bonds in the molecule with a second epoxy resin can be used.

Preferably, the second epoxy resin is a bisphenol A type epoxy resin, more preferably an ND type epoxy resin. Examples of the low-viscosity epoxy resin commercially available and commercially available include KES-8128ND (bisphenol A type epoxy resin).

The second epoxy resin is used in an amount of 20 to 60% by weight, preferably 30 to 50% by weight, based on 100% by weight of the total epoxy resin composition. If the content is less than 20% by weight, it is difficult to realize a low viscosity. On the other hand, if the content is more than 60% by weight, excessively low physical properties and a long curing time may occur.

The third epoxy resin uses a polyfunctional or multifunctional epoxy resin. The multifunctional epoxy resin has three or more functional groups, and the multifunctional epoxy resin has two or more functional groups, which promotes the curing of the composition and improves the heat resistance of the cured product. The polyfunctional or multifunctional epoxy resin may have an equivalent weight in the range of 100 to 1,000 g / eq, preferably 150 to 300 g / eq. The weight average molecular weight (Mw) of the epoxy resin may be in the range of 100 to 10,000 g / mol, preferably 100 to 7,000 g / mol, and more preferably 400 to 5,000 g / mol.

The third epoxy resin may be a cycloaliphatic epoxy resin, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a linear aliphatic epoxy resin, Containing epoxy resin, a substituted epoxy resin, a naphthalene-based epoxy resin, a phenol-salicylate aldehyde epoxy resin, a phenol salicylate aldehyde novolac epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, An epoxy resin containing two or more polyfunctional epoxy groups such as an epoxy resin, a polyhydric phenol-type epoxy resin, a tetraphenol-type epoxy resin, and a phenol-dicyclopentadiene epoxy resin. Here, the glycidyl ether type epoxy resin is preferably a bisphenol A type epoxy resin, a bisphenol AP type epoxy resin, a bisphenol AF type epoxy resin, a bisphenol B type epoxy resin, a bisphenol BP type epoxy resin, a bisphenol C type epoxy resin, Epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol P type epoxy resin, bisphenol PH type epoxy resin, bisphenol Z type epoxy resin , And a bisphenol TMC type epoxy resin.

The third epoxy resin in the present invention is preferably a phenol-salicylate aldehyde epoxy resin, a phenol salicylate aldehyde novolak epoxy resin, a phenol novolak epoxy resin, a bisphenol A novolac epoxy resin, a bisphenol AP type epoxy resin, Bisphenol M type epoxy resin, bisphenol Z type epoxy resin, and bisphenol TMC type epoxy resin.

Examples of commercially available polyfunctional epoxy resins include KES-7270 (phenol-salicylaldehyde epoxy resin), KES-3165 (bisphenol A novolac epoxy resin), YDPN-631 (phenol novolak type epoxy resin), YDPN (Cresol novolak type epoxy resin), YDCN-500-5P (cresol novolak type epoxy resin), YDCN-500-4P (cresol novolak type epoxy resin) YDCN-500-80P (cresol novolak type epoxy resin), YDCN-500-90P (cresol novolak type epoxy resin), YDCN- KBPN-110 (bisphenol A (BPA) -novolak type epoxy resin), KBPN-115 (BPA-novolak type epoxy resin), KBPN-120 (BPA-novolak type epoxy resin) ), KDMN-1065, KDCP-130 (dicyclopentadiene (DCPD) type epoxy resin) (manufactured by Kukdo Chemical Co., Ltd.).

For example, amine epoxy resins of the following formulas (1) and (2) or phenol novolac epoxy resins of the formula (3) may be used as the third epoxy resin.

[Chemical Formula 1]

(2)

(3)

(Wherein R is a methyl group, an ethyl group, or a propyl group, and n is an integer of 1 to 10)

The third epoxy resin is used in an amount of 10 to 40% by weight, preferably 10 to 30% by weight, based on 100% by weight of the whole epoxy resin composition. If the content is less than 10% by weight, rapid curing and high heat resistance can not be attained. On the other hand, when the content exceeds 60% by weight, the viscosity increases and the impregnation property is lowered and the curing rate is difficult to control. Use properly within the range.

As described above, the first component (i) of the present invention is a first epoxy resin, which is a basic epoxy resin, a second epoxy resin which is a low viscosity epoxy resin, a third epoxy resin which is a polyfunctional or multifunctional epoxy resin When using resins in combination, fast curing, low viscosity and high heat resistance properties can be achieved.

(ii) a reactive diluent

The epoxy resin composition according to the present invention comprises a reactive diluent.

