KR101222195B1 - Polarity-controlled impact-resistance epoxy composition - Google Patents

Abstract

PURPOSE: A polarity-controlled and impact-resistant epoxy composition is provided to moderately introduce a polymer intermediate for controlling polarity, whereby improving the impact resistance. CONSTITUTION: A polarity-controlled and impact-resistant epoxy composition comprises: a first component which comprises an epoxy resin and a polymer intermediate; a second component which comprises an epoxy resin, a polyamide elastomer which is soluble in the epoxy resin and a monomer which can partially react with the polyamide elastomer; and a third component which comprises an additive mixture containing a core-shell particle and an epoxy resin. The polarity-controlling polymer intermediate is polyethermonoamine and the average molecular weight is 500-5,000. A backbone of the polymer intermediate comprises one or a mixture of ethyleneoxide and/or propyleneoxide.

Description

Polarity-controlled impact-resistance epoxy composition

The present invention relates to an impact resistant epoxy composition having a controlled polarity, and more particularly, by varying the polarity by appropriate selection of the polymer intermediate for controlling polarity, the polarity is controlled at the same time exhibiting the impact resistance properties during thermal curing It relates to an impact resistant epoxy composition.

The epoxy adhesive composition is a reactive adhesive composition comprising an epoxy resin, a curing agent and usually a latent accelerator. At the time of heating, the epoxy group of the epoxy resin reacts with the curing agent connecting the epoxy resin compound by the center-grafting reaction to obtain a cured product.

Such cured products are known to have good mechanical properties and better corrosion resistance than the cured products of other reactive adhesives. This property makes the epoxy based adhesive composition particularly useful for stringent applications where, for example, stringent mechanical requirements must be met in the automotive industry. Adhesives for joining parts of the vehicle structure of a vehicle, for example a car, lorry (truck), bus or train, are called structural adhesives.

Generally, thermosetting epoxy adhesives are used as structural adhesives.

As an alternative to thermoset epoxy adhesives, the use of bicomponent epoxy adhesives as structural adhesives is contemplated. The two component epoxy adhesive comprises two separate components, wherein the first component comprises an epoxy resin and the second component comprises an epoxy reactive compound. Such two-component epoxy adhesives generally cure immediately after the two components are mixed and do not require equipment used for the curing of the precure and thermoset epoxy adhesives. A number of two component epoxy adhesives have been disclosed previously.

U.S. Patent No. 4,728,737 discloses a two-component structural adhesive comprising an epoxy resin component and a curing agent component.

U.S. Patent No. 4,916,187 relates to a two component epoxy resin adhesive composition comprising a first polyepoxide component and a second curing component comprising a solid salt of polyamine and polyphenol finely dispersed in a liquid adduct.

U.S. Patent No. 5,629,380 discloses a two component epoxy adhesive comprising a first component comprising an epoxy catalyst and an amine curing agent and a second component comprising an epoxy resin having more than one functional group.

US Pat. No. 6,577,971 relates to a two component epoxy adhesive composition comprising a first component both comprising an epoxy resin and a silane coupling agent and a second component comprising an aliphatic amine and a polyamine.

Although the above patent documents disclose techniques for a two-component epoxy adhesive composition, techniques for an epoxy composition having improved impact resistance as a function of a toughening agent while controlling polarity have not been disclosed.

The present invention is to solve the above problems, and to provide a polarity-controlled impact-resistant epoxy composition that can obtain a polarity control and improved impact resistance at the same time by appropriately selecting and introducing a polarity-controlled polymer intermediates do.

It is another object of the present invention to provide a method of preparing the impact resistant adhesive composition of which the polarity is controlled.

It is another object of the present invention to provide a method of using the impact resistant adhesive composition of which the polarity is controlled.

It is also an object of the present invention to provide a reactive reagent prepared by using the impact resistant adhesive composition of which the polarity is controlled.

It is another object of the present invention to provide an adhesive tape produced using the impact resistant adhesive composition having the polarity controlled.

