KR102436000B1 - Two-part polyurethane adhesive composition - Google Patents

Abstract

The present invention relates to a two-component polyurethane adhesive composition having excellent adhesion even when the elongation is increased, and having excellent adhesion when bonding between the same material or different materials.

Description

Two-component polyurethane adhesive composition {TWO-PART POLYURETHANE ADHESIVE COMPOSITION}

The present invention relates to a two-part polyurethane adhesive composition.

Reducing vehicle weight can provide several benefits, such as faster acceleration and braking, and greater fuel economy.

Adhesives are replacing many types of mechanical bonds in automobile production, driven by the desire to minimize vehicle weight. In addition, metal parts are being replaced by lighter plastic and composite parts, for example plastics and plastic composites are currently being used as automotive body panels.

On the other hand, mechanical bonding systems used to hold metals may not be suitable for fixing plastics and composites, so some automotive OEMs are looking for a new type of adhesive that solves the above bonding problem to simplify the manufacturing process.

Polyurethanes are well known adhesives and are used to bond together various types of substrates, for example coated or uncoated glass, plastics, carbon fiber reinforced plastics or metals.

In the automotive industry, two-component polyurethane adhesives are used to manufacture or bond vehicle front and rear doors, roof modules, spoilers, trim parts, interior trims, or displays (including navigation and center information displays).

However, when a conventionally used polyurethane adhesive composition is used in an automobile exposed to a wide temperature range of about -40 to 100° C., peeling failure may occur due to the difference in the coefficient of thermal expansion (CTE) between dissimilar materials in the temperature range. have.

In order to prevent such a peeling defect, the cured adhesive material should have excellent elongation properties. In general, however, if the elongation property is excellent, there is a problem in that the adhesive strength is relatively lowered.

Therefore, in order to solve the above problems, the development of a new polyurethane adhesive composition having excellent adhesion even when the elongation is increased is required.

An object of the present invention is to provide a two-component polyurethane adhesive composition having excellent adhesion even when the elongation is increased, and having excellent adhesion when bonding between the same material or different materials.

In the present specification, a prepolymer formed by reacting a carbodiimide-modified diisocyanate with a polyether polyol; isocyanate; and a first solution including inorganic particles and a first polyol having 2 to 4 hydroxyl functional groups and a molecular weight of 1,000 or less; a second polyol having a hydroxyl functional group of 2 to 3 and a molecular weight of 2,000 to 10,000; polyether amines having 2 to 6 amine functional groups; and a second liquid including inorganic particles, wherein the elongation measured based on the ASTM D412 C type specimen specification by mixing and curing the first liquid and the second liquid is 50% or more, a two-component polyurethane adhesive composition is provided

Hereinafter, a two-component polyurethane adhesive composition according to a specific embodiment of the present invention will be described in more detail.

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "having" are intended to designate the presence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that the existence or addition of numbers, steps, elements, or combinations thereof is not precluded in advance.

Since the present invention may have various modifications and various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

According to one embodiment of the invention, a prepolymer formed by reacting a carbodiimide-modified diisocyanate with a polyether polyol; isocyanate; and a first solution including inorganic particles and a first polyol having 2 to 4 hydroxyl functional groups and a molecular weight of 1,000 or less; a second polyol having a hydroxyl functional group of 2 to 3 and a molecular weight of 2,000 to 10,000; polyether amines having 2 to 6 amine functional groups; and a second liquid including inorganic particles, wherein the elongation measured based on the ASTM D412 C type specimen specification by mixing and curing the first liquid and the second liquid is 50% or more, a two-component polyurethane adhesive composition can be provided.

The present inventors conducted a study on the polyurethane adhesive composition, the first liquid and the second liquid each contain the above-described components, and the first liquid and the second liquid are mixed and cured to form a specimen of ASTM D412 C type When the elongation measured based on the standard is 50% or more, it has excellent adhesion when bonding the same material or different materials, and has excellent adhesion even when the elongation increases because the decrease in adhesion due to the increase in elongation is small. and completed the invention.

The elongation measured based on the specimen specification of ASTM D412 C type by mixing and curing the first solution and the second solution may be 50% or more, or 55% or more, or 60% or more, or 65% or more, If the elongation measured based on the specimen specification of ASTM D412 C type by mixing and curing the 1st and 2nd solutions is less than 50%, there is a possibility that the adhesive peeling problem between dissimilar materials may occur.