The reactive diluent is used for the purpose of decreasing the viscosity of the epoxy resin to improve the flowability, defoaming property and permeability. The reactive diluent has high compatibility with the epoxy resin and boiling point and can be used without limitation as long as it is commonly used in the art.

For example, the reactive diluent may be selected from the group consisting of butyl glycidyl ether (BGE), aliphatic glycidyl ether (LGE, C12 to C14), 2-ethylhexyl glycidyl ether (EHGE), phenyl glycidyl ether (PGE) , o-cresol glycidyl ether (CGE), 1,4-butanediol diglycidyl ether (1,4BDGE), 1,6-hexanediol diglycidyl ether (1,6HDDGE), neopentyl glycol diglycidyl (NPGDGE), 1,4-cyclohexanedimethanol diglycidyl ether (CHDMDGE), polypropylene glycol diglycidyl ether (PPEDGE), ethylene glycol diglycidyl ether (EGDGE) and resorcinol And diglycidyl ether (RDGE).

The reactive diluent is used in an amount of 1 to 15% by weight, preferably 5 to 15% by weight, based on 100% by weight of the total epoxy resin composition. If the content is less than 1% by weight, the viscosity is not affected and the impregnability is poor. On the contrary, when the content exceeds 20% by weight, the physical properties of the cured product are excessively lowered. use.

(iii) Amine system  Hardener

The epoxy resin composition according to the present invention uses an amine-based curing agent as a curing agent. Preferably, the amine-based curing agent comprises two primary amines in the molecular structure.

In the epoxy resin composition, physical properties of the curing agent differ depending on the kind of the curing agent, and conventionally used acid anhydride-based curing agents, phenol-based curing agents, and imidazole-based curing agents have a problem of poor fast curability. In the present invention, fast curing properties of the epoxy resin composition are secured by including the amine curing agent as described above.

Examples of the amine-based curing agent include aliphatic amines, polyether polyamines, alicyclic amines, aromatic amines and the like. Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, Hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, and the like. The polyether polyamines may be one of triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and mixtures thereof. Examples of the alicyclic amines include isophoronediamine, 4,4-methylenebis (2-methylcyclohexylamine), 4,4-methylenebiscyclohexylamine, methadecenediamine, N-aminoethylpiperazine, bis 3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, Nandiamine, and the like. Examples of the aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4- , 4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4- Phenylsulfone, and mixtures thereof. Preferably, at least one selected from the group consisting of hexamethylenediamine, isophoronediamine, 4,4-methylenebis (2-methylcyclohexylamine), 4,4-methylenebiscyclohexylamine, bis (aminomethyl) cyclohexane, and norbornenediamine May be used.

The amine-based curing agent is used in an amount equivalent to an equivalent ratio of epoxy resin (epoxy rings in the first, second and third epoxy resins) of 1: 1 in view of the equivalent amount of the epoxy resin. Preferably, 5 to 40% by weight, preferably 5 to 30% by weight, based on 100% by weight of the total epoxy resin composition is used. If the content is less than 5% by weight, the curing is insignificant and rapid curing can not be achieved, and the physical properties of the finally obtained epoxy cured product (for example, coating film) are lowered. On the other hand, Since the hardness and physical properties of the cured product are lowered and the control of the curing rate is not easy, it is suitably used within the above range.

(iv) Boron system  Hardening accelerator

Particularly, the epoxy resin composition according to the present invention uses a boron-based curing accelerator as a curing accelerator.

The curing accelerator is used for fast curing and low-temperature curing, and includes an imidazole-based curing accelerator, an amine-based curing accelerator, a phosphorus-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator. However, when the boron-based curing accelerator is used as in the present invention, the curing accelerator does not show a decrease in the glass transition temperature and the curing speed is lowered There is an advantage to increase.

The type of the boron-based curing accelerator is not particularly limited, and examples thereof include triphenylphosphine tetraphenyl borate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboron monoethylamine, trifluoroboron And may be at least one member selected from the group consisting of lanthanum ethyl ether, trifluoroborane phenolate tetrafluoroborane triethylamine, and tetrafluoroborane amine. Preferably, a trifluoroborane series such as trifluoroboran-n-hexylamine, trifluoroborane monoethylamine, trifluoroborane diethyl ether, and trifluoroborane phenolate is used.

The boron-based curing accelerator is used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on 100% by weight of the total epoxy resin composition. If the content is less than 0.1% by weight, rapid curing can not be achieved. On the other hand, if the content is more than 10% by weight, it is difficult to control the curing rate.

(v) Other additives

In addition, the epoxy resin composition according to the present invention may further include known additives conventionally used in this field.