In order to achieve the above object,

(a) a first component comprising an epoxy resin and a polymer intermediate for controlling polarity;

(b) a second component comprising an epoxy resin, a polyamide elastomer having solubility in the epoxy resin, and a monomer partially reacting with the polyamide elastomer; And

(c) a polarized impact resistant adhesive composition comprising a third component comprising an additive mixture containing an epoxy resin and core-shell particles,

The polymer intermediate for controlling polarity is a polyethermonoamine, and has a weight average molecular weight of 500 to 5,000, and provides a polarized impact resistant adhesive composition comprising ethylene oxide and propylene oxide chains alone or in a mixed form in the main chain. .

To achieve these and other objects,

(a) preparing a first component comprising an epoxy resin and a polymer intermediate for controlling polarity;

(b) forming a second component comprising an epoxy resin, a polyamide elastomer having solubility in the epoxy resin, and a monomer that partially reacts with the polyamide elastomer;

(c) forming a third component comprising an additive mixture containing an epoxy resin and core-shell particles; And

(d) mixing the first component, the second component, and the additive mixture, the method of producing a polarized impact resistant adhesive composition comprising the steps of:

The polymer intermediate for controlling polarity is a polyethermonoamine, having a weight average molecular weight of 500 to 5,000, and a method for preparing a polarized impact resistant adhesive composition comprising ethylene oxide and propylene oxide chains alone or in a mixed form in the main chain. To provide.

According to another aspect of the present invention,

A polarized adhesive composition is applied to the surface of a structure and cured at a temperature of 120 to 180 ° C. to provide a method of using a polarized impact resistant adhesive composition to bond the opposite surface.

According to another aspect of the present invention,

It provides a reactive reagent prepared using a polarized impact resistant adhesive composition.

According to another aspect of the present invention,

An adhesive tape prepared using an impact resistant adhesive composition with controlled polarity is provided.

According to the composition of the present invention, by selecting the polymer intermediate for controlling the polarity appropriately to prepare an epoxy composition, the polarity can be adjusted in various ways, it can act as a toughening agent to obtain an epoxy composition with improved impact resistance during thermal curing.

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

The present invention (a) a first component comprising an epoxy resin and a polymer intermediate for controlling polarity; (b) a second component comprising an epoxy resin, a polyamide elastomer having solubility in the epoxy resin, and a monomer partially reacting with the polyamide elastomer; And (c) a third component comprising an additive mixture containing an epoxy resin and core-shell particles.

The polymer intermediate for controlling polarity is a polyethermonoamine having a weight average molecular weight of 500 to 5,000, and may include ethylene oxide and propylene oxide chains alone or in a mixed form in the main chain. This polymeric intermediate has the properties of reactive intermediates that participate in the final curing reaction.

The polymer intermediate for controlling polarity may be specifically represented by the following Chemical Formula 1:

≪ Formula 1 >

Wherein R is H or Me and x is an integer from 10 to 100.

In addition, the polymer intermediate for controlling polarity may be represented by a compound represented by Formula 2:

<Formula 2>

In the above formula, x and y are each an integer of 5 to 100, and the ratio of x and y is preferably 1:10 to 15: 1.

The compound represented by the formula (2) preferably has a weight average molecular weight of 1,000 to 3,000. When the weight average molecular weight of the compound of Formula 2 is less than 1,000, it is not preferable because the molecular weight is too small to control the polarity, and when the weight average molecular weight exceeds 3,000, it is not preferable because the mechanical properties decrease.

The content of the polymer intermediate for controlling polarity is preferably 2 to 30% by weight based on the total composition. If the content of the intermediate is less than 2% by weight, the addition effect of the intermediate is insignificant and not preferable. If the content of the intermediate is more than 30% by weight, it is not preferable because the mechanical properties are lowered.

The epoxy resin used in the composition of the present invention is a liquid or solid bisphenol A, bisphenol F, epichlorohydrin alone or a mixture, and the epoxy equivalent is preferably 130 to 800.