Meanwhile, the carbodiimide-modified diisocyanate may be included in an amount of 5 to 25% by weight, or 8 to 22% by weight, or 10 to 20% by weight based on 100% by weight of the prepolymer.

If the carbodiimide-modified diisocyanate is less than 5% by weight based on 100% by weight of the prepolymer, there is a risk of a decrease in adhesive strength during bonding between the same or different materials, and if it exceeds 25% by weight, cracks in the cured product after curing As this occurs, adhesion may be reduced.

Meanwhile, the diisocyanate modified with carbodiimide may be methylene diphenyl diisocyanate modified with carbodiimide, for example, Cosmonate LL and LK from Kumho Mitsui, Lupranate MM103C from BASF and Dow Chemical's Isonate 143LP may be used.

Meanwhile, a prepolymer formed by reacting a carbodiimide-modified diisocyanate with a polyether polyol may have an isocyanate equivalent weight of 170 to 240, 2 or more isocyanate functional groups, and a molecular weight of 10,000 or less.

When the isocyanate equivalent of the prepolymer is less than 170, the cured product obtained by mixing and curing the first and second liquids tends to break, and when it exceeds 240, the elongation is excellent, but a phenomenon of reduced adhesion may occur.

The prepolymer may be included in an amount of 10 to 50% by weight, or 25 to 45% by weight based on the total adhesive composition, and when the prepolymer is included in the above content with respect to the total adhesive composition, the adhesive strength of the resulting adhesive can be maximized.

Meanwhile, the prepolymer is formed by reacting a carbodiimide-modified diisocyanate with a polyether polyol, wherein the polyether polyol has a molecular weight of 200 to 3,000 and a hydroxyl functional group of 2 to 3 polyethylene glycol, polypropylene glycol Or it may be at least one of polytetramethylene glycol.

For example, the polyethylene glycol may be PEG 400, PEG 700, PEG 1000, PEG 2000, etc., and the polypropylene glycol is PPG 400, PPG 700, PPG triol 700, PPG 1000, PPG 2000, PPG 3000 and PPG triol. 3000 may be used, and polytetramethylene glycol may be PTHF 400, PTHF 1000, PTHF 2000, or the like.

On the other hand, the prepolymer may be formed by further including one or more isocyanates of aromatic isocyanate, aliphatic isocyanate or derivatives thereof with diisocyanate and polyether polyol modified with carbodiimide.

At this time, the isocyanates that can be included include aromatic isocyanates and derivatives thereof such as 4,4-MDI, 4,2-MDI, 2,2-MDI or polymeric MDI, or aliphatic isocyanates and derivatives thereof such as 1,6-hexamethylene diisocyanate or isophoronediisocyanate. can be

On the other hand, the prepolymer may refer to a prepolymer in which isocyanate functional groups remain in excess, prepared by mixing isocyanate:polyol in an equivalent ratio of 5:1 to 15:1.

Meanwhile, the first solution includes the above-described prepolymer, isocyanate and inorganic particles, and the isocyanate may have an isocyanate equivalent weight of 80 to 240, an isocyanate functional group of 2 to 10, and a molecular weight of 1,500 or less.

At this time, the isocyanate is aromatic isocyanate such as 4,4-MDI, 4,2-MDI, 2,2-MDI, MDI modified with carbodiimide, and derivatives thereof, or aliphatic isocyanate such as 1,6-hexamethylene diisocyanate, isophoronediisocyanate, etc. and derivatives thereof.

The isocyanate may be included in an amount of 0.1 to 25% by weight, or 1 to 20% by weight based on the total adhesive composition, and when the isocyanate is included in the above content with respect to the entire adhesive composition, the adhesive strength of the resulting adhesive can be maximized.

At this time, when the isocyanate content exceeds 25% by weight based on the total adhesive composition, there is a risk of cracking in the specimen after curing.

Meanwhile, the second solution includes a first polyol having 2 to 4 hydroxyl functional groups and a molecular weight of 1,000 or less, and the first polyol may have a hydroxyl equivalent of 30 to 250.

In addition, the first polyol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetramethylene glycol, hexamethylene glycol monomer, dimer, trimer, oligomer or neopentyl glycol ( neopentyl glycol), trimethylolpropane, pentaerythritol, or at least one of their derivatives.

