KR20230102422A - Epoxy foam composition containing a carboxyl group for manufacturing a ship structure and a ship structure formed therefrom - Google Patents

Abstract

The present invention is a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof, c) a silicone compound containing a silicon hydrogen compound , d) a reactive surfactant, and e) a filler; And an amine-based and polyamide-based curing agent including an ionomer, a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent; including, wherein the content of carboxyl groups in the main component is 15 to 30% It provides an epoxy foaming composition containing a carboxyl group for manufacturing a characterized ship structure.
The epoxy foaming composition containing a carboxyl group for manufacturing a ship structure of the present invention has excellent weather resistance while satisfying enhanced mechanical properties by including a curing agent, a silicone compound, and a filler of a specific composition in an epoxy resin. In addition, it has a uniform close-cell structure and can be cured at room temperature (24 ° C), so there is no need for additional curing equipment.

Description

Epoxy foam composition containing a carboxyl group for manufacturing a ship structure and a ship structure formed therefrom}

The present invention relates to an epoxy foam composition containing a carboxyl group for manufacturing a ship structure and a ship structure formed therefrom, and more particularly, a carboxyl group for manufacturing a ship structure that provides structural rigidity, light weight, vibration and noise shielding functions. It relates to an included epoxy foam composition and a ship structure formed therefrom.

It is known that many industries, for example the automotive industry, require components that are both strong and light. In an effort to strike this balance between strength and minimal weight, hollow parts built from relatively thin metal sheets are used. However, hollow metal parts are easily deformed. Accordingly, it is also known that the presence of structural foam in the cavities of hollow parts can improve the strength and rigidity of such parts. For flat parts of automobile bodies such as doors, roofs, trunk lids or bonnets, it is known to increase the stiffness and rigidity of these parts by bonding to them sheets based on foamed or non-foamed epoxy or polyurethane resins. there is.

The specific manufacturing method of the foam structure is very diverse. For example, U.S. Patent No. 5,575,526 teaches a structured foam based on various resins, including recipe 2, which contains 54.5% EPON 828 epoxy resin, 7.5% HALOXY 62 epoxy diluent, 6.1% DER 732 Flexible Epoxy, 2.0% EXPANCEL 551DU blowing agent, 8.8% MICROS microspheres, 17.7% 3M K20 microspheres and 3.4% DI-CY dicyandiamide hardener. U.S. Patent No. 5,755,486 discloses materials based on thermally expandable resins, which materials include, for example, epoxy resins, acrylonitrile-butadiene rubber, calcium carbonate, carbon black, fumed silica, and glass spheres. , curing agents, accelerators and blowing agents.

In the case of such an epoxy foam structure, various problems are scattered, but the biggest problem is that it has a relatively short shelf life. Ideally, the components of such a recipe, once associated with each other, should remain stable, should not react under conditions normally encountered during storage and loading, and should not react when stored at room temperature or higher for weeks or months. It is desirable that the properties of do not change.

Another problem of the epoxy foam structure is that it does not satisfy basic mechanical properties, especially strength, and it is difficult to control foaming. . This is due to the nature of the epoxy resin, and it has poor miscibility with fillers or other polymer resins, especially non-polar polymer resins, and changes in shrinkage against stress during curing and thermodynamic correlation with epoxy foam, which is a thermosetting resin. It seems to be due to the occurrence of disharmony, which adversely affects the mechanical properties.

US Patent Publication No. 5,575,526 (May 18, 1994)

In order to solve the above problems, an object of the present invention is to provide an epoxy foaming composition containing a carboxyl group for manufacturing a ship structure.

In addition, an object of the present invention is to provide a ship structure formed from the composition.

In addition, an object of the present invention is to provide an epoxy foam cured product containing a carboxyl group for manufacturing a ship structure.

In order to achieve the above object, the present invention,

a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof, c) a silicone compound containing a silicon hydrogen compound, d) a reactive surfactant, and e) a main material comprising a filler; and

An amine-based and polyamide-based curing agent containing an ionomer, and a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent;

Provides an epoxy foaming composition containing a carboxyl group for manufacturing a ship structure having a carboxyl group content of 15 to 30% of the main component.