It is also possible to add further additives such as fillers, defoamers, leveling agents, adhesion promoters, antioxidants, colorants, light stabilizers, ultraviolet absorbers, thermosetting agents, lubricants, defoamers, dispersants, antistatic agents, plasticizers, organic fillers, . At this time, the content of the additive may be changed according to the user's selection within a range that does not change the physical properties required by the epoxy resin composition of the present invention, for example, 0.1 to 15% by weight based on the total epoxy resin composition.

For example, the main purpose of the filler is to improve the mechanical properties of the resin, and generally, the mechanical properties are improved when the addition amount is increased. It has special applications such as talc, sand, silica, talc, calcium carbonate, reinforcing filler such as mica, quartz, glass fiber, quartz powder, graphite, alumina and aerosil Examples of the metallic material include those which contribute to thermal expansion coefficient, abrasion resistance, thermal conductivity and adhesiveness of aluminum, aluminum oxide, iron, iron oxide and copper and those which impart flame retardancy such as antimony oxide (SB ₂ O ₃ ) , And organic materials include lightweight fillers such as fine plastic spheres (phenol resin, urea resin, etc.)

In addition, a typical product that can be used as the antifoaming agent may be selected from among TEGO Airex 920, 932, BYK 088, and 1790, but is not limited thereto.

As a representative product that can be used as a leveling agent, one of TEGO Glide 410, 440, TEGO Rad 2250, BYK-UV 3500, 3510 can be selected but is not limited thereto.

As the adhesion promoter, an acrylic phosphate-based adhesion promoter such as hydroxyethyl acryloyl phosphate, hydroxyethyl methacrylate phosphate or the like is preferably used, but not limited thereto.

Examples of the antioxidant include Irganox 1010, Irganox 1035, Irganox 1076 and Irganox 1222 (Shiba Gagai, Japan). Examples of the light stabilizer include Tinuvin 292, Tinuvin 144, Tinuvin 622LD Tinuvin P, Tinuvin 234, Tinuvin 320, and Tinuvin 328 (Shiba Gagai, Japan), Sumisorb (Japan), and the like were used as the ultraviolet absorbers. HQ, THQ, and HQMME are preferred as the thermal polymerization inhibitor, and the smoothing agent, defoaming agent, and dispersing agent may be BYK (trade name, manufactured by BYK, etc.) But it is not limited to this.

Pigments or dyes are used to color the resin. Commonly used pigments include titanium dioxide, cadmium red, shading green, carbon black, chrome green, chrome yellow, navy blue, shining blue, and many other coloring agents. Some of these colorants may react with the resin, the cured hue may be discolored at the time of curing, and some may affect the physical properties of the resin.

Examples of the antistatic agent include antioxidants such as polyoxyethylene alkyl ethers, polyoxyethylene amines, glycerin and sorbitol fatty acid esters, and anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfates, and alkyl phosphates, Quaternary ammonium salts or mixtures thereof.

The production of the epoxy resin composition according to the present invention including the above-mentioned composition is not particularly limited in the present invention, and a method commonly used in this field can be used. In an embodiment of the present invention, an epoxy resin and a reactive diluent are mixed while heating, and then a mixture of a curing agent and a curing accelerator is added to prepare an epoxy resin composition.

The epoxy resin composition thus prepared exhibits a low viscosity at a viscosity of from 700 to 3000 cps at 25 DEG C and a fast curing property at a gelling time of from 30 to 40 seconds at 80 DEG C. [ The glass transition temperature is 150 占 폚 or higher, preferably 160-175 占 폚, and has a high heat resistance.

In addition, such an epoxy resin composition exhibits a pot life of 30 minutes or more, which is advantageous in securing a working time.

Usage

The epoxy resin composition according to the present invention can be applied to various fields.

For example, in the field of sealing semiconductor devices in the electric and electronic fields, in the fields of insulating resin sheets such as adhesive films and prepregs, circuit boards, solder resists, underfills, die bonding materials, component replenishing resins, Flooring, road, waterproofing, grouting, and the like. Also, it can be used as general adhesives, fillers, abrasives, and coatings, and can be applied as a resin mold, a winding, a metal plate coating, an accessory coating, a general coating material such as automobile, electric gas appliance, and mechanical steel.

Preferably, the epoxy resin composition of the present invention can be used as a coating composition, wherein the composition satisfies fast curability, low viscosity and high heat resistance, and exhibits a long pot life, thereby facilitating the work. Thus, it is possible to form an epoxy coating film excellent in heat resistance.

