KR102564475B1 - Composition of dismantlable two component type polyurethane adhesives with high mechanical properties and adhesion strength and its dismantlement method - Google Patents

Abstract

The present invention relates to a disassembly two-component structural polyurethane adhesive composition with improved mechanical properties and adhesive strength and a disassembly method thereof, and more specifically, to a resin mix including an acid polyol, a free polymer ( prepolymer) to prepare a two-component structural polyurethane adhesive composition, which has excellent adhesive strength and mechanical properties between two adherends at the operating temperature, but has disassembly properties that allow the two adherends to be easily separated when heated using an oven It relates to a detachable two-component structural polyurethane adhesive composition with improved mechanical properties and adhesive strength, and a disassembly method thereof.

Description

Dismantling two-component structural polyurethane adhesive composition with improved mechanical properties and adhesive strength and its disassembly method

The present invention provides a two-component structural polyurethane adhesive composition that has excellent adhesive strength and mechanical properties between two adherends at a use temperature, but has a disassembly property that easily separates the two adherends when heated using an oven, and its disassembly It's about how.

In general, automotive adhesives are classified into structural adhesives, non-structural anti-vibration adhesives, and sealants, and adhesives having a shear strength of 10 MPa or more are generally referred to as structural adhesives. The purpose is to bond material to material via adhesives, ultimately reducing the use of welding and rivets (reducing overall weight).

On the other hand, the importance of the environment has recently been greatly recognized worldwide, and environmental protection movements and various related laws have been enacted in the form of international agreements, etc. Research is actively progressing. In addition, advanced countries including Europe mandate recycling of automobile parts, and it is important to develop adhesive technology for recycling and reuse of heterojunction materials in order to respond to these regulations.

In this regard, automotive parts are mostly joined with many constituent materials, and among the bonding methods, bonding using an adhesive is widely used because it is simple and economical in combining materials of the same material or different materials. However, parts bonded with adhesive are difficult to dismantle, so there is a problem in that the materials cannot be separated and recovered.

Therefore, if parts bonded by adhesive can be easily separated when necessary, it will be much easier to reuse the combined materials and environmental pollution can be reduced, so the demand for detachable adhesives is increasing.

On the other hand, in detachable adhesives, detachability means that when certain conditions (heating, chemical treatment, etc.) are applied, the adhesive that has been solidified and adhered is softened or decomposed so that the adherend can be easily separated. It means that the adherend can be recycled.

Patent Document 1 as a related art, a first component consisting of an isocyanate compound having a content of 10 to 60% by weight relative to the total composition; And without contact with the first component before use, i) 10 to 40% by weight of a polyol compound, ii) 5 to 30% by weight of a colored pigment, iii) glycidyl ester-based resin, epoxy novolak-based, respectively, based on the total composition 5 to 40% by weight of an elastic resin composed of resin or bisphenol A novolak-based resin, iv) 0.01 to 10% by weight of a filler, and dibutyl tin dilaurate (DBTL) as a first hardening accelerator for promoting room temperature curing, and A two-component polyurethane adhesive composition including a second component consisting of 5 to 20% by weight of v) a hardening accelerator containing an amine-based compound as a second hardening accelerator for high-temperature curing acceleration has been proposed.

And in Patent Document 2, 30 to 50 parts by weight of polyether polyol, 40 to 60 parts by weight of castor oil, 5 to 15 parts by weight of silica, and 0.001 to 0.003 parts by weight of catalyst based on 100 parts by weight of the environmentally friendly filler are added to the mixer; Stirring the environmentally friendly filler, polyether polyol, castor oil, silica, and dibutyl tin dilaurate (DBTDL) in the mixer; Preparing a subject by heat-treating the stirred eco-friendly filler, polyether polyol, castor oil, silica and DBTDL (Dibutyl Tin Dilaurate) in a vacuum at 100 ° C to 200 ° C to remove moisture and defoaming; Preparing a curing agent composed of 100 parts by weight of diphenylmethane diisocyanate (polymeric: POLYMERIC) containing methylene bisphenyl having a molecular weight of about 350 to 400; and mixing the prepared subject matter and the curing agent in a ratio of 4:1 to 6:1 to complete the composition.