In addition, in order to achieve the above other object, the present invention provides a ship structure formed from the composition.

In addition, in order to achieve the above another object, the present invention provides a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin comprising a mixture thereof, c ) a main material containing a silicone compound containing a silicon hydrogen compound, d) a reactive surfactant, and e) a filler; And An amine-based and polyamide-based curing agent containing an ionomer, a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent; As an epoxy foam cured product cured by mixing a two-component composition comprising,

The composition is mixed with 20 to 50 parts by weight of the curing agent based on 100 parts by weight of the main material,

Provided is an epoxy foam cured product for manufacturing a ship structure having a compressive strength of 500 to 700 psi.

The epoxy foaming composition containing a carboxyl group for manufacturing a ship structure according to the present invention satisfies enhanced mechanical properties by including a specific composition of a curing agent, a silicone compound, and a filler in an epoxy resin and has a specific gravity of 0.17 g/cc to 0.25 g/cc lightweight epoxy. It has characteristics that can be used as a lightweight filler or core-material with high strength when applied to a hollow structure (BODY-SHELL structure) in a ship structure and marine composite material structure by obtaining a foamed cured product.

It is thermodynamically stable, and it is possible to manufacture a foam molding at room temperature (24 ℃), so there is no need for additional curing equipment for curing the epoxy foam.

In addition, it has a uniform close-cell structure, has improved water resistance compared to, for example, urethane foam cured products, and has characteristics of reducing the production of environmentally harmful substances by generating foam gas by itself through chemical reactions.

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

According to one aspect of the present invention, a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof, c) a silicone hydrogen compound a main material including a silicone compound containing; d) a reactive surfactant; and e) a filler; And an amine-based and polyamide-based curing agent including an ionomer, a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent; a ship having a carboxyl group content of 15 to 30% among the main components Provided is an epoxy foaming composition containing a carboxyl group for manufacturing a structure.

In the present invention, the first epoxy resin is a thermosetting resin having one or a plurality of epoxy groups, and contains not only an epoxy group but also one or a plurality of functional groups to induce chemical bonding with other compositions to increase the miscibility of the composition and mechanical properties of the foam. do The epoxy resin is also called polyepoxide, and in principle may be a saturated, unsaturated, cyclic or acyclic aliphatic, alicyclic, aromatic or heterocyclic polyepoxide. Examples of polyepoxides may include polyglycidyl ethers produced by reaction of epichlorohydrin or epibromohydrin or polyphenols in the presence of an alkali.

Examples of the polyphenol include resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis(4-hydroxyphenyl)-2,2-propane), bisphenol F (bis(4-hydroxyphenyl)methane) ), bis(4-hydroxyphenyl)-1,1-isobutane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane and 1,5-hydroxy oxynaphthalene and the like, among which polyphenols of the bisphenol A type or the bisphenol F type can be used as a base to improve the heat resistance, impact resistance and moisture resistance of the foam, and are therefore preferable.

Another polyepoxide is a combination of polycarboxylic acids or polyglycidyl esters of hydroxycarboxylic acids, such as glycidol or epichlorohydrin, with aliphatic or aromatic polycarboxylic acids, such as oxalic acid, succinic acid, glue from the reaction products of tartaric acid, phthalic acid, tetrahydrophthalic acid, terephthalic acid, dimer fatty acids or p-hydroxybenzoic acid or beta-hydroxy naphthoic acid, or from the epoxidation products of olefinically unsaturated cycloaliphatic compounds, or from natural oils and fats or It is derived from synthetic polyolefins. Other suitable polyepoxides include glycidylated aminoalcohol compounds and aminophenol compounds, hydantoin diepoxides and urethane-modified epoxy resins.

The epoxy resin as described above may include one or more functional groups. As described above, the epoxy resin having a functional group may lower the viscosity of the composition and impart amorphousness, and may function as a reactive diluent by increasing miscibility with other non-polar or polar compositions.

The multifunctional epoxy resin may have one or more, more preferably two or more functional groups in one unit structure constituting a repeating unit. Examples of the functional group include a hydroxy group, an alkoxy group, a halogen group, an aldehyde group, a carbonyl group, a carboxyl group, an amine group, a nitrile group, a nitro group, an amide group, and an imide group, and these may be used alone or in combination of two or more.

