KR102445302B1 - Thermal curable adhesive composition, composite structure having adhesive layer and its preparation method - Google Patents

Abstract

The present invention relates to a thermosetting adhesive composition that has excellent adhesive strength and enables the formation of an adhesive layer exhibiting improved impact strength in a wide temperature range including low temperatures, a structure including an adhesive layer formed using the same, and a method for manufacturing the same. The thermosetting adhesive composition may include a silane-modified epoxy resin; liquid rubber; Polyurethane resin including a polymer block derived from polytetrahydrofuran; and a thermal curing agent curable at a temperature of 80° C. or higher.

Description

A thermosetting adhesive composition, a structure including an adhesive layer, and a method for manufacturing the same

The present invention relates to a thermosetting adhesive composition that has excellent adhesive strength and enables the formation of an adhesive layer exhibiting improved impact strength in a wide temperature range including low temperatures, a structure including an adhesive layer formed using the same, and a method for manufacturing the same.

Epoxy-based thermosetting adhesives having an epoxy resin as a main component are widely used to bond various substrates such as wood, resin, and metal to each other due to their high heat resistance and excellent adhesive strength.

In particular, recently, the epoxy-based thermosetting adhesive has been widely used for metal-to-metal bonding and metal-to-plastic bonding included in automobile body structures or other mechanical and electronic structures across various products and uses. Among them, in order to reduce the number of welds required for frame manufacturing and reduce overall process cost during the automobile manufacturing process, the application of the epoxy-based thermosetting adhesive is gradually expanding. Furthermore, in future industrial fields such as aerospace fields and wind power generation fields, interest in the epoxy-based thermosetting adhesive is increasing, and its application is expanding in order to simplify the overall process and reduce costs.

As such, as the field of application and use of the epoxy-based thermosetting adhesive is expanded, the level of physical properties required for this is gradually increasing. In particular, in the case of automobiles, as actual usage conditions range from a minimum of -40°C to a maximum of 80°C, the adhesive layer formed from the adhesive is required to maintain excellent adhesive strength and impact strength in a wider temperature range.

However, in the case of the epoxy-based adhesive composition developed to date, the impact strength of the adhesive layer formed therefrom is greatly reduced at a low temperature reaching -40 ° C., and its adhesive strength is also insufficient, so its application is limited.

Accordingly, research to develop an adhesive that maintains excellent impact strength in a wider temperature range, such as adding a rubber-based reinforcing material, various modified resins, or inorganic fillers to the existing adhesive composition is continuing.

In spite of such continuous research and efforts, an adhesive that exhibits excellent impact strength and adhesive strength at such low temperatures has not yet been properly developed.

An object of the present invention is to provide a heat-curable adhesive composition capable of forming an adhesive layer having excellent adhesive strength and exhibiting improved impact strength in a wide temperature range including low temperatures.

In addition, the present invention is to provide a structure including an adhesive layer formed from the adhesive composition and a method for manufacturing the same.

the present invention

silane-modified epoxy resin;

liquid rubber;

Polyurethane resin including a polymer block derived from polytetrahydrofuran; and

A thermosetting agent that can be cured at temperatures above 80℃

It provides a thermosetting adhesive composition comprising a.

The present invention also comprises the steps of applying the thermosetting adhesive composition of the present invention on a substrate; And at a temperature of 80 ° C. or higher, heat curing the applied composition to form an adhesive layer, it provides a method of manufacturing a structure.

In addition, the present invention provides a structure comprising a substrate and an adhesive layer including a cured product of the heat-curable adhesive composition of the present invention. In such a structure, the adhesive layer may include a binder layer in which a silane-modified epoxy resin is crosslinked through a thermal curing agent, a liquid rubber dispersed in the binder layer, and a polyurethane resin.

Hereinafter, a thermosetting adhesive composition according to embodiments of the present invention, a structure having an adhesive layer formed therefrom, and a method for manufacturing the same will be described in detail.

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of 'comprising' specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

On the other hand, according to an embodiment of the invention,

silane-modified epoxy resin; liquid rubber; Polyurethane resin including a polymer block derived from polytetrahydrofuran; And there is provided a heat curable adhesive composition comprising a heat curing agent curable at a temperature of 80 ℃ or more.

The present inventors continued research to develop an adhesive capable of forming an adhesive layer exhibiting excellent impact strength in a wide temperature range, particularly at low temperatures up to -40°C.

As a result of continuous research by the present inventors, by adding a polyurethane resin having a polymer block derived from polytetrahydrofuran to the silane-modified epoxy resin as a reinforcing material, improved impact/ It has been found that, together with peel strength, it is possible to form an adhesive layer exhibiting excellent adhesive strength, the invention has been completed.