However, the conventional two-component urethane-based adhesive has a problem of not having disassembly.

In order to solve this problem, in Patent Document 3, 100 parts by weight of an ester-based polyol and 10 to 60 parts by weight of diisocyanate are maintained in order to maintain excellent adhesion at ordinary times and to enable separation of the adhesive portion through a simple operation using microwaves when necessary. Disintegrable polyurethane prepared by mixing 2 to 10 parts by weight of a chain extender, 10 to 30 parts by weight of a chemical foaming agent, 1 to 8 parts by weight of a nanometal filler, 2.5 to 30 parts by weight of a decomposition promoter, and a solvent The composition of the adhesive and its disassembly method were proposed.

In contrast, the applicant of the present invention has a two-component structural polyurethane adhesive composition that not only has disassembly realized with higher efficiency than the prior art, but also has excellent adhesive strength and mechanical properties between two adherends at a use temperature. And the present invention was completed by developing a disassembly method thereof.

Patent Document 1: Korean Patent Registration No. 10-1666464 "Two-component Polyurethane Adhesive Composition" Patent Document 2: Republic of Korea Patent Registration No. 10-1212040 "Method for producing two-component non-solvent urethane adhesive composition and composition prepared thereby" Patent Document 3: Republic of Korea Patent Registration No. 10-1222112 "Composition of detachable polyurethane adhesive and disassembly method thereof"

The present invention prepares a two-component structural polyurethane adhesive composition by mixing a resin mix containing acid polyol with a pre-polymer, thereby providing excellent adhesive strength and It has mechanical properties, but the task is to have disassembly so that the two adherends are easily separated when heated using an oven.

In the two-component structural polyurethane adhesive composition of the present invention, a resin mix is mixed with a free polymer, the resin mix is composed of an acid polyol, and the free polymer is 30 to 40% by weight of polycaprolactone diol and diphenyl 60 to 70% by weight of methane diisocyanate, and based on 100 parts by weight of the free polymer, the resin mix contains 18.4 to 25.8 parts by weight of polycaprolactone diol, 13 to 14 parts by weight of polycaprolactone triol, and 0.85 parts by weight of the acid polyol. ~ 21.9 parts by weight, trimethylolpropane tris [poly(propylene glycol), amine terminated] ether 1 ~ 2 parts by weight, 1,4-butanediol 6 ~ 7 parts by weight, zinc oxide 0.31 ~ 0.54 parts by weight and calcium carbonate 0.16 ~ 0.17 part by weight is mixed, and the acid polyol is DMBA (2,2-Bis (hydroxymethyl) butyric acid) 14.8 ~ 15.8 mol parts and DMPA (2,2-Bis (hydroxy-methyl) propionic acid) 13.41 ~ 14.41 mol parts And BES (N, N-bis (2-hydroxyethyl) -2- aminoethanesulfonic acid) 21.31 ~ 22.32 parts by mole, any one of 91 ~ 280 parts by mole of polytetramethylene glycol (PTMG) and diphenyl methanediisocyanate , MDI) 30 to 31 molar parts, a detachable two-component structural polyurethane adhesive composition with improved mechanical properties and adhesive strength is used as a solution to the problem.

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On the other hand, in the disassembly method of the disassembly two-component structural polyurethane adhesive composition of the present invention, it is preferable to disassemble by heating at 200 to 250° C. using an oven.

The present invention has an effect of having excellent adhesive strength and mechanical properties between two adherends at a use temperature, but having disassembly properties in which the two adherends can be easily separated when heated using an oven.

The present invention for achieving the above effects relates to a detachable two-component structural polyurethane adhesive composition with improved mechanical properties and adhesive strength and a disassembly method thereof, and only parts necessary for understanding the technical configuration of the present invention are described, and other It should be noted that the description of parts will be omitted so as not to obscure the subject matter of the present invention.

Hereinafter, a detachable two-component structural polyurethane adhesive composition having improved mechanical properties and adhesive strength and a disassembly method thereof according to the present invention will be described in detail.

