KR102602066B1 - Two-part adhesive composition comprising Bisphenol-Z polyurethane - Google Patents

Abstract

The present invention provides a two-component adhesive composition consisting of a first agent containing an epoxy resin and a bisphenol-Z polyurethane and a second agent containing a curing agent, and the cured product prepared therefrom has excellent shear strength against dissimilar materials. As a result, it can be used for adhesion of dissimilar materials in the automotive or aerospace fields.

Description

Two-part adhesive composition comprising Bisphenol-Z polyurethane}

The present invention provides a new two-component adhesive composition containing bisphenol-Z polyurethane and a cured product prepared by curing the same.

Adhesive materials are manufactured including various curable resins, and depending on the curable resin used, they are classified into acrylic adhesives, vinyl acetate adhesives, ethylene vinyl alcohol (EVA) adhesives, epoxy adhesives, or hot melt adhesives.

The epoxy adhesive has excellent mechanical strength, durability, and adhesiveness, and has been widely used in the automotive, aerospace, and electrical/electronic fields.

In particular, in recent years, there has been a trend in the automotive and aerospace fields to use dissimilar materials such as aluminum, polymer resin, and composite materials for the purpose of reducing weight, and to solve the problems that arise from this, making welding very difficult, the use of epoxy adhesives has further increased. It is judged that it will be

However, conventional epoxy adhesives have too rigid characteristics and thus have low impact strength and flexural strength, which limits their use in fields that require high resistance.

To solve this problem, conventional epoxy adhesives have improved impact resistance by including a toughening agent, but they still have problems with increased viscosity and low dispersion, and in particular, their shear capacity for dissimilar materials is greatly reduced. There was no improvement.

Therefore, research and development is still required to solve the problem of epoxy adhesives containing toughening agents and further improve their adhesion ability to dissimilar materials.

Korean Patent Publication No. 10-2018-0122190 A Korean Patent Publication No. 10-2015-0057173 A

In order to solve the dispersion problem and low brittleness of the conventional epoxy adhesive, the purpose of the present invention is to provide a two-part adhesive composition containing bisphenol-Z polyurethane.

Another object of the present invention is to provide a two-component adhesive composition with excellent shear strength for different materials and a cured product manufactured therefrom in order to improve the problems of welding and adhesion of different materials due to weight reduction in the automobile and aerospace fields. It is done.

In order to solve the above problems, the present invention provides a first agent comprising an epoxy resin and a bisphenol-Z polyurethane represented by the following formula (1); and

a second agent containing a curing agent;

It provides a two-component adhesive composition comprising a.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are independently hydrogen or C1-C3 straight or branched chain alkyl,

A ₁ and A ₂ are independently C3-C30 straight or branched chain alkylene,

X ₁ and X ₂ are independently linkers containing a urethane bond,

A ₃ and A ₄ are independently C1-C6 straight or branched chain alkylene,

A ₅ and A ₆ are independently C1-C4 straight or branched chain alkylene,

R ₃ and R ₄ are independently hydrogen or C1-C6 straight or branched chain alkyl,

x and y are independently integers from 1 to 15,

j and k are independently 0 to 4 integers.)

According to one embodiment, in Formula 1, X ₁ and X ₂ may be independently represented by Formula 2 or Formula 3 below.

[Formula 2]

(In Formula 2 above,

A ₇ is C1-C20 straight or branched chain ylkylene,

r is an integer from 1 to 50,

n and m are independently integers from 1 to 15,

p is an integer from 1 to 12.)

[Formula 3]

(In Formula 3 above,

r is an integer from 1 to 15.)

According to one embodiment, the bisphenol-Z polyurethane may be represented by the following formula (4).

[Formula 4]

(In Formula 4 above,

x and y are independently 5 to 10 integers,

r and s are independently integers from 25 to 30,

p and q are independently integers from 1 to 6.)

According to one embodiment, the bisphenol-Z polyurethane may have a weight average molecular weight of 5,000 to 50,000 g/mol and a polydispersity index of 1 to 3.

According to one embodiment, the first agent may contain 50 to 200 parts by weight of bisphenol-Z polyurethane based on 100 parts by weight of the epoxy resin.

According to one implementation, the epoxy resin may be a bisphenol-based epoxy resin.

According to one embodiment, the curing agent may be one or two or more selected from aliphatic amine-based curing agents, cycloaliphatic amine-based curing agents, aromatic amine-based curing agents, and acid anhydride-based amine-based curing agents.

According to one embodiment, the first agent may further include one or two or more selected from core-shell type tougheners, fillers, and coupling agents, and the second agent further includes fillers, hardening accelerators, and mixtures thereof. It may be.

According to one embodiment, the first agent may include 1 to 50 parts by weight of filler based on 100 parts by weight of the epoxy resin.

According to one embodiment, the first agent may include 1 to 5 parts by weight of a coupling agent based on 100 parts by weight of the epoxy resin.

According to one embodiment, the second agent may include 0.1 to 50 parts by weight of filler based on 100 parts by weight of the curing agent.

