KR102051296B1 - Polyurethane resin composition - Google Patents

Abstract

The present invention relates to a polyurethane resin composition, wherein the polyurethane resin composition comprises: a first urethane resin; a second urethane resin; a plasticizer; and a catalyst. The polyurethane resin composition of the present invention is excellent in adhesiveness in a wide temperature range, thereby being able to obtain an excellent adhesive effect without applying a primer on a painted surface of a vehicle body.

Description

Polyurethane resin composition {POLYURETHANE RESIN COMPOSITION}

The present invention relates to a one-component polyurethane resin composition used as an adhesive.

In general, polyurethane resins have a urethane bond in the molecule, and are excellent in wear resistance, oil resistance, solvent resistance, and the like, and are used in various fields such as adhesives, injection molding, inks, paints, and foams.

When such a polyurethane resin is used as an adhesive agent, the case where a base material, such as glass, is bonded to the painted surface made of automobiles is mentioned. However, since the conventional polyurethane resin is inferior in adhesiveness with the coating surface made by automobiles, it was necessary to first apply a primer on the coating surface, and then apply a polyurethane resin thereon to adhere a substrate such as glass. As the primer coating process is required as described above, when using a conventional polyurethane resin, there is a problem in that a process of adhering a substrate such as glass on a painted surface of a vehicle is complicated.

In addition, the conventional polyurethane resin has a problem in that the pot life is short, workability is inferior, and adhesiveness at low temperature is also limited and the use environment of the polyurethane resin is limited.

Republic of Korea Patent Publication No. 2009-0019798

The present invention can secure a pot life sufficiently, to provide a polyurethane resin composition excellent in adhesion in a wide temperature range.

The present invention, the first urethane resin; Second urethane resin; Plasticizers; And a catalyst, wherein the catalyst comprises dibutyltin mercaptide, dioctyltin dilaurate and 4,4 ′-(oxydi-2,1-ethanediyl) bismorpholine To provide.

The mixing ratio of the dibutyltin mercaptide, the dioctyltin dilaurate and the 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine is 0.001 to 0.1: 0.01 to 0.3: 0.001 to 0.1 It may be a weight ratio of.

The plasticizer may include one or more selected from the group consisting of a phthalate plasticizer and a phosphate plasticizer.

The phthalate plasticizer may include one or more selected from the group consisting of dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, and butylbenzyl phthalate.

The phosphate plasticizer may include one or more selected from the group consisting of 2-ethylhexyl diphenyl phosphate, tricresyl phosphate and cresyl diphenyl phosphate.

The polyurethane resin composition may further include a pigment.

The polyurethane resin composition is 35 to 70 parts by weight of the first urethane resin; 3 to 14 parts by weight of the second urethane resin; 5 to 30 parts by weight of the plasticizer; 0.001 to 0.5 parts by weight of the catalyst; And it may include 20 to 40 parts by weight of the pigment.

The polyurethane resin composition of the present invention can sufficiently secure pot life consumed in the coating process by including a specific catalyst and a plasticizer, thereby improving workability in the coating process. In addition, the polyurethane resin composition of the present invention has excellent adhesiveness in a wide temperature range (for example, 5 to 35 ℃), when used as an adhesive for bonding a substrate such as glass on the painted surface of the car body, An excellent adhesive effect can be obtained without applying a primer on the coating surface of a vehicle.

Hereinafter, the present invention will be described.

The present invention relates to a one-component polyurethane resin composition which is characterized by ensuring a sufficient pot life in the coating process by including a specific catalyst and a plasticizer, which will be described in detail below.

The polyurethane resin composition of this invention contains a 1st urethane resin, a 2nd urethane resin, a plasticizer, and a catalyst.

The first urethane resin included in the polyurethane resin composition of the present invention may be a urethane prepolymer obtained by the reaction of a polyol compound and an isocyanate compound.

Specific examples of the polyol compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypropylene triol, and the like. The weight average molecular weight of the polyol compound may be 500 to 10,000, specifically 2,000 to 5,000.

Specific examples of the isocyanate compound include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 4,4'-diphenylmethylene diisocyanate (4, 4'-MDI), 2,4'-diphenylmethylene diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. are mentioned.

A plasticizer (first plasticizer) may be used for the reaction of the polyol compound and the isocyanate compound. Specific examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, diisodecyl phthalate, diisononyl phthalate, or mixtures thereof.

