CN113105857A - UV (ultraviolet) moisture-cured hot melt adhesive and preparation method thereof - Google Patents

Abstract

The invention discloses a UV (ultraviolet) moisture-curing hot melt adhesive and a preparation method thereof, wherein the hot melt adhesive comprises a component A, a component B and a photoinitiator; wherein the mass ratio of the component A to the component B to the photoinitiator is as follows: the component A comprises: and B component: and (3) the photoinitiator is 40-60: 40-60: 1-3; the component A comprises the following components in percentage by weight: 21-35% of first polyester polyol, 53-65% of isocyanate trimer, 10-13% of active acrylic monomer and 0.001-0.01% of first catalyst; the component B comprises the following components in percentage by weight: 30-40% of polyether polyol, 15-20% of thermoplastic resin filler, 15-25% of isocyanate monomer, 0.1-1% of second catalyst, 0.1-1% of antioxidant, 0.1-1% of coupling agent, 0.1-1% of water removing agent and 20-30% of second polyester polyol.

Description

UV (ultraviolet) moisture-cured hot melt adhesive and preparation method thereof

Technical Field

The invention relates to the technical field of polyurethane hot melt adhesives, in particular to a UV (ultraviolet) moisture-cured hot melt adhesive and a preparation method thereof.

Background

The reactive polyurethane hot melt adhesive is a single-component adhesive which has a polar group in the structure and contains carbamate in the main chain, has extremely strong adhesion to various materials, can be cured at normal temperature, has good toughness, high and low temperature resistance, good solvent resistance and other comprehensive properties, is simple in adhesion process, is heated to be in a molten state and then constructed, is cured by virtue of reaction of air or moisture on the surface of an adherend after being pressed and cooled, does not have a solvent during use, does not have the problems of VOC emission and the like, does not pollute the environment, belongs to an environment-friendly adhesive, and is widely applied in the industry and the electronic industry.

However, with the continuous update of electronic products, the production efficiency is continuously improved, after the common reactive polyurethane hot melt adhesive is dispensed or sprayed with the adhesive, one day or several days are usually required for complete curing, several hours of pressure maintaining time are usually required for primary curing to achieve basic bonding strength, the production efficiency is affected, a large number of pressure maintaining fixtures are required to be put into, even the defects of the adhesive cannot be found in time, and when the problem of the adhesive is found, a large number of finished products are usually produced, which easily causes waste.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a UV (ultraviolet) moisture-curing hot melt adhesive and a preparation method thereof.

In order to achieve the aim, the invention provides a UV moisture-curing hot melt adhesive which comprises a component A, a component B and a photoinitiator;

wherein the mass ratio of the component A to the component B to the photoinitiator is as follows: the component A comprises: and B component: and (3) the photoinitiator is 40-60: 40-60: 1-3;

the component A comprises the following components in percentage by weight:

the component B comprises the following components in percentage by weight:

preferably, the photoinitiator is one or a mixture of more of a photoinitiator 189, a photoinitiator 1173, a photoinitiator TPO and a photoinitiator 184.

Preferably, the first polyester polyol refers to one or more of polycarbonate polyol, polycaprolactone polyol and polyhexamethylene glycol adipate polyol, and is a linear polyester polyol with the molecular weight of 1000-3000.

Preferably, the isocyanate trimer refers to HDI trimer, which is 90% trimer.

Preferably, the reactive acrylic acid monomer is beta-hydroxyethyl acrylate or beta-hydroxypropyl acrylate or hydroxyethyl methacrylate or hydroxypropyl methacrylate;

the first catalyst refers to dibutyltin dilaurate and stannous octoate.

Preferably, the second polyester polyol is one or two of poly adipic acid glycol ester diol and poly adipic acid butanediol ester diol, and the molecular weight of the second polyester polyol is 2000-4000 linear polyester polyol.

Preferably, the polyether polyol is one or two of polyoxypropylene glycol, polyethylene glycol and polytetrahydrofuran ether glycol, and the molecular weight of the polyether polyol is 2000-4000.

Preferably, the isocyanate monomer is one of diphenylmethane diisocyanate, toluene diisocyanate, polymethylene polyphenyl polyisocyanate and carbodiimide modified isocyanate;

the thermoplastic resin filler is one of amorphous thermoplastic resin and non-reactive acrylic acid-acetic polymer.