The reason why the adhesive layer formed from the adhesive composition of one embodiment exhibits such excellent impact strength and the like is predicted as follows.

First, the silane-modified epoxy resin forms a binder layer of the adhesive layer, and the alkoxysilane group contained in the silane-modified epoxy resin connects the base material and the resin through a chemical bond with a base material such as a metal, and the silane-modified epoxy resin is the It combines with epoxy resin and polyurethane resin and has excellent compatibility with core-shell structured rubber copolymers and polyurethane resins to maintain superior adhesive strength even in harsh environments exposed to low temperature, high temperature, high humidity and salt water. Therefore, it seems that it is possible to improve impact resistance at low temperatures and long-term reliability in harsh environments.

At the same time, by adding a polyurethane resin having a relatively long chain polymer block, that is, a polymer block derived from polytetrahydrofuran, compared to the existing polyurethane resin, flexibility can be imparted to the overall adhesive layer. see. As a result, using the adhesive composition of one embodiment is expected to enable the formation of an adhesive layer exhibiting significantly improved impact/peel strength in a wide temperature range including low temperatures.

Therefore, when the adhesive composition of one embodiment is used, an adhesive layer that maintains excellent adhesive strength while exhibiting improved impact/peel strength in a wide temperature range up to -40°C can be formed. The adhesive composition of this embodiment can be preferably used for bonding various substrates in various industrial fields and uses, including automobile bodies.

Hereinafter, the thermosetting adhesive composition of one embodiment will be described in more detail for each component.

A heat-curable adhesive composition according to an embodiment is a resin for exhibiting adhesiveness, and includes a silane-modified epoxy resin. This silane-modified epoxy resin is crosslinked and cured with a heat curing agent to be described later under heat treatment and curing conditions to enable the formation of an adhesive layer.

As described above, as the silane-modified epoxy resin is included in the heat-curable adhesive composition, the adhesive layer may exhibit more improved impact/peel strength in a wide temperature range including low temperatures.

The silane-modified epoxy resin may be a modified epoxy resin by reacting an epoxy resin with a silane compound.

Specifically, in the silane-modified epoxy resin, an alkoxysilane group represented by the following Chemical Formula 1 is introduced into the epoxy resin according to the reaction between the epoxy resin and the silane compound.

[Formula 1]

-R ² -Si(R ¹ ) ₃

In Formula 1,

R ¹ is each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, at least one is an alkoxy group having 1 to 6 carbon atoms,

R ² is a single bond or an alkylene group having 1 to 10 carbon atoms.

The alkyl group having 1 to 6 carbon atoms may be a methyl group, an ethyl group, or a straight chain, branched chain or cyclic alkyl group having 3 to 6 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms is a methoxy group, an ethoxy group, or a straight chain having 3 to 6 carbon atoms. , may be a branched chain or cyclic alkoxy group, and the alkylene group having 1 to 10 carbon atoms is a methylene group, 1,1-ethylene group, 1,2-ethylene group, or a straight chain, branched chain or cyclic group having 3 to 10 carbon atoms. It may be an alkylene group.

For example, in Formula 1, R ¹ is each independently a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group, but at least one is a methoxy group, an ethoxy group or a propoxy group, and R ² may be a propylene group, a butylene group, a 2,2-dimethylpropylene group, a 2,2-dimethylbutylene group, or a 3,3-dimethylbutylene group.

The silane-modified epoxy resin may be obtained by reacting the above-described epoxy resin with a silane compound represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

NHR ³ -R ² -Si(R ¹ ) ₃

In Formula 2, R ¹ and R ² are as defined in Formula 1, and R ³ is hydrogen, an alkyl group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms.

[Formula 3]

OCN-R ² -Si(R ¹ ) ₃

In Formula 3, R ¹ and R ² are as defined in Formula 1 above.

The aminoalkyl group having 1 to 6 carbon atoms may be an aminomethyl group, 2-aminoethyl group, 1-aminoethyl group, or a linear, branched or cyclic aminoalkyl group having 3 to 6 carbon atoms.

For example, R ³ may be hydrogen, an aminomethyl group, an aminoethyl group, or an aminopropyl group.

Various silane-modified epoxy resins can be provided by mixing and reacting the epoxy resin with an appropriate amount according to the number of epoxy groups included in the epoxy resin using the silane compound.

In addition, the silane-modified epoxy resin may be included in an amount of 15 to 60% by weight, or 17 to 55% by weight, or 18 to 50% by weight, or 20 to 40% by weight based on the total composition of one embodiment. If the content of the silane-modified epoxy resin is too small, the impact strength of the adhesive layer may not be sufficient. .

The heat curable adhesive composition may further include an epoxy resin different from the silane-modified epoxy resin.