The weight average molecular weight of the first urethane resin may be 2,500 to 15,000 when considering the viscosity, flexibility, and the like of the polyurethane resin composition. In addition, the content of the isocyanate group bonded to the terminal of the first urethane resin may be 0.5 to 3.0%.

The content of the first urethane resin may be 35 to 70 parts by weight based on 100 parts by weight of the polyurethane resin composition. When the content of the first urethane resin is out of the above range, the flexibility, adhesion, heat resistance, etc. of the polyurethane resin composition may be lowered.

The second urethane resin contained in the polyurethane resin composition of the present invention is obtained by the reaction of an amino silane, a polyol compound and an isocyanate compound, and may be a urethane resin different from the first urethane resin. Specifically, in order to further improve the adhesiveness of the polyurethane resin composition, the second urethane resin of the present invention may be obtained by reacting a biuret body in which a polyether polyol, an aminoalkoxy silane compound, and an isocyanate are bound.

The polyether polyol absorbs moisture in the air due to the hygroscopicity of the raw material itself to promote hydrolysis of the aminoalkoxy silane compound, and reacts with the burette to form a urethane bond. Specific examples of such polyether polyols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, mixtures thereof, and the like. In addition, the weight average molecular weight of the polyether polyol may be 200 to 2,000.

The aminoalkoxy silane compound improves the adhesiveness, low temperature reactivity of the second urethane resin, and the like. The aminoalkoxy silane compound may be a compound represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

In Chemical Formula 1,

R ¹ is an aryl group of C ₁ to C ₁₀ with C ₆ to C ₁₀ substituted or unsubstituted with an alkyl group and, R ² is an alkylene group of C ₁ to C _10, R ³ and R ⁴ are the same or different from each other, and Each independently represent an alkyl group having ₁ to ₁₀ carbon atoms, and n is an integer of 1 to 3.

[Formula 2]

In Chemical Formula 2,

R ⁵ and R ⁶ are the same as or different from each other, and each independently an alkylene group of C ₁ to C ₃ , R ⁷ to R ¹⁰ are the same or different from each other, and each independently an alkyl group of C ₁ to C ₁₀ , a And b are integers of 1 to 3, respectively.

The compound represented by Formula 2 may be a compound obtained by reacting an amino silane compound with an epoxy silane compound in a molar ratio of 1: 0.1 to 1. At this time, specific examples of the amino silane compound are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N-2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane), N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane (N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane), 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Or N-phenyl-3-aminopropyltrimethoxysilane. In addition, specific examples of the epoxy silane include 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and 3-glycidoxypropyl methyl. Diethoxysilane (3-Glycidoxypropyl methyldiethoxysilane), 3-glycidoxypropyl triethoxysilane, and the like.

Specifically, the aminoalkoxy silane compound represented by Formula 1 may be N-phenyl-gamma-aminopropyltrimethoxy silane as an aminoalkoxy silane compound having an aromatic ring bonded thereto. have. In addition, the aminoalkoxy silane compound represented by Chemical Formula 2 has a molar ratio of 3-aminopropyltriethoxysilane and 3-glycidoxypropyl trimethoxysilane in a 1: 1 ratio. It may be a compound obtained by reaction.

The burette body in which the isocyanate is bonded improves the adhesiveness, crosslinking reactivity and the like of the second urethane resin. Specific examples of the isocyanate bonded to this burette body include hexamethylene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,2-diisocyanate (cyclohexylene-1,2-diisocyanate), hexahydroxylylene diisocyanate, dicyclohexyl-4,4-diisocyanate, 1-methyl-2,4-dii 1-methyl-2,6-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, bis (4-isocyanatocyclohexyl) Methane (bisiso 4-anacyanatocyclohexyl), 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, or mixtures thereof Etc. can be mentioned. Specifically, the burette body is a burette body in which three or more isocyanate groups are bonded, and a 1,3,5-tris (6-isocyanatohexyl) burette (1,3,5-Tris (6-isocyanatohexyl) biuret) or It may be a trimer of hexamethylene diisocyanate.

The content rate (NCO%) of the isocyanate group contained in the burette body to which such isocyanate is bonded may be 15 to 30%.

The weight average molecular weight of the second urethane resin may be 500 to 2,000 when considering the viscosity, adhesiveness, and the like of the polyurethane resin composition. In addition, the content of the isocyanate group bonded to the terminal of the second urethane resin may be 5 to 15%.

The content of the second urethane resin may be 3 to 14 parts by weight based on 100 parts by weight of the polyurethane resin composition. When the content of the second urethane resin is out of the above range, the adhesiveness (particularly, low temperature adhesiveness) of the polyurethane resin composition may be lowered.