According to one embodiment, the second agent may contain 0.1 to 10 parts by weight of the curing accelerator based on 100 parts by weight of the curing agent.

The present invention can provide a cured product manufactured by curing the two-component adhesive composition described above.

According to one implementation, the cured material may have a shear strength measured by ASTM D 1002 of 15 MPa or more.

The present invention relates to a first base layer;

A second base layer adhesively bonded to the first base layer, and

disposed between the first base layer and the second base layer,

An adhesive layer obtained by curing the above-described two-component epoxy adhesive composition can be provided.

According to one embodiment, the first base layer and the second base layer may be the same or different from each other, and may independently be made of metal, steel plate, wood, film, tile, plastic, glass, resin, ceramic, concrete, carbon material, and It may be one or more composite materials selected from fiber.

Since the two-component adhesive composition according to one embodiment of the present invention includes bisphenol-Z polyurethane, the cured product prepared therefrom can have excellent impact resistance.

In addition, the two-component adhesive composition according to one embodiment of the present invention can control the viscosity by adjusting the molecular weight of the bisphenol-Z polyurethane included, so that the physical properties of the cured product manufactured therefrom can be adjusted and applied to various industrial fields. there is.

In addition, the two-component adhesive composition according to one embodiment of the present invention can have excellent shearing ability for dissimilar materials, and can be used in the automotive and aerospace fields.

Figure 1 is an FT-IR measurement result showing that the *-NC0 peak at 2270 cm ^-1 disappears when the compounds represented by c, d, and e in Preparation Examples 1 to 3 are capped with 2-allylphenol.
Figure 2 shows the results of GPC (Gel Permeation Chromatography) measurement of the bisphenol-Z polyurethane prepared in Preparation Example 1.
Figure 3 shows the results of measuring the shear strength of the two-component adhesive composition prepared in Examples 1 to 3 and Comparative Example 1.

Unless otherwise defined, the technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art to which this invention pertains, and the gist of the present invention is summarized in the following description and accompanying drawings. Descriptions of known functions and configurations that may unnecessarily obscure are omitted.

Additionally, as used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, units used without special mention in this specification are based on weight, and as an example, the unit of % or ratio means weight % or weight ratio, and weight % refers to the amount of any one component of the entire composition unless otherwise defined. It refers to the weight percent occupied in the composition.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

The term 'comprise' in this specification is an open description with the same meaning as expressions such as 'comprising', 'contains', 'has' or 'characterized by', and includes elements that are not additionally listed, Does not exclude materials or processes.

The term 'linker containing a urethane bond' in this specification may refer to an alkylene containing *-NHC(=O)-*, and may be a linking group generated by a urethane reaction or a linking group generated by reacting a diisocyanate compound. It may be a term meaning .

In this specification, the term ‘CA-CB’ means a carbon number of A or more and B or less.

Although conventional epoxy adhesives have excellent mechanical properties, they have low brittleness and are difficult to apply in fields requiring high resistance. In order to solve the problem, impact resistance was improved by including a toughening agent, but the viscosity still increased and the epoxy resin was used. Dispersion also caused problems, and in particular, the shear strength for dissimilar materials did not improve significantly.

Therefore, the present inventor manufactured bisphenol-Z polyurethane, and found that a two-component adhesive composition containing it had excellent dispersibility and viscosity with good workability, and that the cured product prepared therefrom had excellent shear strength against dissimilar materials. This invention has been completed.

Hereinafter, the two-component adhesive composition of the present invention will be described.

The present invention relates to a first agent comprising an epoxy resin and bisphenol-Z polyurethane represented by the following formula (1); and

a second agent containing a curing agent;

It provides a two-component adhesive composition consisting of.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are independently hydrogen or C1-C30 straight or branched chain alkyl,

A ₁ and A ₂ are independently C5-C30 straight or branched chain alkylene,

X ₁ and X ₂ are independently linkers containing a urethane bond,

A ₃ and A ₄ are independently C1-C6 straight or branched chain alkylene,

A ₅ and A ₆ are independently C1-C4 straight or branched chain alkylene,

R ₃ and R ₄ are independently hydrogen or C1-C6 straight or branched chain alkyl,

x and y are independently integers from 1 to 15,

j and k are independently 0 to 4 integers.)

By containing bisphenol-Z polyurethane in the first agent, the two-component adhesive composition can solve the problems of low dispersion and increased viscosity of adhesive compositions containing conventional tougheners, and the cured product prepared therefrom In addition to having excellent impact resistance, it can also have excellent shear strength against different materials.

As an embodiment, the first agent may contain 50 to 200 parts by weight of bisphenol-Z polyurethane, and specifically 100 to 150 parts by weight, based on 100 parts by weight of the epoxy resin.

The first agent containing bisphenol-Z polyurethane in the above range can have a high degree of dispersion between the epoxy resin and bisphenol-Z polyurethane and provide a viscosity with good workability, and the cured product produced therefrom contains bisphenol -Z Due to the excellent flexibility of polyurethane, it can have remarkable impact resistance and, furthermore, excellent shear strength against dissimilar materials.