The epoxy resin includes, for example, a bisphenol-based epoxy resin derived from bisphenol A or bisphenol F in which an alkoxysilane group is not substituted, a novolac-based epoxy resin or an oxazolidone-based epoxy resin in which an alkoxysilane group is not substituted, and the like. Of course, two or more selected from these may be used. Among these various epoxy resins, in consideration of excellent adhesive strength and curing properties, bisphenol-based epoxy resins derived from bisphenol A or bisphenol F can be used more preferably, and these bisphenol A epoxy resins and bisphenol F epoxy resins are used together can also be used.

In the present specification, the epoxy resin is a term encompassing a compound for preparing an epoxy resin, such as bisphenol A diglycidyl ether or bisphenol F diglycidyl ether, and the term epoxy resin may be understood as an epoxy compound.

The epoxy resin may be a bifunctional or polyfunctional epoxy resin having two or more epoxy groups for excellent adhesive properties of the thermosetting adhesive composition.

On the other hand, the epoxy resin may have an epoxy equivalent of 170 to 600 in terms of adhesiveness of the overall composition. In a more specific example, as the epoxy resin, one or more bisphenol-based epoxy resins having an epoxy equivalent of 170 or more and less than 300 may be used, along with a bisphenol-based epoxy resin having an epoxy equivalent of 300 or more, or 350 to 600. It can be used by adding. According to this epoxy equivalent range, the adhesive layer formed from the composition of one embodiment may exhibit appropriate curing properties along with excellent adhesive strength.

The above-described epoxy resin may be included in an amount of 5 to 50% by weight, 5 to 35% by weight, or 10 to 30% by weight based on the total composition of one embodiment. This is in consideration of the adhesive strength and curing properties of the overall composition without deteriorating the functions of other reinforcing materials and additives included in the composition of one embodiment.

A heat-curable adhesive composition according to an embodiment includes a liquid rubber.

The liquid rubber is a reaction product of butadiene or butadiene-acrylonitrile copolymer and an epoxy resin. That is, the liquid rubber may be a rubber-modified epoxy resin.

In the liquid rubber, the rubber is a homopolymer or copolymer of a conjugated diene, in particular a diene-nitrile copolymer. The conjugated diene rubber is preferably butadiene or isoprene, with butadiene being particularly preferred. The nitrile is preferably acrylonitrile. A preferred such copolymer is a butadiene-acrylonitrile copolymer.

In the liquid rubber, the rubber contains an average of 1.5 to 2.5, or 1.8 to 2.2 epoxy-reactive end groups per molecule. The epoxy reactive end group may be an amino group or a carboxyl group. The rubber has a number average molecular weight (Mn) of 2000 to 8000 g/mol, or 2000 to 6000 g/mol.

By way of non-limiting example, such commercially available rubbers include Hycar 2000X162, Hycar 1300X31, Hycar 1300X8, Hycar 1300X9, Hycar 1300X18, and the like from CVC Thermoset Specialties.

The liquid rubber may be obtained by reacting an excess of epoxy with the rubber. The epoxy resin described above may be used as the epoxy resin. Preferably, as the epoxy resin, a bisphenol-based epoxy resin of bisphenol A or bisphenol F may be used.

As a non-limiting example, the commercially available liquid rubber is Polydis 3619 manufactured by S&S.

The above-described liquid rubber may be included in an amount of 5 to 40% by weight, or 10 to 35% by weight, or 15 to 33% by weight based on the total composition of one embodiment. As a result, the impact strength of the overall composition can be improved without deteriorating the functions of other reinforcing materials and additives such as the above-described silane-modified epoxy resin.

The heat-curable adhesive composition according to an embodiment may additionally include a core-shell structure rubber copolymer.

The core-shell structure of the rubber copolymer includes a core including a rubber polymer and a shell including a polymer cross-linked or graft-bonded to the core. The core-shell structure rubber copolymer is a reinforcing material added to improve overall impact resistance of the adhesive layer formed of the adhesive composition of one embodiment.

In the rubber copolymer having a core-shell structure, the core may include a diene-based rubber polymer such as butadiene rubber and/or isoprene rubber, or a diene-based rubber copolymer obtained by copolymerizing the diene-based rubber polymer with another monomer or the like.

In a specific example, the diene-based rubber copolymer includes the above-described diene-based rubber, an aromatic vinyl monomer such as styrene, a vinyl cyanide monomer such as (meth)acrylonitrile, and an alkyl (meth)acrylate-based monomer such as methyl acrylate. It may be a copolymer obtained by copolymerizing one or more monomers selected from the group consisting of.