Preferably, the second catalyst refers to one or more of dimorpholinodiethyl ether, dibutyltin dilaurate and stannous octoate;

the antioxidant refers to one or more of an antioxidant 245 or an antioxidant 1010;

the coupling agent refers to one or more of KH550, KH560 or KH 590;

the water removal agent refers to one or more of oxazolidine water removal agent and p-methyl benzenesulfonyl isocyanate water removal agent.

The invention also provides a preparation method of the UV moisture-cured hot melt adhesive, which comprises the following steps:

step S1, preparing a component A prepolymer; putting the isocyanate tripolymer into a reaction bottle, heating to about 85 ℃, preserving heat and filling nitrogen; slowly dripping the active acrylic monomer into a reaction bottle, and keeping the temperature for reaction until NCO is measured to be about 11-12%; adding liquid first polyester polyol dehydrated for 2 hours at 120 ℃ and-0.095 Mpa and a first catalyst, reacting at 100 ℃ under the condition of heat preservation until NCO is 6.0% -7.5%, and finally vacuumizing to remove odor to obtain a component A prepolymer;

step S2, preparing a B component prepolymer; adding second polyester polyol, polyether polyol, thermoplastic resin filler and antioxidant into a reaction kettle according to the formula, and heating to a molten state at the temperature of 120-130 ℃; stirring for 2h under-0.095 Mpa at a speed of 50-150 r/min; introducing nitrogen to normal pressure, and cooling to 75-85 ℃; adding isocyanate monomer into a reaction kettle according to a formula, stirring and reacting for 2-3h, heating to 90-95 ℃, and keeping the temperature for about 1h until NCO is measured to be 2.0% -3.5%; adding a second catalyst, a coupling agent and a water removing agent, stirring and defoaming for 10-30min, and finally vacuumizing and removing odor to prepare a B component prepolymer;

step S3, weighing the prepolymer with the component A in the mass ratio: b component prepolymer: and (3) the photoinitiator is 40-60: 40-60: 1-3, heating and stirring uniformly in vacuum under the condition of keeping out of the sun, and finally cooling, curing and packaging under the conditions of keeping out of the sun and vacuum; and preparing the UV moisture-cured hot melt adhesive.

Compared with the prior art, the invention has the beneficial effects that:

the UV moisture-curing hot melt adhesive prepared by the invention can achieve stronger bonding force in the initial stage under the condition of short ultraviolet irradiation time (10 seconds), greatly shortens the pressure maintaining time, achieves the technical effect of pressure maintaining free, can reduce the emitted VOC gas, improves the production efficiency, and can meet the requirement of high production efficiency.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are one embodiment of the present invention, and not all embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments of the present invention without any creative work belong to the protection scope of the present invention.

Example one

The embodiment provides a UV moisture-curing hot melt adhesive and a preparation method thereof, and the preparation method comprises the following steps:

step S1, preparing a component A prepolymer;

putting 120 g of HDI trimer into a reaction bottle, heating to 85 ℃, preserving heat and filling nitrogen;

then, 23 g of acrylic acid-beta-Hydroxyethyl (HEA) monomer is dripped in, and the mixture is stirred and subjected to heat preservation reaction until the NCO is 12%;

then 100 g of liquid polycaprolactone polyol (Mn 1000) dehydrated for 2h at 120 ℃ and under the environment of-0.095 Mpa and 0.2 g of dibutyltin dilaurate catalyst are added, stirred and subjected to heat preservation reaction at 100 ℃ until NCO is 7.0 percent;

and finally, vacuumizing to remove the odor to prepare the A component prepolymer.

Step S2, preparing a B component prepolymer;

a reaction kettle was charged with 100 g polytetrahydrofuran ether glycol (Mn 2000), 50 g polybutylene adipate (Mn 4000), 0.2 g antioxidant 1010, 35 g amorphous thermoplastic resin (EVA); heating to a molten state at 130 deg.C, and stirring at-0.095 Mpa for 2 hr at 50-150 r/min; introducing nitrogen to normal pressure, and cooling to 80 ℃;

adding 30 g of diphenylmethane diisocyanate (MDI) into a reaction kettle, stirring and reacting for 2h, heating to 90 ℃, and keeping the temperature for about 1h until the NCO is 3.0%;

adding 1.2 g of dimorpholinyl diethyl ether catalyst, 0.6 g of KH590 coupling agent and 0.5 g of p-methyl benzenesulfonyl isocyanate water remover, and stirring and defoaming for 15 min;

and finally, vacuumizing to remove the odor to prepare the B component prepolymer.