The epoxy resin may have two or more epoxy groups in the molecule and may be selected from saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic and heterocyclic polyepoxy compounds, etc. Specifically, it may be any one or two or more selected from bisphenol-type epoxy resin, glycidyl ether-based epoxy resin, glycidyl amine-based epoxy resin, phenol novolak-type epoxy resin, and cresol novolak-type epoxy resin.

As one embodiment, the epoxy resin may be a bisphenol-based epoxy resin.

The two-component adhesive composition containing the bisphenol-based epoxy resin can have excellent dispersion and adhesive performance, and by containing an arylene group, the cured product prepared therefrom can have superior hardness and hardness, so it can be preferred.

Specifically, the bisphenol-based epoxy resin may be any one or two or more selected from bisphenol A-based, bisphenol E-based, bisphenol F-based, bisphenol M-based, bisphenol S-based, and bisphenol H-based, etc., and more specifically, bisphenol A-based. It may be an epoxy resin, a bisphenol F-based epoxy resin, or a mixture thereof.

The bisphenol-based epoxy resin may be liquid at room temperature, and may have an epoxy equivalent weight of 100 to 600 g/eq, or 150 to 550 g/eq.

A two-component adhesive composition containing a bisphenol-based epoxy resin that satisfies the above range can not only provide a viscosity with good workability, but also has more advantageous properties in improving mechanical properties such as impact strength at the adhesive area as well as the above-mentioned effects. You can have it, but this is not limited.

In one embodiment, the curing agent may be one or two or more selected from amine-based curing agents, amide-based curing agents, phenol-based curing agents, and acid anhydride-based curing agents, and may specifically be amine-based curing agents and amide-based curing agents, and are more preferred. Examples include aliphatic amine-based curing agents, aromatic amine-based curing agents, and mixtures thereof, but are not limited as long as they are known to those skilled in the art for curing a two-component adhesive composition and can directly participate in crosslinking of the composition or act in the form of a catalyst. It can be used without.

The aliphatic amine-based curing agent is, for example, diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophorone diamine, 1,3-bisaminomethylcyclohexane, bis(p-aminocyclohexyl)methane (PACM), norbornenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1- It may be one or two or more selected from methylcyclohexane and 1,2-diaminocyclohexane.

The aromatic amine-based curing agent includes, for example, diaminodiphenylmethane (DDM), m-phenylenediamine, diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, and diethyltoluenediamine. , trimethylenebis(4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3, 5-diethyltoluene, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, diaminodiphenyl oxide, 3,3',5,5'-tetramethyl- It may be one or two or more selected from 4,4'-diaminobiphenyl and 3,3'-dimethyl-4,4'-diaminodiphenyl.

For example, the amide-based curing agent may be one or two or more selected from dicyandiamide, a guanidine compound, and an amide-based curing agent added with an acid anhydride.

The phenolic curing agent includes, for example, formaldehyde condensation type resol type phenol resin, non-formaldehyde condensation type phenol resin, novolak-type phenol resin, novolak-type phenol formaldehyde resin, polyhydroxystyrene resin, and cresol type phenol resin. , phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin, novolak-type phenolic resin, dicyclopentadiene-modified phenolic resin, terpene-modified phenolic resin, triphenolmethane -type resin, phenol aralkyl resin, special phenol resin (naphthol aralkyl resin; and polyhydroxystyrene resin (poly(p-hydroxystyrene)), etc. may be any one or two or more selected from the group.

The acid anhydride-based curing agent includes, for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, and methyl nadic acid anhydride. It may be any one or two or more selected from hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

According to another embodiment, the two-component adhesive composition controls the curing time, dispersion, and viscosity, and other additives are added in order for the cured product manufactured therefrom to have excellent impact resistance, abrasion resistance, moisture resistance, and chemical resistance, etc. More can be added.

According to one embodiment, the first agent may further include one or two or more selected from core-shell type tougheners, fillers, and coupling agents, and the second agent may further include fillers, hardening accelerators, and mixtures thereof. You can.

As one embodiment, the first agent may further include 0.5 to 5 parts by weight of a core-shell type toughening agent based on 100 parts by weight of the epoxy resin.

A two-component adhesive composition containing a core-shell type toughener in the above range may be preferred because the core-shell type toughener may be a disperse phase with a high degree of dispersion, and the hardener prepared therefrom may have excellent impact resistance. .

Specifically, the core-shell type toughener may be a particle including a core optionally made of a monomer having two or more double bonds and a shell partially or fully covering the core surface. More specifically, the core may be an elastomer or rubber polymer. The main ingredient may be rubber particles, and the shell may be a graft polymerized polymer, but this is not limited.

In addition, the rubber included in the core-shell type toughener can be selected from acrylic rubber, silicone rubber, urethane rubber, styrene-butadiene rubber, butadiene rubber, etc., where the core and shell are independent of each other, but this is limited if it is commonly used in the field. It's not like that.

The core-shell type toughener may have an average particle size of 0.01 to 20 ㎛, more preferably 0.1 to 5 ㎛, but can be used without limitation as long as it does not impair the physical properties of the two-component adhesive composition.