The shell grafted or cross-linked to the core may include an aromatic vinyl monomer such as styrene; vinyl cyanide monomers such as (meth)acrylonitrile; vinyl acetate-based monomers; halogenated vinyl monomers such as vinyl chloride; glycidyl (meth)acrylate-based monomers such as glycidyl methacrylate; And at least one (co) selected from the group consisting of alkyl (meth) acrylate-based monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate or t-butyl methacrylate It may comprise a polymer, and the (co)polymer of this shell may be grafted or crosslinked to the core.

The rubber copolymer having the core-shell structure may be prepared by a method such as copolymerizing them by an emulsion polymerization method in the presence of a monomer to form the core and the shell after preparing the above-mentioned core. However, such a manufacturing method may follow conventional manufacturing conditions for manufacturing a core-shell structure rubber copolymer, and specific conditions thereof are also described in Synthesis Examples to be described later, so an additional description thereof will be omitted.

In the above-described core-shell structure of the rubber copolymer, the core may have a glass transition temperature (Tg) of -30°C or less, or -100°C to -30°C, and the shell is 50°C or more, or 60°C It may have a Tg of to 120 °C. As such, it is possible to more effectively reinforce the impact strength and mechanical properties of the adhesive layer formed of the composition of one embodiment.

The core-shell structure rubber copolymer may have a number average particle diameter of 250 to 500 nm, and the core has a particle diameter such that the core particle diameter ratio to the total particle diameter of the core-shell structure rubber copolymer is 0.8 to 0.99. can have More specifically, the core may have a number average particle diameter of 200 to 495 nm, or 230 to 450 nm, and may have a structure in which a thin shell surrounds the core.

As the rubber copolymer of the core-shell structure, in addition to having a number average particle diameter of 250 to 500 nm as described above, if necessary, a rubber copolymer having a small particle diameter of less than 250 nm, and/or a large particle diameter of more than 500 nm It may further include a rubber copolymer having a. The particle diameter range and the degree of addition of the core-shell structure rubber copolymer may be determined by those skilled in the art in consideration of the field or use in which the composition of one embodiment is used, and the level of impact strength required.

The above-described core-shell structure rubber copolymer may be included in an amount of 5 to 30% by weight, or 5 to 20% by weight based on the total composition of one embodiment. As a result, the impact strength of the overall composition can be improved without deteriorating the functions of other reinforcing materials and additives such as the above-described silane-modified epoxy resin and liquid rubber.

The heat-curable adhesive composition according to an embodiment includes a polyurethane resin including a polymer block derived from polytetrahydrofuran.

In general, a polyurethane resin is formed by reflecting a polyol and a polyvalent isocyanate as shown in the following general formula 1, and includes a polyol-derived residue (R') and a polyvalent isocyanate-derived residue (R), respectively, and has a urethane linking group connecting them It contains repeating unit structures.

[General formula 1]

Conventional polyurethane resins are typically prepared using ethylene glycol or propylene glycol as the polyol. In contrast, the polyurethane resin included in the composition of one embodiment includes a polymer block formed in the form of a relatively long-chain polymer derived from polytetrahydrofuran as the polyol-derived residue.

Therefore, the polyurethane resin included in the composition of one embodiment has a repeating unit structure including a polymer block derived from polytetrahydrofuran, a residue derived from a polyvalent aliphatic isocyanate, and a urethane linkage connecting them, in some cases , It may further include a residue derived from alkylene glycol having 2 to 5 carbon atoms, such as ethylene glycol or propylene glycol.

As such, as the adhesive composition of one embodiment includes a polyurethane resin having a long-chain polymer block, that is, a polymer block derived from polytetrahydrofuran, it seems that flexibility can be imparted to the overall adhesive layer, as a result It appears that the adhesive layer formed from the composition of one embodiment may exhibit further improved impact/peel strength over a wide temperature range, including low temperatures.

Such a polyurethane resin can be obtained by polymerizing a polyol containing polytetrahydrofuran and optionally alkylene glycol, and a polyvalent isocyanate of divalent or higher in the presence of a urethane curing catalyst. An example of the reaction conditions thereof is also described in Synthesis Examples to be described later.

The polyurethane resin may be obtained using polytetrahydrofuran having an OH equivalent of 400 to 2200, or 450 to 1000, and may have a weight average molecular weight (Mw) of 5000 to 500000 g/mol as a whole. Accordingly, while the low-temperature impact/peel strength of the adhesive layer is further improved, it is possible to suppress a decrease in other physical properties of the adhesive layer, such as basic adhesive strength.