Step S3, weighing 120 g of the prepolymer of the component A, 80 g of the prepolymer of the component B, 1.0 g of the photoinitiator TPO and 1.0 g of the photoinitiator 184, heating and stirring uniformly in vacuum under the condition of keeping out of the sun, and finally cooling, curing and packaging under the conditions of keeping out of the sun and vacuum; a UV moisture-curable hot melt adhesive of example one was prepared.

Example two

The second embodiment provides a UV moisture-curable hot melt adhesive and a preparation method thereof, wherein the preparation method comprises the following steps:

step S1, preparing a component A prepolymer;

putting 120 g of HDI trimer into a reaction bottle, heating to 85 ℃, preserving heat and filling nitrogen;

then, 19 g of acrylic acid-beta-Hydroxyethyl (HEA) monomer is dripped in, and the mixture is stirred and subjected to heat preservation reaction until the NCO is 11.5%;

then 66 g of liquid carbonate polyol (Mn ═ 2000) dehydrated for 2h in an environment of 120 ℃ and-0.095 Mpa and 0.2 g of dibutyltin dilaurate catalyst are added, and stirred at 100 ℃ for heat preservation reaction until NCO is 6.0%;

and finally, vacuumizing to remove the odor to prepare the A component prepolymer.

Step S2, preparing a B component prepolymer;

adding 90 g of polypropylene oxide glycol, 60 g of polyhexamethylene adipate (Mn is 3500), 0.2 g of antioxidant 1010 and 40 g of non-reactive acrylic acid vinyl chloride BR-113 into a reaction kettle; heating to a molten state at 130 deg.C, and stirring at-0.095 Mpa for 2 hr at 50-150 r/min; introducing nitrogen to normal pressure, and cooling to 80 ℃;

adding 35 g of diphenylmethane diisocyanate (MDI) into a reaction kettle, stirring for reaction for 2h, heating to 90 ℃, and keeping the temperature for about 1h until the NCO is 3.5%;

adding 1.4 g of dimorpholinyl diethyl ether catalyst, 0.7 g of KH590 coupling agent and 0.4 g of p-methyl benzenesulfonyl isocyanate water remover, and stirring and defoaming for 15 min;

and finally, vacuumizing to remove the odor to prepare the B component prepolymer.

Step S3, weighing 100 g of the prepolymer of the component A, 100 g of the prepolymer of the component B and 2.0 g of the photoinitiator TPO, heating and stirring uniformly in vacuum under the condition of keeping out of the sun, and finally cooling, curing and packaging under the conditions of keeping out of the sun and vacuum; a UV moisture-curable hot melt adhesive of example two was prepared.

EXAMPLE III

The third embodiment provides a UV moisture-curable hot melt adhesive and a preparation method thereof, wherein the preparation method comprises the following steps:

step S1, preparing a component A prepolymer;

putting 100 g of HDI trimer into a reaction bottle, heating to 85 ℃, preserving heat and filling nitrogen;

then, 19 g of acrylic acid-beta-Hydroxyethyl (HEA) monomer is dripped in, and the mixture is stirred and subjected to heat preservation reaction until the NCO is 11.5%;

then 33 g of liquid carbonate polyol (Mn ═ 2000), 33 g of liquid polycaprolactone polyol (Mn ═ 2000), 0.2 g of dibutyltin dilaurate catalyst, which are dehydrated for 2 hours in an environment of 120 ℃ and-0.095 Mpa, are added, and the mixture is stirred and reacted at 100 ℃ until the NCO is 6.0 percent;

and finally, vacuumizing to remove the odor to prepare the A component prepolymer.