The viscosity of the multifunctional epoxy resin may be 2,000 to 20,000 cPs at 25 ° C, preferably 8,000 to 15,000 cPs, more preferably 11,500 to 13,500 cPs It is preferable in terms of workability and miscibility. In addition, the epoxy equivalent may be 100 to 700 g / eq, more preferably 150 to 350 g / eq is preferable because heat resistance, impact resistance, moisture resistance, etc. of the coating film can be maintained.

In addition, the foaming composition may further include one or more epoxy resins to supplement heat resistance, impact resistance, and flexibility in addition to the multifunctional epoxy resin. In the present invention, the first epoxy resin is mixed with a second epoxy resin including a bisphenol-based epoxy or modified epoxy resin, and a mixture thereof.

The bisphenol-based epoxy resin in the present invention is mixed in a liquid form to increase miscibility with the composition, and especially to increase miscibility with other compositions and prevent pinholes in the composition to increase mechanical strength, so low viscosity, specifically 25 ° C. 8,000 to 20,000 cPs, preferably 12,000 to 15,000 cPs.

The bisphenol-based epoxy resin may have a structure represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ may each independently be hydrogen or a (C1-C10)alkyl group, specifically methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, isopentyl, A neopentyl group or a tert-pentyl group.

In the present invention, the modified epoxy resin is intended to greatly increase the flexibility, which is a disadvantage of the epoxy resin, to improve mechanical properties, especially when modified with raw materials containing CARBOXYL GROUP and EPOXY compounds containing CARBOXYL GROUP, Free rotation movement is improved, which can increase flexibility. At this time, DIMER FATTY ACID MODIFIESD EPOXY (dimer acid modified epoxy), Kukdo Chemical YD-172, YD-171, EPIKOTE KER-872, HUNTSMAN HyPox DA-323, DIMER FATTY ACID, MONOMER FATTY ACID, CTBN MODIFIED EPOXY, ATBN MODIFIED EPOXY, ETBN MODIFIED EPOXY, VTBNX MODIFIED EPOXY, CTBN, ATBN, ETB, VTB, PTBN and HTBN can be used, and these modified epoxy resins act as plasticizers in the composition to improve physical properties such as flexibility and water resistance. can be granted. Specifically, the modified epoxy resin has a viscosity of SEMI-SOLID at 25 ° C and an epoxy equivalent weight (EEW) of 350-400 g / eq, and in particular, in the case of dimer acid-modified epoxy, the viscosity is 350 to 1000 cPs, preferably 600 to 800 cPs , or SEMI-SOLID.

The first epoxy resin and the second epoxy resin in the present invention are preferably included in 80 to 90% by weight of 100% by weight of the total main material. At this time, the content of carboxyl among the main components including the first epoxy resin and the second epoxy resin accounts for 15 to 30%.

When added below the above range, the mechanical properties of the composition may be reduced, and when the above range is exceeded, the flexibility of the composition may deteriorate, resulting in miscibility with other compositions.

In the present invention, the silicone compound containing silicon hydride shows high reactivity with the functional group of the epoxy resin, and in particular, the composition can be foamed by generating hydrogen or combustible gas through a hydroxyl group.

Examples of the silicone compound include organosilanes, organosilazanes, polymethylsiloxanes, organohydrogenpolysiloxanes, and organosiloxane oligomers. Specifically, organosilanes such as trimethylchlorosilane, dimethylchlorosilane, and methyltrichlorosilane chlorosilanes; organic trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, and n-propyltrimethoxysilane; diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxysilane; triorganoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; partial condensates of these organoalkoxysilanes; organosilazanes such as hexamethyldisilazane; Polymethylsiloxane, organohydrogenpolysiloxane, organosiloxane oligomers having a silanol group or alkoxy group may be used, but are not limited thereto, and organosilazanes, polymethylsiloxanes, and organosiloxane oligomers are preferred. Preferably it is polymethylsiloxane.