As a non-limiting example, the weight average molecular weight (Mw) may be measured using an Agilent PL-GPC 220 instrument equipped with a 300 mm-long PolarGel MIXED-L column (Polymer Laboratories). The measurement temperature is 65 °C, tetrahydrofuran or dimethylformamide is used as a solvent, and the flow rate is measured at a rate of 1 mL/min. Samples are prepared at a concentration of 10 mg/10 mL and then supplied in an amount of 100 μL. The Mw and Mn values are derived with reference to a calibration curve formed using polystyrene standards. The molecular weight (g/mol) of polystyrene standards is 580/ 3,940/ 8,450/ 31,400/ 70,950/ 316,500/ 956,000/ 4,230,000.

The polyurethane resin including the polymer block derived from polytetrahydrofuran may be prepared using a general polyvalent aliphatic isocyanate of divalent or higher. For example, the polyvalent aliphatic isocyanate may be at least one compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and methylenedicyclohexyl diisocyanate.

In addition, the polyurethane resin may have a structure in which an isocyanate group at the terminal is capped with an amine compound, an alcohol compound, a phenol compound, an oxime compound, or a bisphenol compound. Due to the end-capping structure, it is possible to prevent the basic physical properties of the adhesive layer from being lowered or the impact strength of the adhesive layer from being sufficiently improved due to the addition of the polyurethane resin.

The polyurethane resin is a method of controlling the number of functional groups of the polyvalent isocyanate, or additionally using various branching agents or chain extenders, etc., to have a linear, branched or crosslinked structure, or to have a structure in which they are mixed. may be

The polyurethane resin may be included in an amount of 2 to 35% by weight, or 5 to 30% by weight, or 10 to 25% by weight based on the total composition of one embodiment. As a result, it is possible to further improve the impact/peel strength of the adhesive layer under a wide temperature range, and it is possible to suppress a decrease in the adhesive strength of the adhesive layer due to the addition of the polyurethane resin.

The thermosetting adhesive composition according to an embodiment includes a thermosetting agent curable at a temperature of 80°C or higher, or 100°C or higher.

The heat curing agent is a component that crosslinks and cures with the silane-modified epoxy resin under the application of heat to form an adhesive layer, and the silane at a temperature of 80° C. or higher to form an appropriate adhesive layer while reducing damage to the substrate to be bonded. It may react with the modified epoxy resin to cause crosslinking and curing reactions.

The type of the thermal curing agent is not particularly limited, and any thermal curing agent previously known to be usable in the epoxy-based thermal curing composition may be used.

For example, the thermal curing agent is a dicyandiamide-based curing agent; Melamine-type hardening|curing agents, such as a melamine; diallyl melamine-based curing agent; guanamine-based curing agents such as acetoguanamine or benzoguanamine; aminotriazole-based curing agents such as 3-amino-1,2,4-triazole; hydrazide-based curing agents such as adipic acid dihydrazide, stearic acid dihydrazide or isophthalic acid dihydrazide; Cyanoacetamide-based curing agent; Or it may be an aromatic polyamine-based curing agent such as diaminodiphenylsulfone. The thermal curing agent may include one or more compounds selected from the group consisting of the exemplified compounds.

Among these various thermal curing agents, in consideration of appropriate curing properties and processability of the adhesive composition and excellent adhesive strength of the adhesive layer, dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide, or 4,4 '-diaminodiphenylsulfone and the like can be preferably used.

The above-described thermal curing agent may be used in an amount of 1.5 to 10% by weight, or 2.5 to 10% by weight, or 2.5 to 7% by weight, based on the total composition, and its content is determined by those skilled in the art in consideration of the content of the silane-modified epoxy resin. can be appropriately determined.

On the other hand, the heat-curable adhesive composition according to an embodiment, in addition to each component described above, a curing catalyst, a general inorganic filler in the form of primary particles, a reactive diluent having a mono-epoxy group, a plasticizer, a non-reactive diluent, a coupling agent, a flow control agent, a thixotropic agent It may further include one or more additives selected from the group consisting of modifiers.

As each of these additives, any additive applied to the epoxy-based heat-curable adhesive may be used without any particular limitation.

For example, as the curing catalyst for controlling the curing rate and temperature of the adhesive composition, p-chlorophenyl-N,N-dimethylurea or 3-phenyl-1,1-dimethyl urea, 3,4- urea catalysts such as dichlorophenyl-N,N-dimethylurea; tertiary-acryl or alkylene amine catalysts such as benzyldimethylamine or 2,4,6-tri(dimethylaminomethyl)phenol; piperidine-based catalysts; Alternatively, an imidazole-based catalyst such as C1-C12 alkylene imidazole or N-aryl imidazole may be used.

The curing catalyst may be included in an appropriate amount in consideration of the required curing rate and temperature, for example, may be included in an amount of 0.1 to 2.0% by weight in the total composition.

The composition of one embodiment may further include an inorganic filler, which may be an inorganic filler in the form of primary particles.