The present invention is characterized in that a resin mix is mixed with a pre-polymer, and the resin mix is composed of an acid polyol.

The free polymer is a basic base material of the adhesive according to the present invention and is composed of 30 to 40% by weight of polycaprolactone diol and 60 to 70% by weight of diphenyl methanediisocyanate (MDI).

Wherein, the content of polycaprolactone diol is less than 30% by weight and the content of diphenylmethane diisocyanate exceeds 70% by weight, or the content of polycaprolactone diol exceeds 40% by weight and the content of diphenylmethane diisocyanate If it is less than 30% by weight, there is a concern that the free polymer may not be properly synthesized or the yield of urethane synthesis may decrease.

The resin mix is for imparting properties of a structural adhesive, and based on 100 parts by weight of the free polymer, 18.4 to 25.8 parts by weight of polycaprolactone diol and 13 to 14 parts by weight of polycaprolactone triol Part, acid polyol 0.85 ~ 21.9 parts by weight, trimethylolpropane tris [poly (propylene glycol), amine terminated] ether (Trimethylolpropane tris [poly (propylene glycol), amine terminated] ether) 1 ~ 2 parts by weight, 1, 4-butanediol (1,4-Butanediol) 6 to 7 parts by weight, zinc oxide (ZnO) 0.31 to 0.54 parts by weight and calcium carbonate (CaCO ₃ ) 0.16 to 0.17 parts by weight is mixed.

Here, if the composition of each material constituting the resin mix is out of the above range, there is a concern that the properties of the adhesive may not be properly imparted or disassembly may not be obtained.

On the other hand, the acid polyol included in the resin mix is added to the two-component structural polyurethane adhesive composition to improve mechanical properties and adhesive strength, and to impart efficient disassembly, DMBA (2,2-Bis(hydroxymethyl)butyric acid ) 14.8 ~ 15.8 molar parts, DMPA (2,2-Bis (hydroxy-methyl) propionic acid) 13.41 ~ 14.41 molar parts, and BES (N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid) 21.31 ~ 22.32 molar parts 91 to 280 parts by mole of polytetramethylene glycol (PTMG) and 30 to 31 parts by mole of diphenyl methanediisocyanate (MDI).

Here, when the composition of each material constituting the acid polyol is out of the above respective ranges, there is a concern that mechanical properties, adhesive strength and disassembly properties may be insufficient.

Meanwhile, in the present invention, an oven is used as a method for disassembling the disassembly two-component structural polyurethane adhesive composition.

More specifically, it is dismantled by heating to 200 ~ 250 ℃ using an oven, and the oven is not limited to a specific product, and various types of ovens already known that may have the above temperature range can be applied. On the other hand, if the temperature range is out of the above range, there is a concern that the disassembly efficiency is lowered.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.

1. Preparation of acid polyols

(Production Examples 1 to 6)

Acid polyols were prepared with the compositions shown in [Table 1] and [Table 2] below.

(unit: parts by mole) division Preparation Example 1 Preparation Example 2 Preparation Example 3 DMBA 14.8 - - DMPA - 13.41 - BES - - 21.32 PTMG 280 140 91 MDI 30 30 30

(unit: parts by mole) division Production Example 4 Preparation Example 5 Preparation Example 6 DMBA 15.8 - - DMPA - 14.41 - BES - - 22.32 PTMG 280 140 91 MDI 30 30 30

2. Preparation of two-component structural polyurethane adhesive

(Examples 1 to 26, Comparative Example 1)

A two-component structural polyurethane adhesive was prepared by mixing the compositions shown in [Table 3] to [Table 8] below as a resin mix with respect to 100 parts by weight of the free polymer. At this time, in the case of the prepolymer, in Examples 1 to 13, a prepolymer composed of 30% by weight of polycaprolactone diol and 70% by weight of diphenylmethane diisocyanate was used, and in Examples 14 to 26, 40% by weight of polycaprolactone diol and diphenyl A prepolymer consisting of 60% by weight of methane diisocyanate was used.