Step S2, preparing a B component prepolymer;

adding 45 g of polypropylene oxide glycol (Mn ═ 2000) and 45 g of polytetrahydrofuran ether glycol (Mn ═ 2000), 60 g of polyhexamethylene adipate glycol (Mn ═ 3500), 0.2 g of antioxidant 1010 and 40 g of non-reactive acrylic acid acetate BR-113 into a reaction kettle; heating to a molten state at 120 ℃, and stirring for 3 hours under the condition of-0.095 Mpa, wherein the stirring speed is 50-150 r/min; introducing nitrogen to normal pressure, and cooling to 80 ℃;

adding 42 g of carbodiimide modified isocyanate (liquefied MDI) into a reaction kettle, stirring and reacting for 2h, then heating to 90 ℃, and keeping the temperature for about 1h until the NCO is 3.0 percent;

adding 1.3 g of dimorpholinyl diethyl ether catalyst, 0.8 g of KH560 coupling agent and 0.4 g of p-methyl benzenesulfonyl isocyanate water remover, and stirring and defoaming for 15 min;

and finally, vacuumizing to remove the odor to prepare the B component prepolymer.

Step S3, weighing 80 g of the prepolymer of the component A, 120 g of the prepolymer of the component B and 2.0 g of the photoinitiator TPO, heating and stirring uniformly in vacuum under the condition of keeping out of the sun, and finally cooling, curing and packaging under the conditions of keeping out of the sun and vacuum; a UV moisture-curable hot melt adhesive of example three was prepared.

Comparative example No. four

The fourth comparative example provides a preparation method of a reactive polyurethane hot melt adhesive, which comprises the following steps:

mixing 90 g of polyoxypropylene glycol, 60 g of poly (hexanediol adipate) (Mn 3500), 0.2 g of 1010 antioxidant, and 50 g of non-reactive acrylic acid type BR-113; putting into a reaction bottle, heating to a molten state at 130 ℃, stirring for 2h under the condition of-0.095 Mpa, introducing nitrogen to normal pressure, and cooling to 80 ℃;

adding 40 g of diphenylmethane diisocyanate (MDI) into a reaction kettle, stirring and reacting for 2h, heating to 90 ℃, and keeping the temperature for about 1h until the NCO is 3.5%;

adding 1.2 g of dimorpholinyl diethyl ether catalyst, 0.6 g of KH590 coupling agent and 0.6 g of p-methyl benzenesulfonyl isocyanate water remover, and stirring and defoaming for 15 min;

and finally, vacuumizing to remove the odor to prepare the reactive polyurethane hot melt adhesive.

The obtained hot melt adhesive is made into a standard test piece, the standard test piece is placed into a gluing machine for gluing, after gluing is finished, the hot melt adhesive and parts bonded together are placed into 395nm ultraviolet light for irradiation for 10 seconds, and mechanical property test data for bonding the parts bonded together are obtained, wherein the results are as follows:

as can be seen from the above table, example 1, example 2, example 3 and comparative example 4 have no significant difference in the test items of viscosity at 100 ℃, so example 1, example 2, example 3 and comparative example 4 are mutually versatile in the applicable range; on the test project of 5min bonding strength, the experimental effects of the example 1, the example 2 and the example 3 are far greater than that of the comparative example 4; on the test item of the bonding strength for 1h, it can be seen that the experimental effects of the examples 1, 2 and 3 are greater than those of the comparative example 4, but it can be seen that the difference in the bonding strength is decreasing; on the 24h test item of the bonding strength, it can be seen that the experimental effect of the examples 1, 2 and 3 is slightly larger than that of the comparative example 4, but it can be seen that the difference of the bonding strength is small, the bonding strength of the comparative example 4 is gradually strengthened, and if the time is long enough, the bonding strength of the comparative example 4 should be consistent with that of the examples 1, 2 and 3.

The following conclusions can be drawn: the UV moisture-curing hot melt adhesive prepared by the invention can reach stronger bonding force in the initial stage under the condition of short ultraviolet irradiation time (10 seconds), greatly shortens the pressure maintaining time, achieves the technical effect of pressure maintaining free, can reduce the emitted VOC gas, improves the production efficiency, and can be suitable for the requirement of high production efficiency, such as: and bonding of electronic components.