In addition, the first polyol may be included in an amount of 0.1 to 10% by weight, or 1 to 5% by weight based on the total adhesive composition. can be maximized.

In addition, the second solution includes a second polyol having a hydroxyl functional group of 2 to 3 and a molecular weight of 2,000 to 10,000, and the second polyol may have a hydroxyl equivalent of 500 to 5,000.

In addition, the second polyol may include a polyether polyol selected from ethylene oxides, propylene oxides, homopolymers, copolymers of tetramethylene oxides, or polypropylene oxides capped with ethylene oxide.

For example, as the second polyol, PEG 2000, PPG 2000, PPG 3000, PPG triol 3000, PPG 5000, PPG triol 5000, PPG 7000, PPG triol 7000, PTHF 2000, PTHF 3000, PTHF 5000, etc. may be used, In the case of PPG, FA-505, FA-703 from KPX, or Voranol 4701 from Dow Chemical may also be used in a form capped with ethylene glycol at the end.

On the other hand, the second polyol may be included in an amount of 20 to 50% by weight, or 25 to 45% by weight based on the total adhesive composition, and when the second polyol is included in the above content with respect to the total adhesive composition, the adhesive strength of the resulting adhesive is can be maximized.

Meanwhile, the second liquid includes polyether amine having an amine functional group of 2 to 6, and the polyether amine may have an amine equivalent weight of 20 to 1,000.

In addition, the polyether amine may be a polymer in which the amine is substituted with polyethylene oxides or polypropylene oxides, for example, the polyether amine is Huntsman's Jeffamine D-230, D-400, D-2000, HK -511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, T-403 and T-3000 and the like can be used.

On the other hand, the polyether amine may be included in an amount of 0.1 to 10% by weight, or 0.2 to 5% by weight based on the total adhesive composition, and when the polyether amine is included in the amount relative to the total adhesive composition, the adhesive strength of the resulting adhesive can be maximized.

On the other hand, the two-component polyurethane adhesive composition of the embodiment includes inorganic particles, and the inorganic particles are selected from the group consisting of calcium carbonate, calcium oxide, talc, kaolin, carbon black, titanium dioxide, molecular sieve, glass beads and silica. There may be more than one type.

In addition, the inorganic particles may include one or more particles having a size of 0.1 μm or less, one or more particles having a size of 0.1 to 5 μm, and one or more particles having a size of 5 to 20 μm, respectively. .

In this case, the inorganic particles may be used to control the mechanical properties and rheological properties of the above-described two-component polyurethane adhesive composition, and may have a structure such as an angular shape, a spherical shape, a plate shape, and a needle shape.

For example, inorganic silica particles can be used to control thixotropic properties, and the silica particles can be hydrophobic or hydrophilic, and can be formed in angular, spherical, plate-like or needle-like shapes of fumed silica, fused silica and hollow silica. can be a structure.

The inorganic particles may be included in an amount of 10 to 40% by weight, or 15 to 35% by weight based on the total adhesive composition, and when the inorganic particles are included in the above content with respect to the total adhesive composition, the adhesive strength of the resulting adhesive can be maximized. .

On the other hand, the two-component polyurethane adhesive composition of the embodiment may further include a urethane curing catalyst, and the urethane curing catalyst may be included in the second liquid of the adhesive composition.

The urethane curing catalyst is, for example, a tin catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and dibutyltin dimercaptide, a bismuth catalyst such as bismuth tris(2-ethylhexanoate), 1,4-diazabicyclo[2.2.2]octane (DABCO) ), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), etc. or 1,8-diaza bicyclo An amine salt such as [5.4.0]undec-7-ene/phenol salt or 1,8-diazabicyclo[5.4.0]undec-7-ene/2-ethylhexanoic acid salt may be used.

In this case, when a metal catalyst is used as the urethane curing catalyst, it is more preferable to use an amine catalyst or an amine salt mixed with the metal catalyst to control the working time.

On the other hand, when the two-component polyurethane adhesive composition includes a urethane curing catalyst, the content of the urethane curing catalyst may be 0.01 to 2% by weight, or 0.02 to 1% by weight based on the total adhesive composition.