(unit: parts by weight) division Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 polycaprolactone
Dior 26 25 22.2 18.4 22.2 22.2 polycaprolactone
triol 13 13 13 13 13 13 According to Preparation Example 1
acid polyol - 3.5 11.5 21.9 11.5 11.5 Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether One One One One One One 1,4-butanediol 6 6 6 6 6 6 zinc oxide - - - - 0.54 0.54

(unit: parts by weight) division Comparative Example 1 Example 6 Example 7 Example 8 polycaprolactone
Dior 26 25 22.6 19.7 polycaprolactone
triol 13 13 13 13 According to Preparation Example 2
acid polyol - 2 6 10.4 Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether One One One One 1,4-butanediol 6 6 6 6

(unit: parts by weight) division Comparative Example 1 Example 9 Example 10 Example 11 Example 12 Example 13 polycaprolactone
Dior 26 25.8 24.5 23 24.5 24.5 polycaprolactone
triol 13 13 13 13 13 14 According to Preparation Example 3
acid polyol - 0.85 2.5 4.2 2.5 2.5 Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether One One One One One One 1,4-butanediol 6 6 6 6 6 7 Zinc Oxide: Calcium Carbonate - - - - 0.31:0.16 0.31:0.17

(unit: parts by weight) division Comparative Example 1 Example 14 Example 15 Example 16 Example 17 Example 18 polycaprolactone
Dior 26 25 22.2 18.4 22.2 22.2 polycaprolactone
triol 13 13 13 13 13 13 According to Preparation Example 4
acid polyol - 3.5 11.5 21.9 11.5 11.5 Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether One One One One One One 1,4-butanediol 6 6 6 6 6 6 zinc oxide - - - - 0.54 0.54

(unit: parts by weight) division Comparative Example 1 Example 19 Example 20 Example 21 polycaprolactone
Dior 26 25 22.6 19.7 polycaprolactone
triol 13 13 13 13 According to Preparation Example 5
acid polyol - 2 6 10.4 Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether One One One One 1,4-butanediol 6 6 6 6

(unit: parts by weight) division Comparative Example 1 Example 22 Example 23 Example 24 Example 25 Example 26 polycaprolactone
Dior 26 25.8 24.5 23 24.5 24.5 polycaprolactone
triol 13 13 13 13 13 14 According to Preparation Example 6
acid polyol - 0.85 2.5 4.2 2.5 2.5 Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether One One One One One One 1,4-butanediol 6 6 6 6 6 7 Zinc Oxide: Calcium Carbonate - - - - 0.31:0.16 0.31:0.17

3. Evaluation of two-component structural polyurethane adhesives

Mechanical properties, adhesive strength and detachability of the adhesives according to the Examples and Comparative Examples were measured in the following manner, and the results are shown in [Table 9] to [Table 12] below.

(1) mechanical properties

Hardness was measured using a shore A type durometer, and tensile strength, elongation, and E-modulus were measured using a universal tensile tester (UTM, Zwick, Zwick-1435) based on ASTM D 638 test standards.

(2) Adhesion strength and disassembly

Shear adhesion strength (ASTM D1002) was evaluated by applying and bonding to the bonding surface of steel and CFRP (Carbon Fiber Reinforced Plastic), respectively, and then heating the bonded specimens to 200 ~ 250 ℃ using an oven to determine whether they were separated. confirmed. Here, the criterion for 'separation' indicates the strength of the adhesive strength of 0.2 MPa or less.

division Hardness
(shore A) tensile strength
(MPa) elongation rate
(%) E-modulus
(MPa) adhesive strength
(MPa) disintegration
(Separation) Comparative Example 1 72 7.2 195 36 10.2 not separated Example 1 81 9.7 177 181 11.2 separation Example 2 83 12.4 174 185 11.7 separation Example 3 85 9.6 166 177 11.5 separation Example 6 82 11.5 144 180 11.3 separation Example 7 81 9.27 164 169 11.4 separation Example 8 77 8.82 179 159 11.3 separation Example 9 76 10.31 181 160 11.5 separation Example 10 79 10.8 178 174 11.7 separation Example 11 78 9.74 180 163 11.2 separation