It is preferable that the total content of an epoxy resin is 20 to 70 weight% with respect to the whole composition. When the content of the epoxy resin is less than 20% by weight, it is not preferable to cause a decrease in mechanical properties, and when the content of the epoxy resin exceeds 70% by weight, it is not preferable because it results in a decrease in impact resistance performance.

It is preferable that the polyamide elastomer which has solubility in an epoxy resin has a weight average molecular weight of 10,000-100,000, and contains a carboxyl group and an amino group as a functional group. In addition, the glass transition temperature of the polyamide elastomer is preferably 50 to 90 ° C, and is a polyamide having solubility in an epoxy resin. The content of the polyamide elastomer having solubility in the epoxy resin is preferably 5 to 30% by weight based on the total composition.

In addition, the monomer for promoting the reaction between the epoxy resin and the polyamide elastomer in the second component is preferably ethylene oxide based diamine or polytetramethyleneethylene glycol based diamine. Specifically, the monomer is preferably a compound represented by the following Chemical Formulas 3 to 6:

<Formula 3>

CH- [OCH ₂ CH (R)] _X- [OCH ₂ CH (CH ₃ )]-NH ₂

R = H, CH ₃

&Lt; Formula 4 >

NH ₂ CH (CH ₃ ) CH _2- [OCH ₂ CH (CH ₃ )] _x -NH ₂

&Lt; Formula 5 >

NH ₂ CH (CH ₃ ) CH _2- [OCH (CH (CH ₃ ) CH ₂ )] _x- [OCH ₂ CH ₂ ]-[OCH ₂ CH (CH ₃ )] _x -NH ₂

(6)

H ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ NH ₂

Wherein x is each independently an integer of 1 to 15.

The content of the monomer for promoting the reaction of the epoxy resin and the polyamide elastomer is preferably 30 to 70% by weight based on the equivalent amount for completing the reaction of the epoxy resin. If it is less than 30% by weight, the lack of sufficient induction of reaction between the epoxy resin and the polyamide elastomer is not preferable.

The first component and the second component are preferably 65 to 95% by weight based on the total content of the composition. The first component and the second component may be used up to at least 5% by weight, up to 90% by weight, and two components are essential in the composition of the present invention, but are not highly dependent on the content of the first component and the second component, and the polymer for controlling polarity The physical properties of the adhesive composition can be easily controlled according to the content of the intermediate. Therefore, in consideration of the physical properties of the adhesive composition it can be prepared by the first component and the second component in various composition ratios.

The third component, including the additive mixture containing the epoxy resin and the core-shell particles, serves to impart low temperature impact resistance of the adhesive composition. The third component may be used in the range of 5 to 35% by weight based on the total content of the composition in consideration of low temperature impact resistance. If less than 5% by weight or more than 35% by weight based on the total content of the composition is not preferred because impact resistance at low temperatures is a problem.

The epoxy-coreshell additive mixture of the third component may further include heat-active latent curing accelerators and the like. The heat-activated latent curing accelerator may include dicyandiamide or imidazole-based materials. The heat-active latent curing accelerator may comprise one or more selected from inorganic fillers, silane coupling agents, fumed silica, phthaline-based reactive desiccants and mixtures thereof. Representative phthalin-based reactive desiccant is DAP (diallyl phthalate), it can be represented by the following formula (7):

&Lt; Formula 7 >

The phthalin-based reactive desiccant is preferably included in less than 5% by weight based on the total weight of the composition. If the content of the phthalin-based reactive desiccant, which is a curing accelerator, exceeds 5% by weight, it is not preferable because it may cause mechanical property deterioration.

