KR20080033687A - Epoxy resin, method for preparing the same, composition comprising the resin, and adhesive consisting of the composition - Google Patents

Abstract

An epoxy resin for a laminate adhesive is provided to ensure little reactivity with water moisture, to exhibit excellent solubility in solvent, and to increase flexibility of laminated film. An epoxy resin has a structure represented by the following formula 1, wherein R1 is a substituted or unsubstituted and saturated or unsaturated aliphatic hydrocarbon or substituted or unsubstituted aromatic hydrocarbon having C1-12 chain length. An epoxy resin composition comprises the epoxy resin and an epoxy resin hardener. The epoxy resin and epoxy resin hardener are contained in a ratio of epoxy groups to active hydrogens of 0.5-5.0.

Description

Epoxy resin, method for preparing the same, and epoxy resin composition containing the epoxy resin, and an adhesive containing the same as an constituent thereof {Epoxy resin, Method for preparing the same, Composition consisting the resin, and Adhesive consisting of the composition}

The present invention relates to an epoxy resin for an adhesive used to prepare a film laminate, an epoxy resin composition comprising the same, a method for producing the epoxy resin, and a film laminate prepared using an adhesive formed from the epoxy resin composition.

Currently, packaging materials mainly used for packaging various foodstuffs and industrial products are film laminates formed by bonding an outer layer of a thermoplastic film layer and a sealing layer of a thermoplastic film layer with an adhesive. At this time, the adhesive mainly used to form such a film laminate is a two-component polyurethane-based adhesive composed of a main component having an active hydrogen group and a curing agent having an isocyanate group.

However, such a two-component polyurethane adhesive requires a curing accelerator, and there is a problem such as carbon dioxide generation due to the reaction of the isocyanate group constituting the curing agent with moisture in the air.

In order to solve this problem, an adhesive for an epoxy laminate having no isocyanate functionalized compound has been developed, but such an epoxy adhesive has a problem that gas barrier properties are not high.

On the other hand, in order to improve the gas barrier property of the adhesive for epoxy laminates described above, an adhesive for epoxy laminates using an epoxy resin containing an amide group is disclosed in WO 2003/022952. However, since the adhesive has a high water reactivity, water absorption occurs, oxygen blocking properties are poor, solubility in solvents is poor, and the adhesive is difficult to use and has a brittle physical property. In particular, when used as a packaging material for vacuum packaging, there is a problem of poor vacuum aptitude.

Therefore, development of an adhesive for epoxy laminates having low water reactivity and high gas barrier properties has been required.

The present invention has no problems with the conventional adhesives for epoxy laminates as described above, has little reactivity with moisture, has excellent solubility in solvents, and increases the flexibility of the laminated film, and has excellent vacuum aptitude in vacuum packaging. It is an object of the present invention to provide an epoxy resin for an adhesive, an epoxy resin composition comprising the epoxy resin, an epoxy-based adhesive prepared from the composition, and a laminate film laminated using the adhesive and a packaging material made of the film.

Moreover, an object of this invention is to provide the manufacturing method of the said epoxy resin and an epoxy resin composition.

The inventors of the present invention have been studied to solve the problems of the conventional epoxy-based laminate adhesive and to achieve the object of the present invention, as a result of the adhesive for the laminate formed from an epoxy resin composition comprising an epoxy resin comprising a structure of the formula In this case, there is little reactivity with water has been found to solve the problem due to the water reactivity of the existing epoxy-based adhesives to complete the present invention.

Accordingly, the present invention provides a novel epoxy resin comprising the structure of formula (1).

In addition, the present invention provides an epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent comprising the structure of the formula (1).

In addition, the present invention provides a film laminate prepared using an adhesive formed from an epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent comprising the structure of the formula (1).

The present invention also provides a packaging material made of the film laminate.

In addition, the present invention provides an epoxy resin comprising the structure of Formula 1 and a method for producing an epoxy resin composition comprising the same.

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

The present invention provides a novel epoxy resin comprising the structure of formula (1).

Formula 1

The epoxy resin including the structure of Chemical Formula 1 has an extremely low reactivity with water by containing -OR ₁ group in Chemical Formula 1, and thus, in the case of an adhesive including the same, the epoxy resin has very low water reactivity and high oxygen barrier property.

In Formula 1, R ₁ is a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon, or substituted or unsubstituted aromatic hydrocarbon having a chain length of C1 to C12.

Preferably, R ₁ is a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon, or substituted or unsubstituted aromatic hydrocarbon of chain length of C1 to C10.

More preferably, R ₁ is substituted or unsubstituted C1 to C10 alkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, cycloalkyl, aryl, biaryl and the like.