The coating method for forming the epoxy coating may be a coating method such as dip coating, spray coating, roll coating or bar coating commonly used in the art. The thickness of the coated coating is preferably 0.5 to 10 Mu m.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[Example]

Example  1 to 6 and Comparative Example  1 to 6: Preparation of epoxy resin composition

Using the following raw materials, an epoxy resin composition was prepared with the compositions shown in Tables 1 and 2.

Specifically, the epoxy resin and the reactive diluent were mixed at 100 DEG C for 2 hours to visually confirm that the raw material was completely dissolved, and then cooled to room temperature to obtain a mixture. Then, a mixture of a curing agent and a curing accelerator was added to the mixture to prepare an epoxy resin composition. The materials used here are as follows:

(A) an epoxy resin

First Epoxy Resin: YD-128 (bisphenol A type epoxy resin, epoxy equivalent 189 g / eq)

Second epoxy resin: KES-8128ND (bisphenol A type epoxy resin, epoxy equivalent 175 g / eq, viscosity 3000 cps)

Third epoxy resin: KES-7270 (phenol-salicylaldehyde epoxy resin, epoxy equivalent 170 g / eq, three functional groups), KES-3165 (bisphenol A novolac epoxy resin, epoxy equivalent 215 g / Three)

(B) Thinner

1,4-BDGE: 1,4-butanediol diglycidyl ether

(C) an amine-based curing agent

DETA: Diethylene triamine

IPDA: isophorone diamine

BAHA: bis (aminomethyl) cyclohexane

(D) Curing accelerator

BPA: bisphenol A

1MI: 1-methylimidazole

BF3MEA: boron trifluoride monoethylamine

BF3DEE: boron trifluoride diethylamine

Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Epoxy
Suzy The first epoxy resin YD-128 12 12 12 12 12 12 The second epoxy resin KES-8128ND 47 47 35 47 47 35 The third epoxy resin KES-3165 12 12 12 KES-7270 12 12 12 12 12 diluent 1,4-BDGE 8 8 8 8 8 8 Hardener DETA IPDA 20 BAHA 20 20 20 20 20 Hardening accelerator BPA 1MI BF3MEA One One One One 0.5 BF3DEE One 0.5

Composition (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Epoxy
Suzy The first epoxy resin YD-128 71 59 59 20 12 12 The second epoxy resin KES-8128ND 12 47 47 35 The third epoxy resin KES-3165 12 KES-7270 12 12 12 12 diluent 1,4-BDGE 8 8 8 8 8 Hardener DETA 20 IPDA BAHA 20 20 20 20 20 Hardening accelerator BPA 0.5 1MI 0.5 BF3MEA One One One One One BF3DEE

Experimental Example  1: Measurement of physical properties

The epoxy resin compositions prepared in the above examples and comparative examples were measured on the basis of physical properties and the results obtained are shown in Table 3.

(1) Measurement of viscosity and pot life

100 g each of the epoxy resin compositions prepared in the above Examples and Comparative Examples were placed in a wide-mouth flask or a beaker to prepare test pieces for measuring viscosity and pot life.

The viscosity of the test piece was measured with a Brook-Filed viscometer (10 rpm, Sp # 4 condition) under conditions of 25% RH and 50% RH, and the time of doubling the initial viscosity was measured to measure the pot life. . In this case, the unit of viscosity is cps, and the unit of potlife is min (min).

(2) Gelling  Measuring Gel Time

After thoroughly mixing the epoxy resin and the curing agent on a hot plate of 80, take out 1 g of the sample and measure the time. Stir with a Teflon bar and raise it until the resin is stretched to the side of the thread The time was measured. In Table 3 below, the unit of gelling time is seconds.

(3) Glass transition temperature ( Tg ) Measure

DSC 2010 and DSC 2910 from TA Instruments Co., Ltd. About 5 mg of sample was heated to 300 캜 at a rate of 10 캜 / min by a DSC measuring machine and then cooled to 30 캜 at a rate of 10 캜 / min. This first heating / cooling process was carried out twice in the same process.

Viscosity (cps) Gelation time (s) Housework time Tg (占 폚) Example 1 820 33 33min 173.3 Example 2 1050 32 30min 165.9 Example 3 2590 35 31min 169.4 Example 4 820 38 34 min 163.1 Example 5 820 39 33min 171.5 Example 6 1350 39 31min 171.9 Comparative Example 1 5900 35 18min 151.6 Comparative Example 2 32000 39 27min 165.4 Comparative Example 3 2900 41 29min 152.5 Comparative Example 4 21500 43 30min 174.5 Comparative Example 5 820 42 30min 135.7 Comparative Example 6 1850 56 45min 121.9

Referring to Table 3 above, it can be seen that the epoxy compositions of Examples 1 to 6 achieve a low viscosity with a viscosity of 850 to 2590 cps. Also, the gelation time was 40 seconds or less, the pot life was 30 minutes or more, and the Tg was at least 163 ° C or more. From these results, it can be seen that the epoxy resin composition according to the present invention satisfies fast curability, low viscosity and high heat resistance at the same time.