The polymethylsiloxane is a polymer containing a methyl group and hydrogen along the siloxane chain and is usually used as a variety of coating and treatment agents such as softeners and waterproofing agents, but reacts with alcohol, aldehydes, ketones, olefins, acids, acid catalysts, bases, etc. same gas can be produced. In addition, the polymethylsiloxane is a siloxane chain in which highly inflammable by-products such as Me3SiH, Me2SiH2, and MeSiH3 are formed according to the characteristics of the siloxane main chain even in the absence of moisture when an acid or base catalyst (eg, Lewis acid or base, clay, etc.) is present. Redistribution of occurs, and through this, an ignitable gas such as silane gas (SiH4) is generated, causing foaming of the composition.

In the present invention, the silicon compound containing silicon hydride preferably contains 3 to 10% by weight based on 100% by weight of the total main composition. When the silicone compound is added below the above range, foaming of the composition may be insufficient, and when the silicone compound is added above the above range, an uncontrolled exothermic reaction may occur, resulting in deterioration of the epoxy resin.

In the present invention, the surfactant is for imparting properties such as lowering of surface tension, wetting, emulsifying, solubilization, dispersibility, and foaming of the composition, and in particular, controlling the size, structure, density, etc. of the cell by dispersing the silicone compound mixed together play a role

In the present invention, it is preferable to use a reactive surfactant among various surfactants as the surfactant. Since the reactive surfactant as described above contains a functional group capable of reacting during curing of the composition, it also acts as a monomer during the curing process to reduce the amount of the surfactant remaining after polymerization, so that it can be manufactured into a foam having more improved mechanical properties. .

Reactive surfactants as described above are mainly composed of alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, and pentyl groups, aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, and anthryl groups, aralkyl groups, and arylene groups. It may contain a hydrophilic group such as a hydrophobic group such as an alkoxy group, a hydroxyl group, or an epoxy group. Examples of such reactive surfactants include silicone surfactants, polyethylene glycol, polypropylene glycol, dodecyl polyoxyethylene ether, tridecyl polyoxyethylene ether, alkyl polyglycoside, alkyl phenol ethoxylate, benzyl alcohol, n- Butyl glycidyl ether, polyoxyethylene alkyl ether, sulfosuccinic acid ester salt of polyoxyethylene alkyl ether, sulfuric acid ester salt of polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene phenyl ether sulfosuccinic acid ester salt, Sulfuric acid ester salt of polyoxyethylene phenyl ether, polyoxyethylene alkylphenyl ether, sulfosuccinic acid ester salt of polyoxyethylene alkylphenyl ether, sulfuric acid ester salt of polyoxyethylene alkylphenyl ether, polyoxyethylene aralkylphenyl ether, polyoxyethylene Sulfosuccinic acid ester salt of ethylene aralkyl phenyl ether, sulfuric acid ester salt of polyoxyethylene aralkyl phenyl ether, phosphoric acid ester salt of polyoxyethylene alkyl phenyl ether, aliphatic or aromatic carboxylate salt of polyoxyethylene alkyl phenyl ether, acidic phosphoric acid (meth)acrylic acid ester type emulsifiers and acid anhydride modified products of rosin glycidyl ester acrylate; and the like. Among them, it is most preferable to use alkyl glycidyl ethers, alkyl phenol ethoxylates, benzyl alcohol, polyethylene glycol, polypropylene glycol, and silicone surfactants from the viewpoint of emulsification.

In the present invention, the surfactant is preferably included in an amount of 1 to 10% by weight based on 100% by weight of the total main composition. When the surfactant is added in less than the above range, the fluidity of the composition is lowered and mixing is not performed properly, and when the surfactant is added in excess of 10% by weight, a rapid curing reaction occurs simultaneously with mixing of the composition due to excessive reactivity, resulting in greatly reduced moldability. can

In the present invention, the filler serves to improve the mechanical properties and heat resistance of the foam, and promotes the foaming action through a reaction with the above-mentioned silicone compound. Examples of such fillers include calcium carbonate, calcium oxide, talc, coal tar, carbon black, glass fibers, carbon fibers, silicates, mica, powdered quartz, aluminum oxide, bentonite, wollastonite, kaolin, fumed silica and silica aerogels. and the like, and these may be used alone or in combination of two or more.