Here, the mixing ratio of the first urethane resin and the second urethane resin may be a weight ratio of 10: 1 to 3. When the mixing ratio of the first urethane resin and the second urethane resin is out of the above range, the adhesiveness of the polyurethane resin composition may be lowered or the curing may be delayed and cracks may occur in the coating film.

The plasticizer (second plasticizer) included in the polyurethane resin composition of the present invention is for imparting flexibility, elasticity, etc. to the polyurethane resin composition, and may include one or more selected from the group consisting of phthalate plasticizers and phosphate plasticizers. Can be. Specific examples of the phthalate-based plasticizers include dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, and diisodecyl phthalate. Di-isodecyl phthalate), butylbenzyl phthalate, or a mixture thereof. Specific examples of the phosphate-based plasticizers include 2-ethylhexyldiphenyl phosphate, tricrecresyl phosphate, cresyldiphenyl phosphate, and mixtures thereof. have. At this time, a mixture of diisononyl phthalate and 2-ethylhexyl diphenyl phosphate may be used as a plasticizer in order to further improve the flexibility and plasticity of the polyurethane resin composition and thermal stability.

The amount of such plasticizer may be 5 to 30 parts by weight based on 100 parts by weight of the polyurethane resin composition. When the content of the plasticizer is out of the above range, the flexibility, plasticity, etc. of the polyurethane resin composition may be lowered.

Catalysts included in the polyurethane resin composition of the present invention include dibutyltin mercaptide, dioctyltin dilaurate and 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine. Specifically, the catalyst is a mixture of dibutyltin mercaptide, dioctyltin dilaurate and 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine. The present invention can control the curing reaction rate of the polyurethane resin composition by including the mixture as a catalyst, it is possible to ensure a sufficient pot life in the coating process.

The mixing ratio of the dibutyltin mercaptide, the dioctyltin dilaurate and the 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine is 0.001 to 0.1: 0.01 to 0.3: 0.001 And a weight ratio of 0.1 to 0.1. When the mixing ratio of the compounds is out of the above range, it may be difficult to control the curing reaction rate of the polyurethane resin composition.

The content of such a catalyst may be 0.001 to 0.5 parts by weight based on 100 parts by weight of the polyurethane resin composition. When the content of the catalyst is out of the above range, the curing reactivity of the polyurethane resin composition may be lowered or the pot life may be shortened, thereby reducing workability.

On the other hand, the polyurethane resin composition of the present invention may further comprise a pigment.

The pigment is to increase the strength and color of the polyurethane resin composition, and specific examples thereof include carbon black, calcium carbonate, titanium dioxide (TiO ₂ ), iron oxide yellow, and iron oxide red. Etc. can be mentioned.

The content of such pigments may be 20 to 40 parts by weight based on 100 parts by weight of the polyurethane resin composition. When the content of the pigment is outside the above range, the strength of the polyurethane resin composition may be lowered, or it may be difficult to control the viscosity of the polyurethane resin composition.

In addition, the polyurethane resin composition of the present invention may further include a thickener commonly used to control the viscosity of the composition.

Since the polyurethane resin composition of the present invention described above includes a specific catalyst, curing reactivity is controlled in the coating process to ensure sufficient pot life. In addition, the polyurethane resin composition of the present invention is excellent in adhesiveness along with flexibility, heat resistance, strength and the like, when used as an adhesive for bonding a substrate such as glass to the coating surface of the vehicle itself, without applying a primer to the coating surface The substrate can be directly bonded.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.

[ Example  One]

1) first urethane resin

Into a glass flask equipped with a stirrer, a condenser, and a thermometer, polypropylene glycol, di-isononyl phthalate, and polypropylene triol were added, and the temperature was gradually raised to 140 ° C for 2 hours. Vacuum decompression was carried out. Next, after cooling to 60 ° C. or less, methylene diphenyl di-isocyanate (MDI) was added thereto to check the exotherm, and the reaction was performed such that NCO% was 1.72% while maintaining a temperature of 80 to 90 ° C. . After completion of the reaction was cooled to 40 ℃ to prepare a first urethane resin having a viscosity of 8,400 cPs and a weight average molecular weight of 9,000.