According to another aspect of the invention, (a) preparing a first component comprising an epoxy resin and a polar intermediate for controlling the polarity; (b) forming a second component comprising an epoxy resin, a polyamide elastomer having solubility in the epoxy resin, and a monomer that partially reacts with the polyamide elastomer; (c) forming a third component comprising an additive mixture containing an epoxy resin and core-shell particles; And (d) mixing the first component, the second component, and the third component, wherein the polarity-resistant impact resistant adhesive composition is prepared, wherein the polar intermediate for controlling the polarity is a polyethermonoamine, and a weight average It is preferable that the molecular weight is 500 to 5,000, and the main chain contains ethylene oxide and propylene oxide chains alone or in a mixed form. As described above, the polymer intermediate for controlling polarity is preferably a compound represented by Formula 1 and Formula 2.

The monomer for promoting the reaction of the epoxy resin and the polyamide elastomer in the second component is preferably ethylene oxide based diamine or polytetramethyleneethylene glycol based diamine. Specifically, the monomer is preferably a compound represented by the following Chemical Formulas 3 to 6.

The polarity-controlled impact resistant adhesive composition according to the present invention preferably produces a mixture comprising a first component and a second component.

According to another aspect of the present invention, the adhesive composition of which the polarity is controlled may be applied to the surface of the structure and cured at a temperature of 120 to 180 ° C. to bond the opposing surface to the impact resistant adhesive composition.

The polarized impact resistant adhesive composition of the present invention can be applied and used in various forms such as paste compositions as well as reactive reagents or adhesive tapes.

Example

<1st component: preparation of epoxy / polar control polymer prepolymer>

100 g of a liquid epoxy resin (bisphenol A type) and 30 g of glycidyl ether reactive diluent are placed in a 1 L SUS container, and a polyether monoamine (Huntsman, trade name: surfonamine, main chain ethylene oxide /) is used as a polarity controlling polymer. The polarity is controlled according to the propylene oxide ratio and the appropriate ratio is selected to change the polarity.) 20 g is mixed with the contents and reacted with stirring slowly at 80 ° C. for 3 hours. After the reaction, slowly cool the contents to room temperature.

<Second Component: Preparation of Epoxy / Polyamide Elastomer Prepolymer>

100 g of liquid epoxy resin (bisphenol A type) was placed in a 1 L SUS container, and 20 g of polyamide elastomer (manufactured by Henkel, trade name: Macromelt, having a carboxyl group and an amine group at the polymer end) and ethylene oxide diamine (manufactured by Henkel, trade name: Jeffamine) 20 g of a molecular weight of 2,000) is mixed with the contents and reacted slowly at 130 ° C. for 3 hours. After the reaction, slowly cool the contents to room temperature.

Third Component: Preparation of Epoxy / Core-Shell Additive Mixture

500 g of liquid epoxy resin (bisphenol A type) is added to a 1.5 L SUS container at room temperature, and 50 g of glycidyl ether reactive diluent (Araldite of Huntsman) is added and mixed for 10 minutes. Mixing uses a high speed stirrer to cool the vessel while stirring using a cooling jacket so that the temperature of the contents in the vessel does not exceed 60 ° C. As an additive, 100 g of core-shell rubber particles (or Rohm and Haas core-shell rubber particles) of LG Chem are slowly added into the container and mixed for 1 hour to be dispersed. 50 g of silica, 2.5 g of silane, 60 g of DICY, and 5 g of imidazole promoter are added in succession and mixed for 1 hour.

<Adhesive formulation with controlled polarity 1>

400g of epoxy solution mixed with various additives (reactive diluent, silane, core-shell rubber particles, silica, accelerator) in a 1.5L SUS container and 150g of epoxy / polar control polymer prepolymer and 250g of epoxy / polyamide elastomer prepolymer The vessel was cooled by using a cooling jacket while mixing at a high speed and stirring for 30 minutes at high speed so as not to exceed 60 ° C. After mixing, the contents were slowly cooled to room temperature.