The UV moisture-curing hot melt adhesive prepared by the invention has two characteristics of UV photocuring and rapid curing, overcomes the defect of long pressure maintaining and positioning time of a pure moisture-curing hot melt adhesive, can avoid using a large number of jigs, increase the repeated utilization rate of the jigs, reduce the number of manufactured jigs, simultaneously can ensure that the final bonding force is strong, has no characteristics of odor and the like, and meets the requirement of high production efficiency of components such as electronic appliances and the like.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The UV moisture-curing hot melt adhesive is characterized by comprising a component A, a component B and a photoinitiator;

wherein the mass ratio of the component A to the component B to the photoinitiator is as follows: the component A comprises: and B component: and (3) the photoinitiator is 40-60: 40-60: 1-3;

the component A comprises the following components in percentage by weight:

the component B comprises the following components in percentage by weight:

2. the UV moisture-curable hot melt adhesive according to claim 1, wherein the photoinitiator is one or a mixture of a plurality of photoinitiators 189, 1173, TPO and 184.

3. The UV moisture-curable hot melt adhesive according to claim 1, wherein the first polyester polyol is one or more of polycarbonate polyol, polycaprolactone polyol and polyhexamethylene adipate polyol, and is a linear polyester polyol having a molecular weight of 1000-3000.

4. The UV moisture-curable hot melt adhesive according to claim 1, wherein the isocyanate trimer is HDI trimer which is 90% trimer.

5. The UV moisture-curable hot melt adhesive according to claim 1, wherein the reactive acrylic acid monomer is beta-hydroxyethyl acrylate or beta-hydroxypropyl acrylate or hydroxyethyl methacrylate or hydroxypropyl methacrylate;

the first catalyst refers to dibutyltin dilaurate and stannous octoate.

6. The UV moisture-curable hot melt adhesive according to claim 1, wherein the second polyester polyol is one or both of polyhexamethylene adipate glycol and polybutanediol adipate glycol, and is a linear polyester polyol having a molecular weight of 2000-4000.

7. The UV moisture-curable hot melt adhesive according to claim 1, wherein the polyether polyol is one or two of polyoxypropylene glycol, polyethylene glycol and polytetrahydrofuran ether glycol, and has a molecular weight of 2000-4000.

8. The UV moisture-curable hot melt adhesive according to claim 1, wherein the isocyanate monomer is one of diphenylmethane diisocyanate, toluene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimide-modified isocyanate;

the thermoplastic resin filler is one of amorphous thermoplastic resin and non-reactive acrylic acid-acetic polymer.

9. The UV moisture-curable hot melt adhesive according to claim 1, wherein the second catalyst is one or more of dimorpholinodiethyl ether, dibutyltin dilaurate and stannous octoate;

the antioxidant refers to one or more of an antioxidant 245 or an antioxidant 1010;

the coupling agent refers to one or more of KH550, KH560 or KH 590;

the water removal agent refers to one or more of oxazolidine water removal agent and p-methyl benzenesulfonyl isocyanate water removal agent.

10. A preparation method of a UV (ultraviolet) moisture-curing hot melt adhesive is characterized by comprising the following steps:

step S1, preparing a component A prepolymer; putting the isocyanate tripolymer into a reaction bottle, heating to about 85 ℃, preserving heat and filling nitrogen; slowly dripping the active acrylic monomer into a reaction bottle, and keeping the temperature for reaction until NCO is measured to be about 11-12%; adding a liquid first polyester polyol dehydrated for 2 hours at 120 ℃ and-0.095 Mpa and a first catalyst, and carrying out heat preservation reaction at 100 ℃ until NCO is 6.0-7.5%; finally, vacuumizing and deodorizing to prepare a component A prepolymer;

step S2, preparing a B component prepolymer; adding second polyester polyol, polyether polyol, thermoplastic resin filler and antioxidant into a reaction kettle according to the formula, and heating to a molten state at the temperature of 120-130 ℃; stirring for 2h under-0.095 Mpa at a speed of 50-150 r/min; introducing nitrogen to normal pressure, and cooling to 75-85 ℃; adding isocyanate monomer into a reaction kettle according to a formula, stirring and reacting for 2-3h, heating to 90-95 ℃, and keeping the temperature for about 1h until NCO is measured to be 2.0% -3.5%; adding a second catalyst, a coupling agent and a water removing agent, stirring and defoaming for 10-30 min; finally, vacuumizing and deodorizing to prepare the B component prepolymer;

step S3, weighing the prepolymer with the component A in the mass ratio: b component prepolymer: and (3) the photoinitiator is 40-60: 40-60: 1-3, heating and stirring uniformly in vacuum under the condition of keeping out of the sun, and finally cooling, curing and packaging under the conditions of keeping out of the sun and vacuum; and preparing the UV moisture-cured hot melt adhesive.