More preferably, fumed silica is used as the filler. The fumed silica has a structure in which a large number of hydroxyl groups are arranged on the surface of silicon and improves low brittleness, which is the biggest disadvantage of epoxy resins. At the same time as improving the mechanical properties, the silanol group on the surface reacts with the silicon compound to promote the generation of foaming gas.

In addition to the above components, the filler may include various inorganic or organic particles used as thixotropic agents or rheological modifiers. For example, organic or inorganic fibers such as wollastonite fibers, carbon fibers, ceramic fibers, aramid fibers, phenolic resins, epoxy resins, or polyester-based hollow beads, (meth)acrylic acid ester copolymers, polystyrene, styrene/ Microparticles of polymers such as (meth)acrylate copolymers and, in particular, polyvinylidene chloride and copolymers of vinylidene chloride and acrylonitrile or (meth)acrylic acid esters, fly ash, cashew nuts, cork, coke etc. may be further included.

Among these, the filler may further increase mechanical properties and foaming effect by adding fibers based on aramid fibers, carbon fibers, aluminum fibers, glass fibers, polyamide fibers, polyethylene fibers, or polyester fibers.

The filler preferably comprises 1 to 10% by weight based on 100% by weight of the main material. When less than 1% by weight is added, the above-described properties, in particular, the foaming effect of the silicone compound may be insufficient, and when added in excess of the above range, phase separation of the composition may occur and mechanical properties may rather deteriorate.

In the present invention, the main material does not limit the manufacturing method. For example, first, 3 to 10% by weight of a silicone compound is mixed with 80 to 90% by weight of a first epoxy resin, a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof After that, it is stirred at a speed of 300 to 700 rpm under a temperature of 70 to 80 ° C. with a homogenizer or impeller. Then, 1 to 10% by weight of a reactive surfactant and 1 to 10% by weight of a filler are added thereto and stirred at the same speed using residual heat. As described above, a filler is added to the composition into which the reactive surfactant is added, and the mixture is sufficiently stirred.

The main material according to the present invention may further add additives of various components in addition to the above components. In this case, the additive may be any one or a plurality selected from a diluent, a thermoplastic polymer powder, a coupling agent, a plasticizer, a rheology modifier, a wetting agent, an adhesive, a stabilizer, and a colorant, and in addition to these, a foam accelerator, a coupling agent, etc. free

For example, the foam accelerator may further include urea, an organic acid, an oxide of platinum, amine, lead, tin, zinc, calcium, cadmium, or the like, and a salt thereof, but the present invention is not limited thereto.

In addition, coupling agents include silanes and organic metalates, such as organic silanes, titanates, zirconates, and the like, and other than these, commercially available coupling agents are not limited to the type.

In the present invention, the curing agent is for curing the epoxy of the main material, and can be cured at room temperature, and is a two-component composition in which the main material and the curing agent must be separately measured and mixed, but has excellent chemical resistance, heat resistance, impact resistance, and moisture resistance. Due to its characteristics, it can be used for various purposes such as composite materials, insulation materials, mold materials, adhesives, etc. for aviation, ship, automobile, etc. desired in the present invention.

In the present invention, the curing agent may be more preferably a mixture of an amine-based curing agent and a polyamide-type curing agent. The above curing agent reacts with a multifunctional epoxy resin, particularly a bisphenol-based epoxy resin, to greatly increase mechanical strength.

In the present invention, the amine-based curing agent serves to improve the chemical resistance, water resistance and heat resistance of the composition by increasing the crosslinking density of the composition. can include

Examples of the above amine-based curing agent include 1,3-benzenedimethaneamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, and 2,5-dimethylhexamethylene. Diamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra( Hydroxyethyl) ethylenediamine, triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamine, isophorone diamine, metacene diamine, N-aminoethyl pipette Razine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5, 5) Undecane, norbornenediamine, tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4- Diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino1,2-diphenylethane, 2, 4-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α -(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene. The use of methanamine increases the curing speed at room temperature, and can impart a higher glass transition temperature, improved chemical resistance, and mechanical properties of the composition.