In comparison, when the low viscosity epoxy resin is not used as in Comparative Examples 1 and 3, it can be seen that the viscosity exhibits a high viscosity at 5900 cps and 3300 cps.

In addition, it can be seen that the composition of Comparative Example 3 in which the polyfunctional or multifunctional epoxy resin is not used has a Tg of 152 deg. C and a low heat resistance.

From the above results, it can be seen that it is important to blend each component at an appropriate ratio in order to simultaneously realize the viscosity characteristic, the quick curing characteristic and the high heat resistance characteristic. In addition, the epoxy resin composition of the present invention secures these properties and exhibits a long pot life, indicating that it is possible to form a coating film having excellent workability and excellent heat resistance.

Claims (10)

An epoxy resin, a reactive diluent, an amine curing agent and a boron curing accelerator,
The epoxy resin may be a basic epoxy resin; Low viscosity epoxy resin; And a polyfunctional or multifunctional epoxy resin. The method according to claim 1,
The basic epoxy resin has a weight average molecular weight of 300 to 5,000 g / mol and an epoxy equivalent of 150 to 400 g / eq; The low viscosity epoxy resin has a viscosity of 1,000 to 6,000 cps, a weight average molecular weight of 300 to 10,000 g / mol and an epoxy equivalent of 150 to 1,000 g / eq; The polyfunctional or multifunctional epoxy resin preferably has three or more functional groups, a weight average molecular weight of 100 to 10,000 g / mol, an epoxy equivalent of 100 to 1,000 g / eq; And an epoxy resin. The method according to claim 1,
The basic epoxy resin is preferably a bisphenol A type epoxy resin, a bisphenol B type epoxy resin, a bisphenol BP type epoxy resin, a bisphenol C type epoxy resin, a bisphenol C2 type epoxy resin, a bisphenol E type epoxy resin, a bisphenol F type epoxy resin, An epoxy resin, a bisphenol S type epoxy resin, a bisphenol P type epoxy resin, and a bisphenol PH type epoxy resin. The method according to claim 1,
The low viscosity epoxy resin may be a cycloaliphatic epoxy resin, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a linear aliphatic epoxy resin, Wherein the epoxy resin composition is at least one selected from the group consisting of a recycled-containing epoxy resin, a substituted epoxy resin, a naphthalene-based epoxy resin, and derivatives thereof. The method according to claim 1,
The polyfunctional or multifunctional epoxy resin may be a cycloaliphatic epoxy resin, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a linear aliphatic epoxy A phenol-salicylate aldehyde epoxy resin, a phenol salicylate aldehyde novolak epoxy resin, a phenol novolac epoxy resin, a cresol novolak epoxy resin, a bisphenol-based epoxy resin, Wherein the epoxy resin composition is at least one selected from the group consisting of A-type novolak epoxy resin, polyhydric phenol-type epoxy resin, tetraphenol-type epoxy resin and phenol-dicyclopentadiene epoxy resin. The method according to claim 1,
The epoxy resin composition
5 to 25% by weight of a basic epoxy resin
20 to 60% by weight of a low viscosity epoxy resin,
10 to 40% by weight of a multifunctional or multifunctional epoxy resin,
1 to 15% by weight of a reactive diluent,
5 to 30% by weight of an amine-based curing agent, and
0.1 to 5% by weight of a boron-based curing accelerator. The method according to claim 1,
Wherein the amine-based curing agent comprises two or more primary amino groups in the molecular structure. The method according to claim 1,
The amine-based curing agent is selected from the group consisting of hexamethylenediamine, isophoronediamine, 4,4-methylenebis (2-methylcyclohexylamine), 4,4-methylenebiscyclohexylamine, bis (aminomethyl) cyclohexane and norbornene A diamine, and a diamine. The method according to claim 1,
The boron-based curing accelerator may be selected from the group consisting of triphenylphosphine tetraphenyl borate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboron monoethylamine, trifluoroborane diethylether, Wherein the epoxy resin composition is at least one selected from the group consisting of tetrafluoroborane triethylamine, tetrafluoroborane triethylamine, tetrafluoroborane amine, and tetrafluoroborane amine. The method according to claim 1,
Wherein the epoxy resin composition has a viscosity at 25 DEG C of 700 to 3000 cps, a gelation time at 80 DEG C of 50 seconds or less, and a glass transition temperature of 150 DEG C or more.