In addition, when a metal catalyst is used as the urethane curing catalyst, the content of the metal catalyst may be 0.01 to 0.5% by weight, or 0.02 to 0.3% by weight based on the total adhesive composition.

On the other hand, the two-component polyurethane adhesive composition of the embodiment may further include other general adjuvants or additives.

The auxiliary or additive includes, for example, a plasticizer, a coupling agent, a flow control agent, a thixotropic agent or a defoamer, and BYK-067A may be used as an example of the defoamer.

The adjuvant or additive may be included in an amount of 0.001 to 5% by weight based on the total adhesive composition.

On the other hand, the two-component polyurethane adhesive composition of the embodiment includes the first liquid and the second liquid of the above-described components, wherein the thixotropic index (TI) of the first liquid may be 3 to 7, The thixotropic index of the two liquids may be 4 to 10.

The thixotropic indices of the first liquid and the second liquid may have different or identical values, respectively, and in this case, the thixotropic index of the second liquid may have a wider range than the thixotropic index of the first liquid.

When the thixotropic index of the first solution is 3 to 7, the phase separation phenomenon between the organic material and the inorganic material does not occur, and thus storage stability may be increased. Similarly, the thixotropic index of the second solution is 4 to 10 In this case, the phase separation phenomenon between the organic material and the inorganic material does not occur, and thus storage stability may be increased.

In addition, the thixotropic index values of the first solution: the second solution may be 1.0:0.6 to 1.0:3.3.

When the thixotropic index value of the first solution: the second solution is less than 1.0:0.6 or exceeds 1.0:3.3, it may be difficult to mix when the first solution and the second solution are mixed.

On the other hand, the volume ratio of the first liquid to the second liquid in the two-component polyurethane adhesive composition may be 40:60 to 60:40, or 45:55 to 55:45.

When the volume ratio of the first solution: the second solution is less than 40:60, there is a risk of lowering the adhesive strength after curing, and when it exceeds 60:40, there may be a problem in that the cured product is cracked.

Meanwhile, when the first and second liquids are mixed and cured to bond substrates of two different components selected from iron, carbon fiber reinforced plastic (CFRP), magnesium, glass, and polycarbite, their adhesive strength is 10 MPa or more, or 11 MPa or more, or 12 MPa or more.

The two-component polyurethane adhesive composition of the embodiment may have excellent adhesion when bonding the same material or different materials, specifically, two types of iron, carbon fiber reinforced plastic (CFRP), magnesium, glass, and polycarbite selected from When bonding between dissimilar materials, it may have an adhesive strength of 10 MPa or more.

At this time, the adhesive force may mean peel strength, and can be measured by the lap shear strength method based on DIN EN ISO 1465.

For example, after preparing a lap specimen of 100 mm x 25 mm x 1.6T for a substrate of two different components selected from iron, carbon fiber reinforced plastic (CFRP), magnesium, glass and polycarbite, the embodiment of The two-component polyurethane adhesive composition is applied to an area of 10 mm x 25 mm, and after curing at 70° C. for 1 hour, the adhesive force between each material can be measured using Instron's UTM (Universal Test Machine) equipment.

The two-component polyurethane adhesive composition of the above embodiment can generally be cured at about 50 to 100 °C, and sometimes can be cured at room temperature.

On the other hand, the two-component polyurethane adhesive composition of the above embodiment may be used to manufacture or combine a vehicle front/rear door, a roof module, a spoiler, a trim part, an interior interior material, or a display, wherein the display is used for navigation and CID (Center Information Display) ) may be included.

In addition, the two-component polyurethane adhesive composition of the embodiment is wood, cold-rolled steel sheet, electro-galvanized steel sheet, hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel sheet, zinc/nickel/magnesium coated steel sheet, aluminum, aluminum alloy, magnesium, magnesium Alloys, carbon fiber reinforced polymer (CFRP), glass fiber reinforced polymer (GFRP), carbon-containing sheet molding compound (SMC), glass-containing sheet molding compound, various plastic materials other than PC, PET, or glass materials can be used for bonding. can

According to the present invention, there can be provided a two-component polyurethane adhesive composition having excellent adhesion even when the elongation is increased, and having excellent adhesion when bonding between the same material or different materials.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

Synthesis Example 1: Synthesis of Prepolymer 1

In a polymerization reactor substituted with nitrogen, polymeric MDI (Lupranate M20S, BASF) 137.74 g, methylene diphenyl diisocyanate modified with carbodiimide (Cosmonate LL, Kumho Mitsui) 35.02 g, PPG 700 (triol, Mn=700, KPX) G) 12.51 g and PPG 1000 (diol, Mn=1,000, KPX) 50.03 g were added and heated to synthesize prepolymer 1.