As an embodiment, the first agent may contain 1 to 50 parts by weight, specifically 5 to 30 parts by weight, and more specifically 10 to 20 parts by weight, based on 100 parts by weight of the epoxy resin. It can be.

A two-component adhesive composition further containing a filler in the above range can reduce the curing shrinkage rate, control the curing heat generation, and reduce the thermal expansion rate, and the cured product obtained by curing the same can have better thermal conductivity, chemical resistance, mechanical strength, and wear resistance. It may be preferred.

Examples of the filler include quartz, limestone, mica, fumed silica, calcium carbonate, magnesium carbonate, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, hydrotalcite, magnesium hydroxide, calcium hydroxide, wollastonite, bentonite, and silica. , any one or two or more selected from the group consisting of alumina, titanium oxide, barium sulfate, calcium sulfate, talc, and glass fiber can be used.

As one embodiment, the first agent may contain 1 to 5 parts by weight of the coupling agent, and specifically 1 to 2 parts by weight, based on 100 parts by weight of the epoxy resin.

The first agent containing the coupling agent in the above range can have excellent dispersibility as the coupling agent acts as an intermediary for the contained compound, and the cured product prepared therefrom has excellent mechanical strength, water resistance, heat resistance, transparency, and Adhesion can be improved.

The coupling agent may be a silane-based coupling agent, and the silane-based coupling agent may be in various forms depending on the reactor.

The functional groups of the silane-based coupling agent include, for example, methoxy, ethoxy, amino, vinyl, epoxy, methacryloxy, acryloxy, It may be one or two selected from ureido, chloropropyl, mercapto, sulfido, and isocyanato, but is not limited thereto.

As one embodiment, the second agent may contain 0.1 to 50 parts by weight of the filler based on 100 parts by weight of the curing agent, specifically 1 to 30 parts by weight, and more specifically 5 to 15 parts by weight. You can.

For example, the filler may be the same as or different from the filler included in the first agent, but is not limited thereto.

As an embodiment, the second agent may contain 0.1 to 10 parts by weight, specifically 1 to 5 parts by weight, and more specifically 1 to 3 parts by weight, based on 100 parts by weight of the curing agent. However, this is not limited.

An adhesive composition further containing a curing accelerator in the above range may be preferred because it can shorten the curing time, has excellent workability, and the mechanical strength of the cured product manufactured therefrom can be superior.

Specifically, the curing accelerator may be one or two or more selected from imidazole-based accelerators, urea-based accelerators, and tertiary amine-based accelerators, but any curing accelerator can be used without limitation as long as it is recognized by a person skilled in the art.

Examples of the imidazole-based accelerator include 2-methyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2 ,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2-undecylimidazole, 3-heptadecylimidazole, 2-phenyl Imidazole, 2-phenylimidazoline, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, It may be any one or two or more selected from 1-cyanoethyl-2-undecylimidazole.

As an example, the urea-based accelerator is any one selected from p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3,4-dichlorophenyl-N,N-dimethylurea, etc. There can be two or more.

Examples of the tertiary amine accelerator include benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol, 2-(dimethylaminomethyl)phenol, tri(dimethylaminomethyl)phenol, 1,5-diazabicyclo[ Any one or two or more selected from 4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undeca-7-ene, etc. may be mentioned.

Hereinafter, the bisphenol-Z polyurethane of the present invention will be described in more detail.

Bisphenol-Z polyurethane represented by Formula 1 can solve the dispersion of adhesive compositions containing conventional tougheners and the insufficient dynamic strength of cured products manufactured therefrom.

The structure may be prepared through a first reaction of reacting bisphenol-Z with alkylene oxide and a second reaction of reacting the reactant of the first reaction with a lactone-based compound.

For example, the alkylene oxide may be one or two or more selected from 2-methyloxylane, 2-ethyloxylane, and 2-propyloxylane.

In addition, the lactone-based compound may be, for example, one or two or more selected from α-lactone-based compounds, β-beta-lactone-based compounds, γ-lactone-based compounds, δ-lactone-based compounds, and ε-lactone-based compounds.

The bisphenol-Z polyurethane can be preferred because it not only has excellent mechanical properties and impact resistance due to the inclusion of aromatic groups, but also has excellent compatibility with epoxy resins and can be stirred with a high degree of dispersion.

Specifically, in Formula 1, R ₁ and R ₂ may independently be hydrogen or C1-C3 straight chain alkyl, and more specifically, may be hydrogen or methyl.

The R ₁ and R ₂ are derived from an alkylene oxide functional group, and may be preferred because they have the above-described structure and may have better reactions, and the physical properties of the bisphenol-Z polyurethane produced therefrom may not be impaired. can do.

Specifically, in Formula 1, A ₁ and A ₂ may each independently be a C5-C20 straight-chain or branched alkylene, and more specifically, a C5-C12 straight-chain alkylene.

The A ₁ and A ₂ may be structures derived from lactone compounds, and the bisphenol-Z polyurethane having the above-described structure may have excellent flexibility by having a straight chain alkylene, and the adhesive composition containing it has a low viscosity. Not only does it have good workability, but the cured product manufactured from it can have excellent impact resistance and can be preferred.