2) manufacture of the second urethane resin

Polypropylene glycol was added to a glass flask equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 140 ° C and vacuum reduced for 2 hours. Next, the mixture was cooled to 60 ° C. or lower, 1,3,5-tris (6-isoanatohexyl) biuret (1,3,5-Tris (6-isocyanatohexyl) biuret) was added thereto to confirm exotherm, and then 100 ° C. The reaction was carried out such that NCO% was 14.0 to 15.0% while maintaining the temperature of. After cooling to 40 ° C., N-phenyl-gamma-aminopropyltrimethoxy silane was added thereto, and the NCO% was 11.3% while maintaining a temperature of 40 to 45 ° C. Reacted. After the reaction was completed, a second urethane resin having a viscosity of 9,800 cPs was cooled to 40 ° C.

3) Polyurethane Resin Composition

The first urethane resin and the plasticizer prepared above were added to a SUS material mixer equipped with a vacuum pump, having a jacket capable of heating, and capable of high viscosity rotary stirring and scrubbing of walls. Next, after the pigment was added and stirred for 20 minutes, water was removed by performing a reduced pressure for 10 minutes in a vacuum of less than 20 Torr. Then, a catalyst and the second urethane resin prepared above were added and stirred for 30 minutes to prepare a polyurethane resin composition having a viscosity of 14,000 Ps and NCO% of 1.52%.

The composition of each component was prepared as shown in Table 1 when the resin and composition were prepared.

[ Example  2]

A polyurethane resin composition was prepared in the same manner as in Example 1, except that the composition of Table 1 was applied. At this time, in the case of Example 2 was added to adjust the viscosity.

Furtherance Example 1 Example 2 1st urethane resin Polypropylene glycol
(Molecular weight: 2,000, Viscosity: 150-175 cPs) 13 13 Diisononyl phthalate 12.2 12.2 Polypropylene triol
(Molecular weight: 4,800, Viscosity: 850 cPs) 25 25 Methylene diphenyl diisocyanate
(Molecular weight: 250, NCO%: 33.6%) 7 7 2nd urethane resin Polypropylene glycol
(Molecular weight: 400, viscosity: 100 cPs or less) One One N-phenyl-gamma-aminopropyltrimethoxy silane One One 1,3,5-tris (6-isocyanatohexyl) burette
(Molecular weight: 478, Viscosity: 2,000 cPs, NCO%: 23.5%) 6 5 Plasticizer Diisononyl phthalate 10.68 8.38 2-ethylhexyldiphenyl phosphate 0.7 0.7 Pigment Carbon black 23.29 11.79 Calcium carbonate - 13 additive Polyester polyol - 1.4 1,6-hexamethylene diisocyanate - 0.2 Diethyl malonate - 0.2 catalyst Dioctyltin dilaurate 0.02 0.02 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine
(Amine Equivalent: 8.1-8.5) 0.1 0.1 Dibutyltin mercaptide 0.01 0.01 Total (weight part) 100 100

[ Comparative example  1 to 3]

Except that the composition of Table 2 was applied, to prepare a polyurethane resin composition in the same manner as in Example 1. At this time, in the case of Comparative Example 3 was used as a second urethane resin prepared by applying the composition of Table 2.

Furtherance Comparative Example 1 Comparative Example 2 Comparative Example 3 1st urethane resin Polypropylene glycol
(Molecular weight: 2,000, Viscosity: 150-175 cPs) 13 13 13 Diisononyl phthalate 12.2 12.2 12.2 Polypropylene triol
(Molecular weight: 4,800, Viscosity: 850 cPs) 25 25 25 Methylene diphenyl diisocyanate
(Molecular weight: 250, NCO%: 33.6%) 7 7 7 2nd urethane resin Polypropylene glycol
(Molecular weight: 400, viscosity: 100 cPs or less) One One - N-phenyl-gamma-aminopropyltrimethoxy silane One One One 1,3,5-tris (6-isocyanatohexyl) burette
(Molecular weight: 478, Viscosity: 2,000 cPs, NCO%: 23.5%) 5 5 5 Vinyl trimethoxy silane - - One Plasticizer Diisononyl phthalate 11.68 11.67 11.68 2-ethylhexyldiphenyl phosphate 0.7 0.7 0.7 Pigment Carbon black 23.29 23.29 23.29 catalyst Dioctyltin dilaurate 0.02 0.02 0.02 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine 0.1 0.1 0.1 Dibutyltin mercaptide - 0.01 - Dimethyl-4-morpholine ethanamine 0.01 0.01 0.01 Total (weight part) 100 100 100

[ Experimental Example ]

The physical properties of the polyurethane resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3, respectively, were evaluated as follows, and the results are shown in Table 3 below.