These inorganic fillers may be used for additional control of the basic properties of the adhesive composition or rheological properties, and may have various particle shapes such as angular, spherical, plate-like, and needle-like shapes. Examples of such inorganic fillers include silicate-like inorganic fillers of quartz powder, alumina, calcium carbonate, calcium oxide, aluminum hydroxide, magnesium calcium carbonate, barite, or aluminum magnesium calcium silicate. In addition, as another example of the inorganic filler, there may be mentioned silica fine particles that can be added to control the viscosity of the composition of the embodiment, chisability, and the like. As the silica fine particles, either hydrophobic or hydrophilic particles may be used, and more preferably, hydrophobic silica fine particles may be used.

The inorganic filler may be included in an amount appropriately determined by a person skilled in the art within a content range of 2 to 20% by weight based on the total composition. For example, the composition may contain 0.5 to 7% by weight of silica fine particles.

In addition, the composition of one embodiment may further include additives such as a reactive diluent or non-reactive diluent having a mono-epoxy group, a plasticizer, a coupling agent such as a silane coupling agent, a fluidity control agent, or a thixotropy control agent, and the types of these additives and The amount that can be added is known to those skilled in the art.

Meanwhile, the heat-curable adhesive composition may be prepared by mixing each of the above-described components according to a general method.

For example, the silane-modified epoxy resin and the liquid rubber are first mixed, and the remaining additives except for the polyurethane resin, the thermal curing agent, and the curing catalyst are mixed, and then the temperature is finally lowered, the polyurethane resin, the thermal curing agent and It can be prepared by mixing a curing catalyst.

The heat-curable adhesive composition thus prepared may be used to form various structures or composites by bonding various substrates such as wood, metal, and plastic.

According to another embodiment of the invention, applying the above-described heat-curable adhesive composition on a substrate; And at a temperature of 80 ° C. or higher, there is provided a method of manufacturing a structure comprising the step of thermally curing the applied composition to form an adhesive layer.

According to another embodiment of the present invention, there is provided a structure including the substrate and an adhesive layer including a cured product of the heat-curable adhesive composition.

The adhesive composition may be applied to various substrates through a mechanical application method of an extrusion method, a jet spray method such as a swirl or streaming method according to a method well known in the art. When there are a plurality of substrates to be bonded, the adhesive composition may be applied to only one of the substrates, or may be applied to all two or more substrates.

The kind of the substrate to which the adhesive composition is applied is not particularly limited, and may be applied for adhesion or bonding of various substrates, including wood, coated or uncoated metal, aluminum, plastic, or plastic containing glass fiber.

Suitably, the adhesive composition is a steel sheet, for example, a cold-rolled steel sheet, an electro-galvanized steel sheet, a hot-dip galvanized steel sheet, an alloyed hot-dip galvanized steel sheet, or a zinc/nickel/magnesium coated steel sheet, or aluminum or aluminum alloy. It can be applied to these metal substrates for adhesion or bonding.

After the adhesive composition is applied, heat of 80 ℃ or more, or 100 ℃ or more, or 80 to 220 ℃ may be applied to thermally cure the adhesive composition, and as a result, an adhesive layer is formed on the substrate to adhere various substrates Or it can be joined.

The structure thus formed has a structure including a substrate and an adhesive layer including a cured product of the heat-curable adhesive composition described above.

In the structure, the adhesive layer may have a form including a binder layer in which a silane-modified epoxy resin is crosslinked through a thermal curing agent, a liquid rubber dispersed in the binder layer, and a polyurethane resin.

In this structure, the adhesive layer exhibits improved impact/peel strength in a very wide temperature range including low temperatures up to -40°C, and can maintain excellent adhesive strength together. Accordingly, such a structure may be a structure/composite included in an automobile body, or various resin/metal structure/composite materials applied in various future industrial fields such as aerospace fields and wind power generation fields.

According to the present invention, there is provided a heat-curable adhesive composition that exhibits improved impact/peel strength over a very wide temperature range, including low temperatures up to -40°C, and enables the formation of an adhesive layer maintaining excellent adhesive strength.

As the heat-curable adhesive composition exhibits significantly improved impact/peel strength at wide temperatures including very low temperatures where conventional adhesives did not exhibit sufficient impact strength, various industrial fields and uses including automobile bodies and various future industrial fields It can be very preferably used for bonding various substrates in

Hereinafter, preferred embodiments are presented to help the understanding of the present invention. However, the following examples are only for illustrating the invention, and the present invention is not limited thereto.