Specifically, in Formula 1, x and y are derived from the molar ratio of bisphenol-Z and the lactone-based compound, and may be an integer of 4 to 10, more specifically, an integer of 6 to 9.

Bisphenol-Z polyurethane with x and y in the above range can be preferred because its weight average molecular weight can be adjusted, and adhesive compositions containing it can provide viscosity with better workability.

In Formula 1, X _{1 and} It may be.

The adhesive composition containing bisphenol-Z polyurethane in which X _{1 and} may be preferred.

As an embodiment, in Formula 1, X ₁ and X ₂ may be independently represented by Formula 2 or Formula 3 below.

[Formula 2]

(In Formula 2 above,

A ₇ is C1-C20 straight or branched chain ylkylene,

r is an integer from 1 to 50,

n and m are independently integers from 1 to 15,

p is an integer from 1 to 12.)

[Formula 3]

(In Formula 3 above,

s is an integer from 1 to 15.)

Specifically, X ₁ and X ₂ in Formula 1 may have a structure derived from a diisocyanate-based compound or a diisocyanate-based compound and a polyol.

More specifically, the bisphenol-Z polyurethane manufactured containing only a diisocyanate-based compound is a bisphenol-Z polyurethane prepared containing only a diisocyanate-based compound and a _polyol , wherein in Formula ₁ , In Z polyurethane, X ₁ and X ₂ may have the structure of Formula 2 above.

The diisocyanate-based compounds include, for example, tetra-methylene diisocyanate, penta-methylene diisocyanate, hexa-methylene diisocyanate, hepta-methylene diisocyanate or octa-methylene diisocyanate, and 2-methylpentamethylene 1,5-diisocyanate. ,2-ethyltetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1,6- Diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 1,4- or 1,3-bis(methyl isocyanate) cyclohexane (HXDI), Cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- or 2,6-diisocyanate and methylene dicyclohexyl (4,4'-, 2,4'- or 2,2'-)diisocyanate It may be one or two or more selected from isocyanate (H12MDI).

For example, the polyol compound may be a polycaprolactone-based polyol or a polytetrahydrofuran (PHTP)-based polyol, and may have a weight average molecular weight of 500 to 5,000 g/mol, but this is not limited.

Specifically, in Formula 2, n and m may be derived from a diisocyanate-based compound, and may independently be an integer of 2 to 10, and more specifically, may be an integer of 4 to 8.

Also, specifically, in Formula 2, A ₇ may be a structure derived from polyol, and may be a C1-C20 straight-chain alkyl kylene, and more specifically, a C2-C12 straight-chain alkyl kylene.

Additionally, specifically in Formula 2, r may vary depending on the weight average molecular weight of the polyol and may be an integer of 10 to 30.

In Formula 3, s may be an integer of 2 to 10, which may be the same as or different from n and m in Formula 2.

Bisphenol-Z polyurethane containing X _{1 and} It may be preferred because it may have impact properties.

The structure may be a capping group, and bisphenol-Z polyurethane containing this can react with epoxy resin, which can further improve compatibility, and the cured product made from it can effectively improve impact resistance. , it can be preferred because it has a low coefficient of thermal expansion and can have more significant dimensional stability.

In addition, the capping group may be used without limitation as long as it is an aromatic compound having a functional group capable of reacting with isocyanate, and may contain one or more functional groups selected from a hydroxy group (*-OH), a thiol group (*-SH), or an amine group (*-NH ₂ ). It may be an aromatic compound, and for example, it may be a 2-allylphenol-based compound.

Specifically, in Formula 1, A ₃ and A ₄ may independently be C1-C6 straight-chain alkylene, and more specifically, they may independently be C1-C3 straight-chain alkylene.

Also, specifically, in the capping group structure, A ₅ and A ₆ may independently be C1-C4 straight chain alkylene, and more specifically, may independently be methylene or ethylene.

Specifically, in Formula 1, R ₃ and R ₄ may independently be hydrogen or C1-C6 straight chain alkylene, and more specifically, R ₃ and R ₄ may be hydrogen or methyl.

As one embodiment, the bisphenol-Z urethane may be represented by the following formula (4).

[Formula 4]

(In Formula 4 above,

x and y are independently 5 to 10 integers,

r and s are independently integers from 25 to 30.

p and q are independently integers from 1 to 6.)

As one embodiment, the bisphenol-Z polyurethane may have a weight average molecular weight of 5,000 to 50,000 g/mol and a polydispersity index of 1 to 3.

Specifically, the bisphenol-Z polyurethane may have a weight average molecular weight of 5,000 to 30,000 g/mol, and more specifically, 10,000 to 30,000 g/mol.

Additionally, specifically, the bisphenol-Z polyurethane may have a polydispersity index of 1 to 2.

Bisphenol-Z polyurethane with a weight average molecular weight in the above range has excellent compatibility with epoxy resins, and a two-component adhesive composition containing it may have a viscosity with excellent workability and may be preferred.

The present invention provides a cured product prepared by curing the above-described two-component adhesive composition.