Non-limiting examples of R ₁ are substituted or unsubstituted, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, hep Tenyl, octenyl, nonenyl, desenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octinyl, noninyl, decinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cycloheptyl, cyclooctynyl, phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and the like.

The epoxy resin of the present invention is prepared by using the alkoxy aniline of formula 2, 3 or 4 and the acid chloride of the formula (5) as a starting material, the present invention provides a method for producing the epoxy resin of the present invention.

R ₁ in Formula 2, 3 or 4 is the same as defined in Formula 1, R ₂ in Formula 5 is the same as defined in R ₁ described above. Preferably R ₂ is substituted or unsubstituted, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, Octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octinyl, noninyl, decinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl , Cyclooctynyl, phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and the like.

When using the alkoxyaniline of formula (2) as a starting material, the preparation method comprises the steps of: (i) mixing the substituted alkoxyaniline of the formula (2) with the acid chloride of the formula (5), (ii) adding pyridine to the mixture (iii) adding and heating hydrogen to the reaction product (Formula 6) of step (ii), (iv) adding epichlorohydrin (ECH) to the reaction product (Formula 7) of step (iii) And (v) adding bisphenol A or bisphenol F to the reaction product of formula (iv).

The epoxy resin production method using the alkoxy aniline of formula (2) as a starting material is shown in Scheme 1 below.

Scheme 1

In Scheme 1, R ₁ is the same as defined in Formula 1, R ₂ is the same as defined in Formula 5.

When using the alkoxy aniline of formula 3 as a starting material, the method for preparing an epoxy resin of the present invention comprises the steps of (i) mixing a substituted alkoxyaniline of formula 3 and the acid chloride of formula (5), (ii) to the mixture Adding pyridine, (iii) adding NH ₃ and Al ₂ O ₃ to the reaction product of formula (ii), (iv) to the reaction product of formula (iii), and Adding epichlorohydrin (ECH), and (v) adding bisphenol A or bisphenol F to the reaction product of Formula (iv) above.

The preparation method using the alkoxyaniline of the formula (3) as a starting material is shown in Scheme 2 below.

Scheme 2

In Scheme 2, R ₁ is the same as defined in Formula 1, R ₂ is the same as defined in Formula 5.

On the other hand, when using the alkoxy aniline of the formula (4) as a starting material, the method for producing an epoxy resin of the present invention comprises the steps of (i) mixing a substituted alkoxy aniline of the formula (4) and the acid chloride of the formula (5), (ii) the mixture Adding pyridine to (iii) adding epichlorohydrin (ECH) to the reaction product of formula (ii), and (iv) reacting product of formula (iii) ) Bisphenol A or bisphenol F.

The preparation method using the alkoxyaniline of the formula (4) as a starting material is shown in Scheme 3 below.

Scheme 3

Definitions of R ₁ and R ₂ in Scheme 3 are the same as defined in Scheme 1 and Scheme 2.

On the other hand, the present invention provides an epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent comprising the above formula (1) structure.

Epoxy resin curing agents that can be used in the preparation of the epoxy resin composition of the present invention are aliphatic amines, modified aliphatic amines, aromatic amines, tertiary amines, acid anhydrides, polyamide resins, polysulfide resins, Bf3-amine complexes, phenolic resins. It may be a commonly used epoxy resin curing agent such as dicyandiamide.

Most commonly used as epoxy resin curing agents are amines such as diethylene triamine (DETA), triethylene tetraamine (TETA), diethylamino propyl amine (DEAPA), methane diamine (MDA), and N-aminoethyl piperazine ( N-AEP), aliphatic polyamines such as M-xylene diamine (MXDA), isophorone diamine (IPDA); Modified aliphatic polyamines such as epoxy polyamine adducts, ethylene or propylene oxide and polyamine adducts, cyanoethylated polyamines; Aromatic amines such as meta phenylene diamine (MPD), 4,4'-dimethyl aniline (DAM), diamino diphenyl sulfone (DDS), aromatic amine eutectics, aromatic amine adducts.

In addition, acid anhydrides such as aliphatic acid anhydrides such as dodecyl succinic anhydride, alicyclic acid anhydrides, aromatic acid anhydrides and halogen-based acid anhydrides may also be used as curing agents for the epoxy resin composition of the present invention.

Examples of acid anhydride curing agents include hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylnadic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, dodecyl succinic acid, and chloric acid. Contains anhydrides.

In addition, phenolic novolac resins and alkyl-substituted phenolic novolac resins may also be used.