Synthesis Example 1: Preparation of silane-modified epoxy resin

50 g of bisphenol A epoxy resin (Kukdo Chemical, product name: YD128) with an epoxy equivalent of 190 in a nitrogen-substituted polymerization reactor, 50 g of bisphenol F epoxy resin with an epoxy equivalent of 170 (Kukdo Chemical, product name: YDF-170), and 0.85 g of 3-aminopropyltrimethoxysilane were mixed and added, and reacted at 100° C. to prepare an alkoxy-containing epoxy resin.

Synthesis Example 2: Preparation of a polyurethane resin including a polymer block derived from polytetrahydrofuran

In a nitrogen-substituted polymerization reactor, 109.76 g of polytetrahydrofuran having an OH equivalent of 500, 36.92 g of hexamethylene diisocyanate, 2.51 g of propylene glycol, 22.75 g of t-butylphenol, and 0.1 g of tin catalyst were mixed and added in a ratio of 75 The reaction was carried out at ℃ to prepare a polyurethane resin.

Examples 1, 2 and Comparative Examples 1 to 3: Preparation of heat-curable adhesive composition

The heat-curable adhesive compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared according to the components and compositions summarized in Table 1, and the following method.

First, put the liquid rubber and epoxy resin in a planetary mixer and mix at 80 ℃ for 5 hours. In addition, the remaining fillers and additives except for the polyurethane resin, the thermal curing agent and the curing catalyst were put into the planetary mixer and stirred at 80° C. for 3 hours. Finally, the temperature was lowered to 40 °C, a heat curing agent, a curing catalyst, and a polyurethane resin were added, mixed for 1 hour, and then the temperature was further lowered to room temperature to complete the kneading. As such, the thermosetting adhesive compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared.

content (wt%) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Bisphenol A Epoxy Resin ¹ - 5 14 14 - Silane-modified epoxy resin ² 31 18 31 - 25 liquid rubber ³ 24 30 - 41 30 Polyurethane Resin A ⁴ 10 12 - 10 - Resin B ⁵ - - 20 - 10 Core-Shell Rubber Copolymer ⁶ 10 10 10 10 10 colorant ⁷ 0.05 0.05 0.05 0.05 0.05 heat curing agent ⁸ 5.95 5.95 5.95 5.95 5.95 curing catalyst ⁹ One One One One One inorganic filler CaCO ₃ 10 10 10 10 10 CaO ¹⁰ 5 5 5 5 5 Fumed Silica ¹¹ 3 3 3 3 3

In Table 1, specific types and physical properties of each component are summarized below.

1. Bisphenol A epoxy resin having an epoxy equivalent of 190 used in the preparation of the epoxy resin of Synthesis Example 1 (Kukdo Chemical, product name: YD128)

2. Silane-modified epoxy resin: Silane-modified epoxy resin prepared in Synthesis Example 1

3. Liquid rubber (S&S, product name: Polydis3619, reaction product of carboxyl-terminated butadiene-acrylonitrile copolymer and epoxy resin)

4. Polyurethane resin A: polyurethane resin prepared in Synthesis Example 2 (Mw: 13000)

5. Polyurethane resin B: DY965 from Huntzman

6. Core-shell rubber copolymer: MX 153 from kaneka

7. Colorant: Pigment violet 23

8. Thermal curing agent: 1200G by Airproduct (ingredient name: dicyandiamide)

9. Curing Catalyst: Amicure UR7/10 from Evonik

10. CaO: Yoshizawa's HALP_P_Z (primary particle form with a particle size of 3 microns)

11. Fumed Silica: TS720 from Cabot

Test Example: Formation of an adhesive layer and evaluation of physical properties

(1) Impact/Peel Strength Test

Specimens including an adhesive layer formed from the compositions of Examples and Comparative Examples were prepared, and impact/peel strength was measured and evaluated by the following method.

Five specimens having a length of 90 mm, a width of 25 mm, and a thickness of 1.6 mm were prepared. Cold rolled steel having a strength of 440 MPa was used as a substrate for the specimen. The bonding area was set to be 25 mm x 30 mm, and the adhesive layer was maintained at 0.2 mm intervals using glass beads. Each adhesive composition was applied to the substrate and cured at 180° C. for 20 minutes to form an adhesive layer.

A 45 kg weight was freely dropped on the adhesive layer of the specimen at a height of 1.5 m under a temperature of -40°C to measure and evaluate the impact/peel strength of each adhesive layer.

(2) Shear strength (adhesive strength) test

The same specimen as in the impact/peel strength test was prepared.

After leaving the specimen at 23 °C and 60 RH for one week, the shear strength (adhesive strength) of the adhesive layer was measured 5 times at 23 °C under the condition of 10 mm/min, and the average value was taken.