The equivalent ratio of isocyanate: polyol, the content of methylene diphenyl diisocyanate modified with carbodiimide, and the isocyanate equivalent of the synthesized prepolymer 1 are as follows.

* NCO/OH equivalent ratio = 8.2

* Carbodiimide modified MDI: 15 wt%

* Prepolymer 1 NCO equivalent: 213 g/eq.

* NCO Reactor: Confirmed by 2270cm-1 peak of IR spectrum

Synthesis Example 2: Synthesis of Prepolymer 2

In a polymerization reactor substituted with nitrogen, polymeric MDI (Lupranate M20S, BASF) 144.74 g, methylene diphenyl diisocyanate modified with carbodiimide (Cosmonate LL, Kumho Mitsui) 36.81 g and PPG 1000 (diol, Mn=1,000, KPX) g) 80.52 g was added and heated to synthesize prepolymer 2.

The equivalent ratio of isocyanate:polyol, the content of methylene diphenyl diisocyanate modified with carbodiimide, and the isocyanate equivalent of the synthesized prepolymer 2 are as follows.

* NCO/OH equivalent ratio = 8.2

* Carbodiimide modified MDI: 14 wt%

* Prepolymer 2 NCO equivalent: 226 g/eq.

* NCO Reactor: Confirmed by 2270cm-1 peak of IR spectrum

Synthesis Example 3: Synthesis of Prepolymer 3

In a polymerization reactor substituted with nitrogen, polymeric MDI (Lupranate M20S, BASF) 144.74 g, carbodiimide-modified methylene diphenyl diisocyanate (Cosmonate LL, Kumho Mitsui) 36.81 g and PPG 2000 (diol, Mn=2,000, KPX) g) Prepolymer 3 was synthesized by adding 93.18 g and heating.

The equivalent ratio of isocyanate: polyol, the content of methylene diphenyl diisocyanate modified with carbodiimide, and the isocyanate equivalent of the synthesized prepolymer 3 are as follows.

* NCO/OH equivalent ratio = 14.2

* Carbodiimide modified MDI: 13 wt%

* Prepolymer 3 NCO equivalent: 223 g/eq.

* NCO Reactor: Confirmed by 2270cm-1 peak of IR spectrum

Comparative Synthesis Example 1: Synthesis of Prepolymer A

Polymeric MDI (Lupranate M20S, BASF) 109.85 g in a nitrogen-substituted polymerization reactor, methylene diphenyl diisocyanate modified with carbodiimide (Cosmonate LL, Kumho Mitsui) 88.82 g, PPG 2000 (diol, Mn=2,000, KPX) g) 101.43 g was added and heated to synthesize prepolymer A.

* NCO/OH equivalent ratio = 14.3

* Carbodiimide modified MDI: 30 wt%

* Prepolymer A NCO equivalent: 226 g/eq.

* NCO Reactor: Confirmed by 2270cm-1 peak of IR spectrum

Comparative Synthesis Example 2: Synthesis of Prepolymer B

Polymeric MDI (Lupranate M20S, BASF Corporation) 60.42g, carbodiimide-modified methylene diphenyl diisocyanate (Cosmonate LL, Kumho Mitsui Corporation) 141.19g, PPG 1000 (diol, Mn=1,000, KPX) in a nitrogen-substituted polymerization reactor G) 15.91 g and PPG 2000 (diol, Mn=2,000, KPX) 100.49 g were added and heated to synthesize prepolymer B.

* NCO/OH equivalent ratio = 10.7

* Carbodiimide modified MDI: 44 wt%

* Prepolymer B NCO equivalent: 247 g/eq.

* NCO Reactor: Confirmed by 2270cm-1 peak of IR spectrum

Comparative Synthesis Example 3: Synthesis of Prepolymer C

Polymeric MDI (Lupranate M20S, BASF) 62.76g, liquid MDI (MI, BASF) 126.35g, PPG 1000 (diol, Mn=1,000, KPX) 16.53g and PPG 2000 (diol, Mn) in a nitrogen-substituted polymerization reactor = 2,000, KPX) 104.38 g was added and heated to synthesize prepolymer C.