division Hardness
(shore A) tensile strength
(MPa) elongation rate
(%) E-modulus
(MPa) adhesive strength
(MPa) disintegration
(Separation) Comparative Example 1 72 7.2 195 36 10.2 not separated Example 2 83 12.4 174 185 11.4 separation Example 4 83 12.7 161 194 11.7 separation Example 5 84 11.2 143 179 11.5 separation Example 10 79 10.8 178 174 11.3 separation Example 12 82 11.6 151 183 11.4 separation Example 13 78 10.63 146 171 11.2 separation

division Hardness
(shore A) tensile strength
(MPa) elongation rate
(%) E-modulus
(MPa) adhesive strength
(MPa) disintegration
(Separation) Comparative Example 1 72 7.2 195 36 10.2 not separated Example 14 81 9.7 177 181 11.2 separation Example 15 83 12.4 174 185 11.7 separation Example 16 85 9.6 166 177 11.5 separation Example 19 82 11.5 144 180 11.3 separation Example 20 81 9.27 164 169 11.4 separation Example 21 77 8.82 179 159 11.3 separation Example 22 76 10.31 181 160 11.5 separation Example 23 79 10.8 178 174 11.7 separation Example 24 78 9.74 180 163 11.2 separation

division Hardness
(shore A) tensile strength
(MPa) elongation rate
(%) E-modulus
(MPa) adhesive strength
(MPa) disintegration
(Separation) Comparative Example 1 72 7.2 195 36 10.2 not separated Example 15 83 12.4 174 185 11.4 separation Example 17 83 12.7 161 194 11.7 separation Example 18 84 11.2 143 179 11.5 separation Example 23 79 10.8 178 174 11.3 separation Example 25 82 11.6 151 183 11.4 separation Example 26 78 10.63 146 171 11.2 separation

As shown in [Table 9] to [Table 12], the examples according to the present invention, compared to the comparative examples, prepare a two-component structural polyurethane adhesive composition by mixing a resin mix containing an acid polyol with a free polymer, It can be seen that the mechanical properties and adhesive strength are excellent and have efficient disassembly.

As described above, the disassembly two-component structural polyurethane adhesive composition having improved mechanical properties and adhesive strength and the disassembly method thereof according to the present invention have been described through the above preferred examples and their superiority confirmed, but those skilled in the art It will be understood that various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention described in the following claims.

Claims (4)

In the two-component structural polyurethane adhesive composition,
A resin mix is mixed with the pre-polymer, and the resin mix is composed of an acid polyol,
The free polymer is
It is composed of 30 to 40% by weight of polycaprolactone diol and 60 to 70% by weight of diphenylmethane diisocyanate,
With respect to 100 parts by weight of the free polymer, the resin mix
18.4 to 25.8 parts by weight of polycaprolactone diol, 13 to 14 parts by weight of polycaprolactone triol, 0.85 to 21.9 parts by weight of the acid polyol, trimethylolpropane tris [poly(propylene glycol), amine terminated] ether 1 to 2 It is made by mixing 6 to 7 parts by weight of 1,4-butanediol, 0.31 to 0.54 parts by weight of zinc oxide and 0.16 to 0.17 parts by weight of calcium carbonate,
The acid polyol is
DMBA (2,2-Bis(hydroxymethyl)butyric acid) 14.8 to 15.8 molar parts and DMPA (2,2-Bis(hydroxy-methyl)propionic acid) 13.41 to 14.41 molar parts and BES (N,N-bis(2-hydroxyethyl) -2-aminoethanesulfonic acid) 21.31 ~ 22.32 parts by mole, polytetramethylene glycol (PTMG) 91 ~ 280 parts by mole and diphenyl methanediisocyanate (MDI) 30 ~ 31 parts by mole
A demountable two-component structural polyurethane adhesive composition with improved phosphorus mechanical properties and adhesive strength. delete delete In the dissolution method of the composition according to claim 1,
A disassembly method of a disassembly two-component structural polyurethane adhesive composition with improved mechanical properties and adhesive strength, characterized in that it is dismantled by heating to 200 ~ 250 ℃ using an oven.