CN112322228A

CN112322228A - Novel high-heat-resistance quick-packaging hot melt adhesive and preparation method thereof

Info

Publication number: CN112322228A
Application number: CN202010281274.8A
Authority: CN
Inventors: 朱克波
Original assignee: Guangzhou Jiayan Adhesive Co ltd
Current assignee: Guangzhou Jiayan Adhesive Co ltd
Priority date: 2020-04-10
Filing date: 2020-04-10
Publication date: 2021-02-05

Abstract

The invention discloses a novel high-heat-resistance quick-packaging hot melt adhesive and a preparation method thereof, and relates to the technical field of hot melt adhesives, wherein the hot melt adhesive comprises the following components in percentage by weight: 35-50% of metallocene olefin polymer, 2-10% of alpha-olefin copolymer, 1-8% of reinforced rubber chain segment polymer, 30-55% of tackifying resin, 15-25% of Fischer-Tropsch wax and 1-5% of antioxidant. The metallocene olefin polymer is selected as the main component of the hot melt adhesive, and simultaneously the alpha-olefin copolymer with good compatibility and the reinforced rubber chain polymer are matched to form a composite matrix component, so that the good adhesive property and high and low temperature resistance of the hot melt adhesive are ensured; the application of a proper amount of Fischer-Tropsch wax reduces the wiredrawing property and the melt viscosity of the composite matrix component, and improves the fluidity and the curing speed of the hot melt adhesive; the use of a suitable tackifying resin provides higher peel strength to the hot melt adhesive itself and sufficient assurance that the hot melt adhesive will produce good bonding to the packaging substrates.

Description

Novel high-heat-resistance quick-packaging hot melt adhesive and preparation method thereof

Technical Field

The invention relates to the technical field of hot-melt adhesives, in particular to a novel high-heat-resistance quick-packaging hot-melt adhesive and a preparation method thereof.

Background

The packaging hot melt adhesive is widely applied to the field of sealing and packaging on an automatic production line in the food industry. The traditional packaging hot melt adhesive mainly adopts EVA type, has excellent adhesive property to common corrugated paper, paperboard and the like, has good compatibility with a compounding agent, has wide selection range of the compounding agent, and can be compounded into the hot melt packaging adhesive with reasonable cost performance according to the use requirement.

However, the EVA hot melt adhesive also has obvious defects: the hot melt adhesive has strong smell in a hot melt state, poor adhesion performance to materials such as PE, films and gloss oil surfaces, poor high and low temperature resistance and the like. Aiming at the defects of the EVA hot melt adhesive, the novel polyolefin packaging hot melt adhesive starts to rise, has little smell and strong adhesive property to various packaging materials in the hot melt state, and is an ideal substitute product of the traditional EVA hot melt adhesive.

In the prior art, the advantages and the disadvantages of the polyolefin packaging hot melt adhesive are effectively enhanced and improved, for example, Chinese patent CN105111968A, the advantages of zero carbonization, easy melting, small adhesive consumption and the like of the polyolefin packaging hot melt adhesive are enhanced compared with EVA hot melt packaging adhesive; for another example, chinese patent CN103881618A is an improvement to the disadvantage of slow curing of polyolefin packaging hot melt adhesive.

However, in the food production industry of cans, soy sauce and the like, high-speed automation of box sealing packaging, high heat resistance, diversified box sealing materials and low odor of box sealing glue are unique requirements, and the requirements are difficult to meet by the existing products. Therefore, the technical personnel in the field provide a novel high heat-resistant quick packaging hot melt adhesive and a preparation method thereof, so as to solve the problems in the background technology.

Disclosure of Invention

The invention aims to provide a novel high-heat-resistance quick-packaging hot melt adhesive and a preparation method thereof, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the novel high-heat-resistance quick-packaging hot melt adhesive comprises the following components in percentage by weight:

35-50% of metallocene olefin polymer

2 to 10% of an alpha-olefin copolymer

1-8% of reinforced rubber chain segment polymer

30-55% of tackifying resin

15-25% of Fischer-Tropsch wax

1-5% of an antioxidant;

the metallocene olefin polymer is a copolymer of low-crystallinity propylene and ethylene, and has the following density: and (2) carrying out high-speed harvest at the speed of 0.855-0.875 g/cm, and MFR: 3-1000 g/10 min;

the alpha-olefin copolymer is a copolymer which is obtained by grafting an alpha-olefin oligomer with the average molecular weight of 3000-10000 by using ethylene, propylene, butylene, ester or acid anhydride under the action of a catalyst, and has the average molecular weight of 10000-30000 and the softening point of 80-180 ℃;