* NCO/OH equivalent ratio = 10.7

* Carbodiimide modified MDI: not used

* Prepolymer C NCO equivalent: 233 g/eq.

* NCO Reactor: Confirmed by 2270cm-1 peak of IR spectrum

Example: Preparation of two-component polyurethane adhesive composition

According to the composition of Table 1 below, each component was mixed to prepare a two-component polyurethane adhesive composition of Examples 1 to 3 and Comparative Examples 1 to 3, respectively.

(1) Preparation of the first solution

First, the synthesized prepolymer, isocyanate and inorganic particles were put in a planetary mixer and mixed at 30 °C for 2 hours. After defoaming, one side of the 50ml two-component cartridge was filled with about 20ml.

(2) Preparation of the second liquid

The first polyol, the second polyol, polyetheramine and inorganic particles were put in a planetary mixer and mixed at 30 °C for 2 hours. A curing catalyst was added, and the mixture was further mixed for an additional 1 hour and then degassed. About 20ml was filled in the other side of the 50ml two-component cartridge.

(3) Preparation of two-component polyurethane adhesive composition

After filling both sides of the 50ml two-component cartridge, it was further defoamed at room temperature for about 30 minutes and then stored in a constant temperature/humidity room.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Prepolymer 1 37 Prepolymer 2 33 Prepolymer 3 33 Prepolymer A 38 Prepolymer B 33 Prepolymer C 33 MI ¹ 5 5 Desmodur N3400 ² 5 5 FA-505 ³ 37 35 35 34 34 34 Trimethylolpropane 2 3 3 3 3 3 Polyetheramine ⁴ 3 3 3 4 4 4 UCAT SA-1 ⁵ One One 0.7 One One 0.7 DABCO T-12 ⁶ 0.3 0.3 Kaolin ⁷ 10 10 10 10 10 10 Fumed Silica ⁸ 2.9 2.9 2.9 2.9 2.9 2.9 molecular sieve ⁹ 7 7 7 7 7 7 Carbon Black ¹⁰ 0.1 0.1 0.1 0.1 0.1 0.1

1: BASF's liquid MDI2: Covestro's HDI dimer

3: KPX EO capped PPG triol

4: Huntsman Jeffamine D-400

5: San-Apro DBU/Phenol salt

6: Air Products dibutyltin dilaurate

7: Imerys 3 micron size

8: Aerosil 200 from Evonik

9: Grace Sylosiv A3, 6-9 micron size

10: Cabot Monarch 280

<Experimental example>

The elongation and adhesion of the cured product after curing of the two-component polyurethane adhesive composition according to the Examples and Comparative Examples were measured as follows, and the results are shown in Table 2 below.

1. Measurement of elongation of cured product

After connecting a 24-stage cartridge mixer to a 50ml two-component cartridge, squeeze out an initial amount of about 5ml and discard it. After that, the 1T thick Teflon mold was well filled to prevent air bubbles from entering, and the cover was covered and cured at 70° C. for 1 hour. Dog bone was prepared by cutting the hardened specimen to ASTM D412 C type size. Stable Micro Systems' Texture Analyzer equipment was used to measure elongation of the cured product.

2. Adhesion Measurement

After connecting a 24-stage cartridge mixer to a 50ml two-component cartridge, squeeze out an initial amount of about 5ml and discard it. Thereafter, 100mm x 25mm x 1.6T lap specimens were prepared for various types of substrates, applied to an area of 10mm x 25mm, and the thickness was adjusted using 0.2mm glass beads. After curing at 70° C. for 1 hour, the adhesion between each material was measured using Instron's UTM (Universal Test Machine) equipment.

elongation
(%) Steel-Steel
(MPa) Al-Al
(MPa) CFRP-CFRP
(MPa) Steel-CFRP
(MPa) Mg-Glass
(MPa) PC-Glass
(MPa) Example 1 65 19 17 23 20 15 17 Example 2 95 17 14 20 17 12 17 Example 3 110 15 14 18 15 12 15 Comparative Example 1 65 9 7 11 11 6 6 Comparative Example 2 55 11 9 13 10 6 5 Comparative Example 3 90 7 5 8 9 5 4

As shown in Table 2, it was confirmed that the two-component polyurethane adhesives of Examples 1 to 3 had excellent adhesive strength when bonding between the same type and different materials even when the elongation was increased.