1. Viscosity: measured by Brookfield viscometer (model name: DV2T, for measuring high viscosity).

2. Specific gravity: It was measured by submersion method at the temperature of the specified standard.

3. Solid content: 1g of sample was spread evenly on an aluminum can having a diameter of 5cm, and the weight difference was measured by baking at 150 ° C. × 15 minutes in a fan oven as a ratio.

4. Hardness: Samples were cured for 5 weeks to a thickness of 5 mm and then measured with a Shore A durometer.

5. TFT: After the sample was apply | coated to the coating surface on the conditions of 20 degreeCx65% relative humidity, the time which does not adhere with a non-adhesive tape was measured in minutes.

6. Low temperature adhesiveness: After leaving the sample for 5 minutes at the specified temperature and humidity, attach it to the coated surface and cure for 7 days at 20 ℃ × 65% relative humidity. The area of the sample adhered to the painted surface was expressed in% (0% if none of the coated surfaces were attached, and 100% if all surfaces were attached).

7. Knirf Cut: After attaching the sample to the painted surface and curing for 7 days under the condition of 20 ℃ × 65% relative humidity, cut it with a knife and check the adhesiveness with the painted surface to indicate the area of the sample attached to the painted surface in%. (0% if none of the coating surface is attached and 100% if all the surface is painted).

8. Shear Strength: Samples were made into 5 mm thick dogbone shaped cured specimens and measured with a universal testing machine (UTM).

9. Pot life: After leaving the sample for 5 minutes at the specified temperature and humidity, attach it to the surface and cure for 7 days at 20 ℃ × 65% relative humidity. The area of the sample attached to the painted surface is expressed in% (0% if none of the painted surfaces are attached, and 100% if all painted surfaces are attached).

standard Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Viscosity 10000-22000 Ps 14,000 12,800 13,600 14,100 13,800 (@ 60 ℃) importance 1.22-1.42 1.27 1.29 1.27 1.27 1.27 (@ 20 ℃) Solid content (%) More than 95% 99% 99% 99% 99% 99% (150 ℃ * 15 minutes) Hardness (Hs) 45-70 60 53 58 55 55 (Shore A) TFT (minutes) 60 or less 40 51 48 43 38 (20 ° C, 65%, 3hr) Low temperature adhesiveness over 90 100% 90% 30% 60% 0% (5 ℃ * 50%, 14 days) Knirf cut 20 ℃ 100% 100% 100% 100% 70% Shear strength (Mpa) 3.0 or higher 4.5 3.1 4.1 4.7 3.8 (20 ° C, 65%, 168hr) 5 minutes pot life
(Standard: 90% or more) (20 ℃ * 65%) 100% 100 80% 90% 40% (35 ℃ * 90%) 100% 95% 30% 5% 0%

Referring to Table 3, the polyurethane resin composition according to the present invention can be confirmed that the pot life is sufficiently secured workability, excellent low-temperature adhesiveness.

Claims (7)

First urethane resin;
Second urethane resin;
Plasticizers; And
Contains a catalyst,
Wherein the catalyst comprises dibutyltin mercaptide, dioctyltin dilaurate and 4,4 ′-(oxydi-2,1-ethanediyl) bismorpholine. The method according to claim 1,
The mixing ratio of the dibutyltin mercaptide, the dioctyltin dilaurate and the 4,4 '-(oxydi-2,1-ethanediyl) bismorpholine is 0.001 to 0.1: 0.01 to 0.3: 0.001 to 0.1 Polyurethane resin composition which is the weight ratio of. The method according to claim 1,
The plasticizer is a polyurethane resin composition comprising one or more selected from the group consisting of phthalate plasticizer and phosphate plasticizer. The method according to claim 3,
The phthalate plasticizer is a polyurethane resin composition comprising one or more selected from the group consisting of dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate and butylbenzyl phthalate. The method according to claim 3,
Polyurethane resin composition wherein the phosphate plasticizer comprises at least one selected from the group consisting of 2-ethylhexyl diphenyl phosphate, tricresyl phosphate and cresyl diphenyl phosphate. The method according to claim 1,
Polyurethane resin composition further comprising a pigment. The method according to claim 6,
35 to 70 parts by weight of the first urethane resin;
3 to 14 parts by weight of the second urethane resin;
5 to 30 parts by weight of the plasticizer;
0.001 to 0.5 parts by weight of the catalyst; And
Polyurethane resin composition comprising 20 to 40 parts by weight of the pigment.