The polyamide-based curing agent is directly polymerized with an epoxy resin to impart a plurality of functional groups to the epoxy resin, and in particular, the amide group hydrogen bonds with the above-mentioned filler, in particular, a functional group such as fumed silica to further increase the heat resistance and durability of the composition play a role

The polyamide-based curing agent may be an aliphatic polyamide or an aromatic polyamide, and the type thereof may be freely changed according to the purpose of use of the foam. For example, when the foam requires flexibility, it is preferable to use aliphatic polyamide rather than aromatic polyamide, and to further improve heat resistance or mechanical properties, it is preferable to use aromatic polyamide.

In the present invention, the polyamide-based curing agent is, for example, any one selected from polyamidoamine, diethylene triamine, triethylenetetraamine, tetraethylene pentaamine, 3,3-amino bispropylamine and m-xylenediamine Or a plurality may be mentioned, and among them, the use of polyamidoamine is preferable because it can also adjust heat resistance by freely adjusting the molecular chain length of polyamidoamine while satisfying flexibility.

In addition, the curing agent may further include an auxiliary curing agent in addition to the amine-based and polyamide-type curing agents, and the content is 5 parts based on 100 parts by weight of the main material to 15 parts by weight.

Examples of the auxiliary curing agent include imidazole, p-chlorophenyl-N,N-dimethylurea (MONURON), 3-phenyl-1,1-dimethylurea (FENURON) or 3,4-dichlorophenyl-N,N- substituted ureas such as dimethylurea (DIURON), amino compounds such as for example tertiary aryl- or alkylamines such as benzyldimethylamine, tris(dimethylamino)phenol, piperidine or piperidine derivatives, amine salts and Examples of quaternary ammonium compounds or cycloamines include 1,3-bis(amino methyl)cyclohexane, P-amino dicyclohexylmethane, isophorone diamine, or metaxylene diamine among aromatic amines, preferably imidazole, metaxylene diamine and tris(dimethylamino)phenol, more preferably imidazole and metaxylene diamine, most preferably metaxylene diamine.

In the present invention, it is preferable to add 50 to 90% by weight of a polyamide type curing agent to 10 to 50% by weight of an amine-based curing agent. If it is out of the above range, it is not good because the mechanical properties of the composition may deteriorate or miscibility between each composition may decrease.

In addition, the curing agent may further include one or a plurality of ionomers in addition to the amine-based and polyamide-based curing agents to improve mechanical properties by increasing chemical bonding between the compositions.

The ionomer means that a part of the carboxylic acid group of a copolymer of ethylene acrylic acid or ethylene methacrylic acid is substituted with a metal cation, and preferred ionomers used in the present invention include olefin copolymers such as ethylene and zinc ( It contains carboxylic acids neutralized with metal ions such as Zn), sodium (Na), magnesium (Mg) or lithium (Li). A copolymer may be used.

Commercially used ionomers include SURLYN 8140 as a grade neutralized by sodium and SURLYN 9910 as a grade neutralized by zinc, but are not limited thereto.

The ionomer is preferably added in an amount of 0.1 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total curing agent. When added below the above range, the effect of improving physical properties due to the addition of the ionomer does not appear, and when added above the above range, the curing rate rapidly increases due to an excessive increase in interfacial miscibility, and the moldability and mechanical properties of the composition may deteriorate. there is.

As described above, the foam molded foam according to the present invention is prepared in the form of a composition by first mixing the components constituting the main material, then mixing a polyamide-based curing agent and an amine-based curing agent, and mixing other additives thereto. desirable. At this time, it is preferable to mix the composition at a temperature of 100° C. or less, more preferably at room temperature (around 20° C.) during the addition of the curing agent.

In addition, the composition ratio of the main material and the curing agent is not limited in the present invention, but mixing 20 to 50 parts by weight of the curing agent with respect to 100 parts by weight of the main material is preferable because it can satisfy moldability and foaming characteristics.

The mixed composition may be stored intermediately or directly transferred to equipment for further processing, such as an injection molding machine, an extruder or a calendering machine. In particular, in order to manufacture an expanded molded foam, it is preferable to put the composition into an injection mold, foam and harden it, and maintain the temperature of the mold at room temperature.

Since the epoxy foaming composition of the present invention additionally uses a raw material having a carboxyl group of a linear molecular chain in order to compensate for the brittleness of the brittleness of the breaking property while having a small deformation amount, the epoxy foaming composition has the carboxyl content of the resin component. The content is 15 to 30%.