The cured product is obtained by mixing the first agent and the second agent and curing it at 10 to 70 ° C. More specifically, the first agent and the second agent may be mixed at a mass ratio of 1:1 to 3:1. This does not limit this as it adjusts the content of the hardener according to the unit price of the epoxy resin.

As one embodiment, the cured product may have a shear strength measured by ASTM D 1002 of 15 MPa or more, specifically 15 to 30 MPa.

The cured product having a shear strength in the above range has excellent adhesion ability of dissimilar materials such as steel-aluminum, steel-composite material, and aluminum-composite material, and can be used in the automotive and aerospace fields.

The present invention relates to a first base layer;

A second base layer adhesively bonded to the first base layer, and

disposed between the first base layer and the second base layer,

An adhesive layer obtained by curing the above-described two-component epoxy adhesive composition is provided.

In one embodiment, the first base layer and the second base layer are the same or different from each other and are independently used in metal, steel plate, wood, film, tile, plastic, glass, resin, ceramic, concrete, carbon material, and fiber. It may be one or more composite materials selected.

Hereinafter, the present invention will be described by way of examples. That is, the present invention can be better understood by the following examples, and the following examples are for illustrative purposes of the present invention. However, the embodiments of the present invention are not intended to limit the scope of protection limited by the appended patent claims.

Bisphenol-Z polyurethane manufacturing

[measurement method]

1. Infrared spectroscopy (FT-IR) spectrum measurement

Completion of synthesis was confirmed by measurement with FT-IR (Thermo Fisher Scientific Inc, Nicolet 6700).

2. GPC (Gel Permeation Chromatography) measurement

It was measured using Gel Permeation Chromatography (GPC, Agilent Technologies, 1260 series), and THF was used as a solvent. Number average molecular weight, weight average molecular weight, and polydispersity index were measured using the above method.

[Production Example 1]

[Formula 1]

Bisphenol-Z (40 g, 0.149 mol), propylene oxide (19 g, 0.328 mol), 1,2-dimethylimidazole (0.8 g, 0.0559 mol), and Toluene (40 g, 0.376 mol) were added to a pressure-resistant round flask and then 103 Stir at ℃ for 5 hours. Afterwards, the solvent Toluene was removed using a rotary concentrator evaporator, and a was obtained as in Formula 1 above.

[Formula 2]

Afterwards, the obtained a (42 g, 0.109 mol), ε-caprolactone (200 g, 1.75 mol) and Tin(Ⅱ)2-ethylhexanoate (4.4 g, 0.011 mol) were placed in a 2-neck round flask and then placed in a nitrogen atmosphere. The mixture was stirred at 130° C. for 6 hours, and b was obtained as in Preparation Formula 2 above.

[Formula 3]

Put the obtained b (160 g, 0.08 mol) and 1 g of 1,1,1-Tris(hydroxymethyl) propane into a 500 ml reactor, dissolve the solid in an 80°C oil bath, and vacuum the inside of the reactor to remove unnecessary moisture. The back was removed and nitrogen was charged to block the inflow of external air. (All subsequent reactions proceed in a nitrogen environment.)

Afterwards, hexamethylene diisocyanate (26 g, 0.16 mol) and di-n-buthylbis(dodecylthio)tin (0.4 ml, 4%) were added into the reactor and reaction was performed for 40 minutes to obtain c shown in formula 3. did.

Additionally, 2-allylphenol was added inside the reactor to cap *-NCO of c, and FT-IR measurement was performed using the above measurement method to confirm that the *-NCO peak disappeared around 2270 cm ^-1 in Figure 1-a. and the reaction was terminated, finally obtaining bisphenol-Z polyurethane.

Afterwards, the number average molecular weight, weight average molecular weight, and polydispersity index of the prepared bisphenol-Z polyurethane measured by the GPC measurement method are shown in Table 1 below.

[Production Example 2]

[Formula 4]

500 ml of b (80 g, 0.04 mol), Polytetrahydrofuran (weight average molecular weight: 2,000 g/mol, 80 g, 0.04 mol), and 1,1,1-Tris(hydroxymethyl)propane obtained in Preparation Example 1 above. Put it in the reactor, melt the solid in an 80°C oil bath, create a vacuum inside the reactor to remove unnecessary moisture, and fill it with nitrogen to block the inflow of external air (all subsequent reactions are carried out in a nitrogen environment).

Afterwards, hexamethylene diisocyanate (26 g, 0.16 mol) and di-n-buthylbis(dodecylthio)tin (0.4 ml, 4%) were added into the reactor and the reaction was performed for 40 minutes to obtain d according to Formula 4 above. did.

Additionally, 2-allylphenol was added inside the reactor to cap *-NCO of d, and FT-IR measurement was performed using the above measurement method, showing that *-NCO'peak disappeared around 2270 cm ^-1 in Figure 1-b below. After confirmation, the reaction was terminated, and finally bisphenol-Z polyurethane was obtained.

Afterwards, the number average molecular weight, weight average molecular weight, and polydispersity index of the prepared bisphenol-Z polyurethane measured by the GPC measurement method are shown in Table 1 below.