<Adhesive formulation with controlled polarity 2>

500g of epoxy solution mixed with various additives (reactive diluent, silane, core-shell rubber particles, silica, accelerator) in a 1.5L SUS container, 100g of epoxy / polar control polymer prepolymer and 50g of epoxy / polyamide elastomer prepolymer The vessel was cooled by using a cooling jacket while mixing at a high speed and stirring for 30 minutes at high speed so as not to exceed 60 ° C. After mixing, the contents were slowly cooled to room temperature. It can be used as a low viscosity adhesive by reducing the epoxy / polyamide content. The content of core-shell rubber particles is kept high in the overall formulation so that the impact peel strength at low temperatures is maintained to some extent.

Evaluation and Results

In order to prepare the specimen, the adhesive compound was evenly applied to the specimen surface at room temperature. The applied adhesive was cured by heating in an electric oven at 160 占 폚 for 30 minutes or 120 占 폚 for 60 minutes. The curing temperature can be adjusted, and the lower the temperature, the longer the cure time is adjusted.

Impact - peel  strength Peel strength  : N / mm )

For the composition of the examples, a test object was prepared from the steel sheet for measurement of the impact peel strength. The tensile shear strength at room temperature and the measurement results of the impact peel strength according to ISO 11343 at room temperature, 23 캜 and -40 캜 are shown in Table 1 below.

T- peel  strength ( kg / 25 mm )

The tensile bond strength was measured by holding a specimen at room temperature for 4 minutes at 23 DEG C and then performing a tensile strength test according to ASTM D1876. The measurement results are shown in Table 1 below.

Lap sheer  strength ( MPa )

The shear bond strength was measured at a room temperature of 23 DEG C for 16 minutes, and then a shear bond strength test according to ASTM D1002 was conducted. The measurement results are shown in Table 1 below.

Test Items Temperature condition Adhesive formulation 1 Adhesive formulation 2 Impact Peel sterngth
(N / mm) 23 ℃ 27 25 -40 ° C 18 19 T-Peel strength
(Kg / 25mm) 23 ℃ 34 32 Lap shear strength
(MPa) 23 ℃ 27 28

From the peel strength and tensile strength of Table 1, it can be seen that the impact resistant adhesive composition of the present invention possesses not only high shear strength but also impact peel energy.

Claims (23)

(a) a first component comprising an epoxy resin and a polymer intermediate for controlling polarity;
(b) a second component comprising an epoxy resin, a polyamide elastomer having solubility in the epoxy resin, and a monomer partially reacting with the polyamide elastomer; And
(c) a polarized impact resistant adhesive composition comprising a third component comprising an additive mixture containing an epoxy resin and core-shell particles,
The polymer intermediate for controlling polarity is a polyethermonoamine, having a weight average molecular weight of 500 to 5,000, and polarized impact resistant adhesive, characterized in that the main chain comprises ethylene oxide and propylene oxide chains alone or in a mixed form. Composition.
The method of claim 1,
Polarity-controlled impact-resistant adhesive composition, characterized in that the polymer intermediate for controlling polarity of the first component is a compound represented by the following formula (1).
&Lt; Formula 1 >

In this formula,
R is H or Me,
x is an integer from 10 to 100.
The method of claim 1,
Polarity-controlled impact resistant adhesive composition, characterized in that the polymer intermediate for controlling polarity of the first component is a compound represented by the following formula (2).
(2)