Claims (18)

a prepolymer formed by reacting one or more isocyanates of aromatic isocyanates, aliphatic isocyanates or derivatives thereof, diisocyanates modified with carbodiimides and polyether polyols; isocyanate; and a first liquid containing inorganic particles and
a first polyol having 2 to 4 hydroxyl functional groups and a molecular weight of 1,000 or less; a second polyol having a hydroxyl functional group of 2 to 3 and a molecular weight of 2,000 to 10,000; polyether amines having amine functional groups of 2 to 6; and a second liquid containing inorganic particles,
The carbodiimide-modified diisocyanate contains 10 to 20 wt% based on 100 wt% of the prepolymer,
By mixing and curing the first liquid and the second liquid, the elongation measured based on the specimen specification of ASTM D412 C type is 50% or more,
When the first and second liquids are mixed and cured to bond substrates of two different components selected from iron, carbon fiber reinforced plastic (CFRP), magnesium, glass, and polycarbite, their adhesive strength is 10 MPa or more ,
A two-component polyurethane adhesive composition.
delete According to claim 1,
The carbodiimide-modified diisocyanate is methylene diphenyl diisocyanate modified with carbodiimide (carbodiimide modified MDI), a two-component polyurethane adhesive composition.
According to claim 1,
The prepolymer has an isocyanate equivalent weight of 170 to 240, 2 or more isocyanate functional groups, and a molecular weight of 10,000 or less, a two-part polyurethane adhesive composition.
According to claim 1,
The polyether polyol is at least one of polyethylene glycol, polypropylene glycol or polytetramethylene glycol having a molecular weight of 200 to 3,000 and a hydroxyl functional group of 2 to 3, a two-component polyurethane adhesive composition.
According to claim 1,
The isocyanate has an isocyanate equivalent weight of 80 to 240, an isocyanate functional group of 2 to 10, and a molecular weight of 1,500 or less, a two-part polyurethane adhesive composition.
According to claim 1,
wherein the first polyol has a hydroxyl equivalent weight of 30 to 250, the second polyol has a hydroxyl equivalent weight of 500 to 5,000, and the polyether amine has an amine equivalent weight of 20 to 1,000. .
According to claim 1,
The first polyol is a monomer, dimer, trimer, oligomer or neopentyl glycol, trimethylol of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetramethylene glycol, hexamethylene glycol. A two-part polyurethane adhesive composition comprising at least one of propane, pentaerythritol and derivatives thereof.
According to claim 1,
The second polyol comprises a polyether polyol selected from ethylene oxides, propylene oxides, homopolymers, copolymers of tetramethylene oxides, or polypropylene oxides capped with ethylene oxide, two-component polyurethane adhesive composition.
According to claim 1,
The polyether amine is a polymer in which the amine is substituted with polyethylene oxides or polypropylene oxides, a two-component polyurethane adhesive composition.
According to claim 1,
The inorganic particles include at least one selected from the group consisting of calcium carbonate, calcium oxide, talc, kaolin, carbon black, titanium dioxide, molecular sieves, glass beads and silica, two-component polyurethane adhesive composition.
According to claim 1,
The inorganic particle is a two-component polyurethane adhesive composition comprising at least one particle having a size of 0.1 μm or less, 0.1 to 5 μm, and 5 to 20 μm, respectively.
According to claim 1,
A two-component polyurethane adhesive composition further comprising a urethane curing catalyst.
According to claim 1,
Thixotropic Index (TI) of the first liquid is 3 to 7, two-component polyurethane adhesive composition.
According to claim 1,
The thixotropic index (TI) of the second liquid is 4 to 10, a two-component polyurethane adhesive composition.
According to claim 1,
The volume ratio of the first liquid: the second liquid is 40:60 to 60:40, a two-component polyurethane adhesive composition.
delete According to claim 1,
A two-part polyurethane adhesive composition for use in manufacturing or bonding vehicle front/rear doors, roof modules, spoilers, trim parts, interior upholstery or displays.