In the preparation of the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the epoxy resin curing agent comprising the formula (1) may generally be a blending range used in the production of the cured epoxy resin. For example, an epoxy resin and an epoxy resin hardener can be mix | blended so that ratio of the active hydrogen of an epoxy group to an epoxy resin hardener in an epoxy resin is 0.5-5.0. More preferably, the ratio of epoxy group to active hydrogen is in the range of about 1-3.

The epoxy resin composition of the present invention as described above is used as a main component of the adhesive for film laminate, and the adhesive for laminate having the epoxy resin composition of the present invention as a main component is also included in the present invention.

Laminate adhesives containing the epoxy resin composition of the present invention as a main component have low humidity reactivity and are useful for producing film laminates having excellent oxygen barrier properties.

The adhesive for laminates containing the epoxy resin composition of the present invention as a main component may further include a curing accelerator.

Examples of curing accelerators include imidazole and tertiary amine, and specifically, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-undecylimidazole. , 2-ethyl-4-methylimidazolezine and 1-benzyl-2-methylimidazole, N, N-benzyldimethylamine, and 2,4,6-tris (dimethylaminomethyl) phenol.

In addition, the adhesive for laminates of the present invention, depending on the purpose of use, diluents, fillers, coupling agents for improving adhesion, wetting agents such as BYK 331, BYK 333 (available from BYK Chemie GmbH), flow modifiers and the like. It may further include.

Examples of commonly used diluents include reactive diluents such as butyl glycidyl ether, phenyl glycidyl ether, aliphatic glycidyl ether; And non-reactive diluents such as dibutyl phthalate, dioctyl phthalate, nonyl-phenol and the like.

The adhesive for laminates comprising the epoxy resin composition of the present invention as a main component can be used when laminating various films using known lamination methods, and film laminates prepared using the adhesive for laminates of the present invention are also included in the present invention. do.

Laminating methods that can be used to produce film laminates using the adhesive for laminates of the present invention include, for example, extrusion laminating, dry laminating, solvent-free laminating, thermal bonding, coextrusion, and the like.

In the case of using an extrusion lamination method, a dilution solution of the adhesive for lamination of the present invention is applied onto a film with a roll, and then the solvent is dried at room temperature to 140 ° C. and cured, and then another film material melted by an extruder is laminated. .

When using the dry lamination method, after apply | coating the dilution solution of the adhesive agent for laminations of this invention with a roll on a film, a solvent is dried and another film material is adhered by a roll etc. on it, and a film laminate is obtained.

In the case of the solventless lamination method, the adhesive for lamination of the present invention heated on a film is applied by a heated roll and another film material is adhered thereon to obtain a film laminate.

When diluting the adhesive for laminates of the present invention for the production of film laminates, the dilution can be made in organic solvents and / or water, examples of organic solvents that can be used include toluene, xylene, glycol ethers, alcohols and the like. do.

Specific examples of organic solvents that can be used for dilution include toluene, xylene, ethyl acetate, methanol, ethanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-propoxyethanol, 1 -Methoxy-2-propanol, 1-propoxy-2-propanol, dimethylformamide, dimethylacetamide, methylpyrrolidone and the like.

Examples of films that can be laminated with adhesives for laminates based on the epoxy resin composition of the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, oriented polypropylene films, unstretched polypropylene, biaxially stretched nylon films, unburned New nylon film, polyester film, polystyrene, polycarbonate, ethylene vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, polybutylene, styrene copolymer, acrylonitrile copolymer, vinyl chloride Films, vinylidene chloride films, polyamides, and the like.

Such film material may be surface treated to promote adhesion of the adhesive layer. Surface treatment may be by a mechanical method or a chemical method, the mechanical method is a method such as sanding, sandblasting, polishing and degreasing with a solvent, etc., chemical method is degreased with a suitable solvent and then immersed in various chemicals and washed with water Drying method;

The adhesive for laminates having the epoxy resin composition of the present invention as a main component has excellent oxygen barrier property and low humidity reactivity, and thus does not require a separate gas barrier layer when manufacturing a laminate film using the adhesive of the present invention. The film laminate produced has a reduced number of constituent layers and a lighter weight than conventional laminate films.

In addition, the film laminated using the adhesive for the laminate of the present invention is increased flexibility, it can be used as a packaging material of various applications, including vacuum packaging.