[Production Example 3]

In Preparation Example 2, b (40 g, 0.02 mol), Polytetrahydrofuran (weight average molecular weight: 2,000 g/mol, 160 g, 0.08 mol), 1,1,1-Tris(hydroxymethyl) propane 1.25 g, and Hexamethylene diisocyanate ( Bisphenol-Z polyurethane was prepared in the same manner except that 32.5 g, 0.19 mol) was added to a 500 ml reactor, and 2-allylphenol was added to cap the *-NCO of d using FT-IR using the above measurement method. By measuring, it was confirmed that *-NCO'peak disappeared around 2270 cm ^-1 in Figure 1-b), and the reaction was terminated and proceeded.

Afterwards, the number average molecular weight, weight average molecular weight, and polydispersity index of the prepared bisphenol-Z polyurethane measured by the GPC measurement method are shown in Table 1 below.

material composition GPC measurements b
(mol) NCO
(mol) PTHF
(mol) M _n
(g/mol) M _w
(g/mol) PDI Manufacturing Example 1 0.08 0.16 0 11,275 17,739 1.57 Production example 2 0.04 0.16 0.04 10,198 17,148 1.68 Production example 3 0.02 0.19 0.08 12,830 20,580 1.60

Adhesive composition manufacturing

[measurement method]

1. Shear strength measurement

Two materials were used: steel (SPRC440, 25×100×1.6 mm), aluminum (AL6061, 25×100×2.0 mm), and composite material (CFRP, 25×100×2.8 mm). Each of the two materials used was steel. -Steel, steel-composite material, or aluminum-composite material was used, and the adhesive composition was applied to the two materials to form an adhesive area of 25×12.7 mm, overlapping them, and then curing at 100°C for 20 minutes.

After curing, it was measured using a universal testing machine (UTM 5982, INSTRON) according to ASTM D1002, and the spin head speed was 1.3 mm/min.

[Example 1]

Bisphenol A diglycidyl (MOMENTIVE, EPIKOTE 828) 26 g, toughener package 24.9 g, filler (calcium carbonate, aluminum hydroxide and calcium oxide, weight ratio 1:1:1) 3 g, coupling agent (3-glycidoxy) Propyltremitoxysilane and alkylsilane, weight ratio 1:1) were added to a paste mixer and stirred under vacuum conditions at room temperature for 5 minutes to prepare the first agent. The toughener package was prepared in Preparation Example 1. Bisphenol-Z polyurethane and core-shell type toughener were mixed and used at a weight ratio of 4:1.

Additionally, 36 g of hardener (Kukdo Chemical, Jeffamine D-230), 3.6 g of filler (limestone and quartz, weight ratio 1:1), and 2.5 g of hardening accelerator (Evonik, Ancamine K54) were added to a paste mixer and mixed at room temperature. The second agent was prepared by stirring under vacuum conditions for 5 minutes.

After that, the first agent and the second agent were mixed, and the measurements were made using the above measurement method and are shown in Table 2 and Figure 2 below.

[Example 2]

In Example 1, the first and second agents were prepared in the same manner, except that the bisphenol-Z polyurethane of Preparation Example 2 was used.

After that, the first agent and the second agent were mixed, and the measurements were made using the above measurement method and are shown in Table 2 and Figure 2 below.

[Example 3]

In Example 1, the first and second agents were prepared in the same manner, except that the bisphenol-Z polyurethane of Preparation Example 3 was used.

After that, the first agent and the second agent were mixed, and the measurements were made using the above measurement method and are shown in Table 2 and Figure 2 below.

[Comparative Example 1]

In Example 1, the first and second agents were prepared in the same manner, except that Huntsman's polyurethane was used.

After that, the first agent and the second agent were mixed, and the measurements were made using the above measurement method and are shown in Table 2 and Figure 2 below.

Comparative Example 2]

In Example 1, the first and second agents were prepared in the same manner, except that the bisphenol-Z polyurethane of Preparation Example 1 was not added.

After that, the first agent and the second agent were mixed, and the measurements were made using the above measurement method and are shown in Table 2 and Figure 2 below.

Shear strength steel-steel
(MPa) Steel-composite
(MPa) Aluminum-composite
(MPa) Example 1 19.81(±0.01) 18.46(±0.03) 15.89(±1.07) Example 2 23.61(±1.17) 23.61(±0.27) 11.83(±0.51) Example 3 24.11(±0.23) 23.6(±0.98) 13.6(±0.89) Comparative Example 1 19.87(±1.67) 16.43(±1.05) 11.82(±0.16) Comparative Example 2 12.5(±0.32) 10.23(±0.28) 6.83(±0.51)

Looking at the shear strength for steel-steel homogeneous materials in Table 1, it was confirmed that Example 3 had the best shear strength and Example 1 had the lowest shear strength in Examples 1 to 3. It was confirmed that the shear strength for steel-steel homogeneous materials was superior to Comparative Example 2, which did not use polyurethane, but was similar to Comparative Example 1.