In this formula,
x and y are integers of 5-100, respectively.
The method of claim 3,
The compound represented by the formula (2) has a polarity-controlled impact resistant adhesive composition, characterized in that the weight average molecular weight of 1,000 to 3,000.
The method of claim 3,
Wherein the ratio of x and y is 1:10 to 15: 1.
The method of claim 1,
Polarity-controlled impact resistance adhesive composition, characterized in that the content of the polar intermediate for controlling the polarity of the first component is 2 to 30% by weight based on the total composition.
The method of claim 1,
The epoxy resin is a liquid and solid bisphenol A, bisphenol F, epichlorohydrin alone or a mixture, the epoxy resin is a polarized impact resistant adhesive composition, characterized in that 130 to 800.
The method of claim 1,
Total content of the epoxy resin is a polarized impact resistant adhesive composition, characterized in that 20 to 70% by weight based on the total composition.
The method of claim 1,
The polyamide elastomer having solubility in the epoxy resin of the second component has a weight average molecular weight of 10,000 to 100,000, and comprises a carboxyl group and an amino group as a functional group.
The method of claim 1,
The content of the polyamide elastomer having solubility in the epoxy resin of the second component is 5 to 30% by weight based on the total composition, the polarity-controlled impact resistant adhesive composition.
The method of claim 1,
The monomer of the second component is a polarized impact resistant adhesive composition, characterized in that it comprises ethylene oxide based diamine or polytetramethyleneethylene glycol based diamine.
The method of claim 11,
The monomer is a polarized impact resistant adhesive composition, characterized in that at least one compound selected from the group consisting of
(3)
CH- [OCH ₂ CH (R)] _X- [OCH ₂ CH (CH ₃ )]-NH ₂
R = H, CH ₃

&Lt; Formula 4 >
NH ₂ CH (CH ₃ ) CH _2- [OCH ₂ CH (CH ₃ )] _x -NH ₂

&Lt; Formula 5 >
NH ₂ CH (CH ₃ ) CH _2- [OCH (CH (CH ₃ ) CH ₂ ) _x- [OCH ₂ CH ₂ ]-[OCH ₂ CH (CH ₃ )] _x -NH ₂

(6)
H ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ NH ₂
Wherein x is each independently an integer of 1 to 15.
The method of claim 11,
The content of the monomer is a polarity-controlled impact resistant adhesive composition, characterized in that 30 to 70% by weight based on the equivalent weight for the reaction of the epoxy resin.
The method of claim 1,
The content of the third component is a polarized impact resistant adhesive composition, characterized in that 3 to 35% by weight based on the total composition.
The method of claim 1,
Wherein said third component further comprises dicyandiamide or an imidazole-based material as a heat-active latent curing accelerator.
16. The method of claim 15,
Wherein the curing accelerator comprises at least one selected from an inorganic filler, a silane coupling agent, a fumed silica, a phthalin-based reactive desiccant, and a mixture thereof.
17. The method of claim 16,
The phthalin-based reactive desiccant represented by the following formula (7), characterized in that less than 5% by weight based on the total weight of the composition, the polarity-controlled impact resistant adhesive composition:
&Lt; Formula 7 >

(a) preparing a first component comprising an epoxy resin and a polymer intermediate for controlling polarity;
(b) forming a second component comprising an epoxy resin, a polyamide elastomer having solubility in the epoxy resin, and a monomer that partially reacts with the polyamide elastomer;
(c) forming a third component comprising an additive mixture containing an epoxy resin and core-shell particles; And
(d) a method of producing a polarized impact resistant adhesive composition comprising mixing the first component, second component and third component,
The polymer intermediate for controlling polarity is a polyethermonoamine, having a weight average molecular weight of 500 to 5,000, and polarized impact resistant adhesive, characterized in that the main chain comprises ethylene oxide and propylene oxide chains alone or in a mixed form. Method of Preparation of the Composition.
19. The method of claim 18,
The monomer of the second component is a method of producing a polarized impact resistant adhesive composition, characterized in that it comprises ethylene oxide based diamine or polytetramethyleneethylene glycol based diamine.
19. The method of claim 18,
A method of making a polarized impact resistant adhesive composition comprising preparing a mixture of a first component, a second component and a third component and precuring it with heat.
18. The polarized controlled adhesive composition according to any one of claims 1 to 17 is applied to the surface of the structure and bonded to the opposite surface by curing at a temperature of 120 to 180 캜. Method of using impact resistant adhesive composition.
Reactive reagent prepared using the impact resistant adhesive composition with a controlled polarity according to any one of claims 1 to 17.
An adhesive tape prepared using the impact resistant adhesive composition whose polarity according to any one of claims 1 to 16 is controlled.