According to another aspect of the present invention, a ship structure formed from the epoxy foam composition is provided.

According to another aspect of the present invention, a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof, c) silicone a main material including a silicone compound containing a hydrogen compound, d) a reactive surfactant, and e) a filler; And an amine-based and polyamide-based curing agent including an ionomer, a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent; The composition is mixed with 20 to 50 parts by weight of the curing agent relative to 100 parts by weight of the main material, and provides an epoxy foamed and cured product for manufacturing ship structures, characterized in that the compressive strength is 500 to 700 psi.

When the carboxyl group content in the main component is 15 to 30%, mechanical properties are improved as a whole. When the carboxyl content is 15 to 30%, the compressive strength at the yield point is 500 to 700 psi, preferably 550 to 650 psi, and increases by 100 to 150% compared to STANDARD: 486.

In addition, in the case of compressive modulus, when the content of carboxyl in the total resin composition is 15 to 30%, 8000 to 40000 psi, preferably 10000 to 40000 psi, more preferably 11000 to 39000 psi, standard (Standard: 7600 psi) increases by 100 to 530%.

In addition, in the case of ultimate tensile strength, when the content of carboxyl in the total resin composition is 15 to 30%, 500 to 700 psi, preferably 500 to 650 psi, 100 to 145% compared to the standard (STANDARD: 486 psi) It increases.

The specific gravity is 0.25 g/cc when the content of carboxyl in the total resin composition is 15 to 30%, the same as standard (0.25 g/cc).

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art.

<Example>

Preparation of epoxy foaming composition containing carboxyl group for manufacturing ship structure

A composition was prepared based on the composition ratio of Table 1 below, but the mixing temperature of the composition was room temperature (20° C.) and the stirring speed was 500 rpm. The prepared composition was pre-gelled for 5 minutes, cured and foamed for 30 minutes in an injection device to complete a specimen having a size of 10 cm × 10 cm × 1 cm.

Main material (% by weight) Curing agent (% by weight) The main material: hardener
(weight ratio) epoxy silicon
compound reactive surfactant filling Amine type Polyadmie type Ionomo (parts by weight) Example 1 85 7 4 4 15 85 - 1:0.3 Example 2 85 7 4 4 15 85 0.5 1:0.3 Example 3 85 7 4 4 15 85 1.5 1:0.3 Comparative Example 1 75 9 8 8 15 85 - 1:0.3 Comparative Example 2 95 3 One One 15 85 - 1:0.3 Comparative Example 3 85 One 7 7 15 85 - 1:0.3 Comparative Example 4 85 12 2 One 15 85 - 1:0.3 Comparative Example 5 85 7 One 7 15 85 - 1:0.3 Comparative Example 6 82 5 12 One 15 85 - 1:0.3 Comparative Example 7 85 9 6 - 15 85 - 1:0.3 Comparative Example 8 82 5 One 12 15 85 - 1:0.3 Comparative Example 9 85 7 4 4 - 100 - 1:0.3 Comparative Example 10 85 7 4 4 55 45 - 1:0.3 Comparative Example 11 85 7 4 4 100 - - 1:0.3

Epoxy in Table 1 includes a first epoxy resin, a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof. In addition, the ionomer means the added amount (parts by weight) relative to 100 parts by weight of the total curing agent.

Physical property measurement

Various physical properties of prepared Examples 1 to 3 and Comparative Examples 1 to 11 were measured.

ⓐ Tensile strength and elongation: Conducted in accordance with ASTM D 638.

ⓑ Flexural strength and flexural modulus: Conducted in accordance with ASTM D 790.

ⓒ IZOD impact strength: conducted in accordance with ASTM D 256.

ⓓ Compressive strength and compressive modulus at yield point (at 3% strain): Conducted in accordance with ASTM D 1621.

ⓔ Apparent overall density: Conducted in accordance with ISO-845.