In Table 1, looking at the shear strength for the steel-composite dissimilar material, it was confirmed that Examples 1 to 3 had excellent shear strengths, with Examples 2 and 3 having excellent shear strengths, and Example 1 having the lowest. It was confirmed that the shear strength of steel-composite dissimilar materials was superior to Comparative Examples 1 and 2 using commercial polyurethane.

In Table 1, looking at the shear strength for the aluminum-composite dissimilar material, it was confirmed that Example 1 was the best, Example 2 was the lowest, and Example 2 was lower than Comparative Example 1 in Examples 1 to 3. .

Therefore, Examples 2 and 3 were manufactured including polyhydrofuran, so the shear strength for steel-steel homogeneous materials was superior to Comparative Example 2 containing commercial polyol, and the same results were obtained for steel-composite heterogeneous materials. It shows. In addition, Example 1 has a similar shear strength to the steel-steel homogeneous material as Comparative Example 1 including commercial polyol, but the shear strength of the steel-composite heterogeneous material is excellent, and in particular, the shear strength to the aluminum-composite heterogeneous material is remarkable. showed the results.

The two-component adhesive composition according to one embodiment can control the shear strength for each material by adjusting the molecular weight of the bisphenol-Z polyurethane included, and has a shear strength for different materials that is equivalent to that of an adhesive composition containing commercially available polyurethane. Or, by being excellent, it was confirmed that it can be applied to industrial fields where excellent dynamic strength is inevitable.

As described above, the present invention has been described with specific details and limited examples and comparative examples, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above-mentioned examples. Those skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (16)

A first agent comprising an epoxy resin and bisphenol-Z polyurethane represented by the following formula (1); and
a second agent containing a curing agent;
Two-part adhesive composition comprising:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are independently hydrogen or C1-C3 straight or branched chain alkyl,
A ₁ and A ₂ are independently C3-C30 straight or branched chain alkylene,
X ₁ and X ₂ are independently linkers containing a urethane bond,
A ₃ and A ₄ are independently C1-C6 straight or branched chain alkylene,
A ₅ and A ₆ are independently C1-C4 straight or branched chain alkylene,
R ₃ and R ₄ are independently hydrogen or C1-C6 straight or branched chain alkyl,
x and y are independently integers from 1 to 15,
j and k are independently integers from 0 to 4. According to clause 1,
In Formula 1,
A _two -component adhesive composition wherein X ₁ and
[Formula 2]

In Formula 2,
A ₇ is C1-C20 straight or branched chain ylkylene,
r is an integer from 1 to 50,
n and m are independently integers from 1 to 15,
p is an integer from 1 to 12.
[Formula 3]

In Formula 3 above,
r is an integer from 1 to 15. According to clause 1,
The bisphenol-Z polyurethane is a two-component adhesive composition represented by the following formula (4):
[Formula 4]

In Formula 4 above,
x and y are independently 5 to 10 integers,
r and s are independently integers from 25 to 30.
p and q are independently integers from 1 to 6. According to clause 1,
The bisphenol-Z polyurethane is a two-component adhesive composition having a weight average molecular weight of 5,000 to 50,000 g/mol and a polydispersity index of 1 to 3. According to clause 1,
The first agent is a two-component adhesive composition comprising 50 to 200 parts by weight of bisphenol-Z polyurethane based on 100 parts by weight of the epoxy resin. According to clause 1,
The two-component adhesive composition wherein the epoxy resin is a bisphenol-based epoxy resin. According to clause 1,
The two-component adhesive composition wherein the curing agent is one or two or more selected from aliphatic amine-based curing agents, cycloaliphatic amine-based curing agents, aromatic amine-based curing agents, and acid anhydride-based amine-based curing agents. According to clause 1,
The first agent further includes one or two or more selected from core-shell type toughening agents, fillers, and coupling agents,
The two-part adhesive composition wherein the second agent further includes a filler, a curing accelerator, and a mixture thereof. According to clause 8,
The first agent is a two-component adhesive composition comprising 1 to 50 parts by weight of filler based on 100 parts by weight of the epoxy resin. According to clause 8,
The first agent is a two-component adhesive composition comprising 1 to 5 parts by weight of a coupling agent based on 100 parts by weight of the epoxy resin. According to clause 8,
A two-component adhesive composition wherein the second agent includes 0.1 to 50 parts by weight of filler based on 100 parts by weight of the curing agent. According to clause 8,
A two-component adhesive composition wherein the second agent includes 0.1 to 10 parts by weight of a curing accelerator based on 100 parts by weight of the curing agent. A cured product prepared by curing a two-component adhesive composition selected from claims 1 to 12. According to claim 13,
The cured product has a shear strength measured by ASTM D 1002 of 15 MPa or more. first base layer;
A second base layer adhesively bonded to the first base layer, and
disposed between the first base layer and the second base layer,
An adhesive layer obtained by curing the two-component epoxy adhesive composition selected from claims 1 to 12. According to clause 15,
The first base layer and the second base layer are the same or different from each other,
The adhesive layer is one or more composite materials independently selected from metal, steel plate, wood, film, tile, plastic, glass, resin, ceramic, concrete, carbon material and fiber.