Impact strength (-40 °C; unit: N/mm) Shear strength (23 °C; unit: MPa) Example 1 30 25 Example 2 33 27 Comparative Example 1 Intensity is so low that it cannot be measured 25 Comparative Example 2 5 12 Comparative Example 3 Intensity is so low that it cannot be measured 22

Referring to Table 2, it was confirmed that the adhesive layer formed of the composition of Examples exhibits very excellent impact strength even at a low temperature of -40°C, and exhibits room temperature adhesive strength equal to or higher than that of Comparative Examples.

In contrast, it was confirmed that the adhesive layer formed of the composition of Comparative Example exhibits very poor impact/peel strength at low temperatures.

Claims (19)

15 to 60 wt% of a silane-modified epoxy resin;
5 to 40% by weight of liquid rubber;
2 to 35 wt% of a polyurethane resin including a polymer block derived from polytetrahydrofuran; and
1.5 to 10 wt% of a thermosetting agent curable at a temperature of 80 °C or higher
A thermosetting adhesive composition comprising a.
The method of claim 1,
Further comprising an epoxy resin, thermosetting adhesive composition.
3. The method of claim 1 or 2,
The silane-modified epoxy resin and the epoxy resin include at least one selected from the group consisting of a bisphenol-based epoxy resin, a novolak-based epoxy resin, and an oxazolidone-based epoxy resin, a thermosetting adhesive composition.
3. The method of claim 2,
The epoxy resin is a thermosetting adhesive composition having an epoxy equivalent of 170 to 600.
The thermosetting adhesive composition according to claim 1, wherein the silane-modified epoxy resin is an epoxy resin and an alkoxysilane group represented by the following formula (1) is bonded:
[Formula 1]
-R ² -Si(R ¹ ) ₃
In Formula 1,
R ¹ is each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, at least one is an alkoxy group having 1 to 6 carbon atoms,
R ² is a single bond or an alkylene group having 1 to 10 carbon atoms.
The method of claim 5, wherein in Formula 1, R ¹ is each independently a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group, at least one is a methoxy group, an ethoxy group or a propoxy group,
R ² is a propylene group, a butylene group, a 2,2-dimethylpropylene group, a 2,2-dimethylbutylene group, or a 3,3-dimethylbutylene group, the thermosetting adhesive composition.
The method of claim 1,
The liquid rubber is a reaction product of a butidiene or butadiene-acrylonitrile copolymer and an epoxy resin, a thermosetting adhesive composition.
The method of claim 1,
The polyurethane resin has a polymer block derived from polytetrahydrofuran, a residue derived from a polyvalent aliphatic isocyanate, and a repeating unit including a urethane linkage connecting them, a thermosetting adhesive composition.
9. The method of claim 8,
The polyurethane resin further comprises a residue derived from alkylene glycol having 2 to 5 carbon atoms, thermosetting adhesive composition.
9. The method of claim 8,
The polyurethane resin is a heat-curable adhesive composition, wherein the terminal isocyanate group is end-capped with an amine compound, an alcohol compound, a phenol compound, an oxime compound, or a bisphenol compound.
9. The method of claim 8,
The polyvalent aliphatic isocyanate comprises at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and methylenedicyclohexyl diisocyanate, heat-curable adhesive composition.
9. The method of claim 8,
The polytetrahydrofuran has an OH equivalent of 400 to 2200,
The polyurethane resin has a weight average molecular weight of 5000 to 500000 g / mol,
A thermosetting adhesive composition.
The method of claim 1,
The thermal curing agent is a dicyandiamide-based curing agent, a melamine-based curing agent, a diallylmelamine-based curing agent, a guanamine-based curing agent, an aminotriazole-based curing agent, a hydrazide-based curing agent, a cyanoacetamide-based curing agent, and an aromatic polyamine-based curing agent A thermosetting adhesive composition comprising at least one selected from the group consisting of.
delete The method of claim 1,
A curing catalyst, a general inorganic filler in the form of primary particles, a reactive diluent having a mono-epoxy group, a plasticizer, a non-reactive diluent, a coupling agent, a rheology modifier, and a thixotropic modifier further comprising at least one additive selected from the group consisting of thermosetting, adhesive composition.
applying the heat curable adhesive composition of claim 1 on a substrate; and
Forming an adhesive layer by thermally curing the applied composition at a temperature of 80° C. or higher
A method of manufacturing a structure comprising a.
A structure comprising a substrate and an adhesive layer comprising a cured product of the heat-curable adhesive composition of claim 1 .
18. The method of claim 17,
The substrate is made of wood, metal or plastic, the structure.
18. The method of claim 17,
The adhesive layer includes a binder layer in which a silane-modified epoxy resin is crosslinked through a thermal curing agent,
A structure comprising a liquid rubber dispersed in the binder layer, and a polyurethane resin.