<Results and evaluation>

tensile strength
(kgf/cm ² ) elongation
(%) flexural strength
(kgf/cm ² ) flexural modulus
(kgf/cm ² ) impact strength
(kgf/cm ² ) compressive strength
(psi) compression
modulus of elasticity
(psi) apparent overall density
(g/cc) Example 1 209 134 217 12,551 33.91 550 12,487 0.25 Example 2 272 88 301 17,583 43.25 615 38,564 0.25 Example 3 254 121 284 15,283 41.32 570 11,467 0.25 Comparative Example 1 208 118 235 12,614 11.3 420 6,500 0.25 Comparative Example 2 271 38 287 14,976 8.2 430 7,200 0.25 Comparative Example 3 261 35 288 13,966 9.07 480 9,600 0.25 Comparative Example 4 214 66 248 15,866 8.5 510 10,500 0.25 Comparative Example 5 238 61 260 16,334 15.4 534 11,100 0.25 Comparative Example 6 235 41 284 14,001 15.41 520 11,050 0.25 Comparative Example 7 153 121 158 10,247 5.4 423 6,500 0.25 Comparative Example 8 234 85 275 15,264 34.12 486 7,600 0.25 Comparative Example 9 241 116 224 14,086 27.61 520 12,000 0.25 Comparative Example 10 239 101 257 14,582 30.24 510 15,110 0.25 Comparative Example 11 162 120 167 12,252 15.4 386 5,500 0.25

Table 2 shows the physical property values of Examples 1 to 3 and Comparative Examples 1 to 11 prepared. It was found that the manufactured expanded molded foam showed high values in all mechanical properties such as tensile strength, elongation, flexural strength, flexural modulus, and impact strength. In particular, in the case of Examples 2 and 3 including the ionomer, it was confirmed that all mechanical properties were increased compared to Example 1, which did not include the ionomer. It seems that the impact strength, etc., has increased as the functional groups such as the chemical bonding with other epoxy resins or fillers have progressed.

The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the scope of the invention which follows may be better understood. Those skilled in the art to which the present invention pertains will understand that the present invention can be embodied in other specific forms without changing its technical spirit or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the claims and equivalent concepts should be construed as being included in the scope of the present invention.

Claims (7)

a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof, c) a silicone compound containing a silicon hydrogen compound, d) a reactive surfactant, and e) a main material comprising a filler; and
An amine-based and polyamide-based curing agent containing an ionomer, and a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent;
Epoxy foaming composition containing a carboxyl group for manufacturing a ship structure, characterized in that the content of the carboxyl group in the main component is 15 to 30%.
According to claim 1,
The first epoxy resin includes one or more hydroxy groups, alkoxy groups, halogen groups, aldehyde groups, carbonyl groups, carboxyl groups, amine groups, nitrile groups, nitro groups, amide groups, and imide groups alone or two or more in one unit structure constituting a repeating unit. An epoxy foaming composition containing a carboxyl group for manufacturing a ship structure, characterized in that.
According to claim 1,
The content of a) and b) is an epoxy foaming composition containing a carboxyl group for manufacturing a ship structure, characterized in that it comprises 80 to 90% by weight based on 100% by weight of the total main material.
According to claim 1,
The amine-based and polyamide-based curing agents contain 10 to 50% by weight of the amine-based curing agent and 50 to 90% by weight of the polyamide-based curing agent based on 100% by weight of the total curing agent. Epoxy foam composition.
According to claim 1,
The curing agent is an epoxy foaming composition containing a carboxyl group for manufacturing a ship structure, characterized in that the temperature of the composition during addition is 20 to 100 ℃.
A ship structure formed from the epoxy foam composition according to any one of claims 1 to 5.
a) a first epoxy resin, b) a liquid bisphenol-based epoxy resin or a modified epoxy resin modified with an aliphatic amine compound, and a second epoxy resin including a mixture thereof, c) a silicone compound containing a silicon hydrogen compound, d) a reactive surfactant, and e) a main material comprising a filler; and
An amine-based and polyamide-based curing agent including an ionomer, and a curing agent containing 0.1 to 2 parts by weight of the ionomer based on 100 parts by weight of the total curing agent;
The composition is mixed with 20 to 50 parts by weight of the curing agent based on 100 parts by weight of the main material,
Epoxy foam cured material for manufacturing ship structures, characterized in that the compressive strength is 500 to 700 psi.