The adhesive for laminates comprising the epoxy resin composition of the present invention as a main component has low humidity reactivity and excellent oxygen barrier property, and film laminates prepared using the adhesive of the present invention have a reduction in the number of constituent layers and The weight can be reduced and the cost is reduced. In addition, the adhesive for the laminate of the present invention has the advantage that the solubility with the solvent is very good to use less harmful to the body, the flexibility of the laminated film by using the adhesive is increased, the advantage of excellent vacuum aptitude during vacuum packaging Has

Claims (14)

Epoxy resins comprising the structure of Formula 1: Formula 1

Wherein R ₁ is a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon, or substituted or unsubstituted aromatic hydrocarbon of chain length of C1 to C12. The epoxy resin of claim 1 wherein R ₁ is a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon, or a substituted or unsubstituted aromatic hydrocarbon of chain length of C1 to C10. The epoxy resin of claim 2 wherein R ₁ is substituted or unsubstituted, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, cycloalkyl, aryl, biaryl. An epoxy resin composition comprising the epoxy resin of claim 1 and an epoxy resin curing agent. The epoxy resin composition according to claim 4, wherein the epoxy resin and the epoxy resin curing agent are included in a ratio such that the ratio of epoxy group to active hydrogen is 0.5 to 5.0. The epoxy resin curing agent according to claim 4 or 5, wherein the epoxy resin curing agent is selected from aliphatic amines, modified aliphatic amines, aromatic amines, tertiary amines, acid anhydrides, polyamide resins, polysulfide resins, Bf3-amine complexes, phenol resins, dishes Epoxy resin composition, characterized in that it is selected from the group consisting of andamides. Adhesive for film lamination which has the epoxy resin composition of any one of Claims 4-6 as a main component. 8. The adhesive of claim 7 further comprising at least one of diluents, fillers, wetting agents, curing accelerators, flow modifiers. A film laminate laminated using the adhesive for film laminate of claim 8. 10. The method of claim 9 wherein the film material is low density polyethylene, linear low density polyethylene, high density polyethylene, oriented polypropylene film, unstretched polypropylene, biaxially stretched nylon film, unstretched nylon film, polyester film, polystyrene, polycarbonate, ethylene Selected from the group consisting of vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, polybutylene, styrene copolymer, acrylonitrile copolymer, vinyl chloride film, vinylidene chloride film, polyamide The film laminate characterized by the above-mentioned. A packaging material made from the film laminate of claim 9 or 10. (i) mixing a substituted alkoxyaniline of formula 2 with an acid chloride of formula 5, (ii) adding pyridine to the mixture, (iii) adding and heating hydrogen to the reaction product (Formula 6) of step (ii), (iv) adding epichlorohydrin (ECH) to the reaction product of formula (iii), and (v) adding the bisphenol A or bisphenol F to the reaction product of formula (iv) above, wherein the epoxy resin of claim 1 comprises: Formula 2

Formula 5

Formula 6

Formula 7

Formula 8

In the above formula, R ₁ is a substituted or unsubstituted chain length of C1 to C12, a saturated or unsaturated aliphatic hydrocarbon, or a substituted or unsubstituted aromatic hydrocarbon, and R ₂ is a substituted or unsubstituted chain length of C1 to C12 Ring, saturated or unsaturated aliphatic hydrocarbons, or substituted or unsubstituted aromatic hydrocarbons. (i) mixing the substituted alkoxyaniline of formula 3 with an acid chloride of formula 5, (ii) adding pyridine to the mixture, (iii) adding NH ₃ and Al ₂ O ₃ to the reaction product of Formula (ii) (Formula 9), (iv) adding epichlorohydrin (ECH) to the reaction product of formula (iii), and (v) A process for preparing the epoxy resin of claim 1 comprising adding bisphenol A or bisphenol F to the reaction product of formula (iv): Formula 3

Formula 5

Formula 7

Formula 8

Formula 9

In the above formula, R ₁ is a substituted or unsubstituted chain length of C1 to C12, a saturated or unsaturated aliphatic hydrocarbon, or a substituted or unsubstituted aromatic hydrocarbon, and R ₂ is a substituted or unsubstituted chain length of C1 to C12 Ring, saturated or unsaturated aliphatic hydrocarbons, or substituted or unsubstituted aromatic hydrocarbons. (i) mixing the substituted alkoxyaniline of formula 4 with an acid chloride of formula 5, (ii) adding pyridine to the mixture, (iii) adding epichlorohydrin (ECH) to the reaction product of formula (ii), and (iv) a process for preparing the epoxy resin of claim 1 comprising adding bisphenol A or bisphenol F to the reaction product of formula (iii): Formula 4

Formula 5

Formula 7

Formula 8

In the above formula, R ₁ is a substituted or unsubstituted chain length of C1 to C12, a saturated or unsaturated aliphatic hydrocarbon, or a substituted or unsubstituted aromatic hydrocarbon, R ₂ is a substituted or unsubstituted chain length of C1 to C12 Ring, saturated or unsaturated aliphatic hydrocarbons, or substituted or unsubstituted aromatic hydrocarbons.