the reinforced rubber chain segment polymer is a hydrogenated styrene block copolymer;

the tackifying resin is any one or mixture of more of aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, modified hydrocarbon resin and hydrogenated derivatives thereof, terpene and hydrogenated derivatives thereof, rosin and modified rosin and hydrogenated derivatives thereof;

the Fischer-Tropsch wax is an alkane polymer synthesized by a Fischer-Tropsch process, the average molecular weight is 800-1000, and the melt viscosity at 140 ℃ is 6-10;

the antioxidant is one or more of hindered phenol or hindered phenol combined with auxiliary antioxidant.

As a further scheme of the invention: the hot melt adhesive comprises the following components in percentage by weight:

35-45% of metallocene olefin polymer

5 to 8% of an alpha-olefin copolymer

1-5% of reinforced rubber chain segment polymer

30-40% of tackifying resin

15-22% of Fischer-Tropsch wax

1-3% of antioxidant.

As a still further scheme of the invention: the metallocene olefin polymer is preferably a copolymer of low crystallinity propylene and ethylene, density: and (2) carrying out high speed fruit harvest at 0.855-0.871 g/cm, MFR: 400-800 g/10 min.

As a still further scheme of the invention: the alpha-olefin copolymer is preferably a novel olefin copolymer obtained by silane grafting or anhydride modifying an amorphous poly-alpha-olefin copolymer polymerized by the Ziegler method.

As a still further scheme of the invention: the tackifying resin is preferably hydrogenated or semi-hydrogenated C5 petroleum resin, C5/C9 petroleum resin, terpene resin with the color of less than No. 3 in melt Gardner color, terpene styrene resin or hydrogenated rosin ester or a mixture of a plurality of the terpene resin, the terpene styrene resin and the hydrogenated rosin ester; the softening point of the tackifying resin by a ring and ball method is 100-120 ℃.

As a still further scheme of the invention: the Fischer-Tropsch wax is preferably any one of Fischer-Tropsch wax PX-105 or Fischer-Tropsch wax PX-100.

As a still further scheme of the invention: the antioxidant is preferably one or a mixture of two of the antioxidant 1010 and the antioxidant 168.

As a still further scheme of the invention: the brookfield viscosity of the hot melt adhesive is as follows: 1800 +/-500/160 ℃, softening point: 125 +/-10 ℃, and the curing time is as follows: 1.5-2.5 s.

A preparation method of a novel high-heat-resistance quick-packaging hot melt adhesive comprises the following steps:

(1) preparing raw materials: preparing the required raw materials according to the weight percentage for later use;

(2) preheating a reaction kettle: starting a reaction kettle for heating and starting stirring, wherein the oil temperature of the reaction kettle is set to be 250 ℃;

(3) heating the oil temperature of the reaction kettle to 160-170 ℃, adding Fischer-Tropsch wax and an antioxidant, and continuously stirring until all the components are completely melted;

(4) raising the temperature of the reaction kettle oil to 250 ℃ and keeping the temperature, adding the metallocene olefin polymer, the alpha-olefin copolymer and the reinforced rubber chain segment polymer, and stirring while vacuumizing until all the components are completely melted;

(5) setting the oil temperature of the reaction kettle at 200 ℃, adding tackifying resin, and stirring while vacuumizing until all components are completely melted;

(6) fully stirring and uniformly mixing, vacuumizing a reaction system until no bubbles exist, introducing nitrogen to normal pressure, and stopping stirring to obtain the novel high-heat-resistance quick-packaging hot melt adhesive.

Compared with the prior art, the invention has the beneficial effects that: the invention discloses a novel high heat-resistant rapid packaging hot melt adhesive and a preparation method thereof, wherein metallocene olefin polymer is selected as a main component of the novel high heat-resistant rapid packaging hot melt adhesive, and simultaneously alpha-olefin copolymer with good compatibility and reinforced rubber chain polymer are compounded to form a composite matrix component, so that good bonding performance and high and low temperature resistance of the composite matrix component are ensured; the application of a proper amount of Fischer-Tropsch wax reduces the wiredrawing property and the melt viscosity of the composite matrix component, and improves the fluidity and the curing speed of the hot melt adhesive; the use of a suitable tackifying resin provides higher peel strength to the hot melt adhesive itself and sufficient assurance that the hot melt adhesive will produce good bonding to the packaging substrates.

1. The adhesive property is strong: compared with the traditional EVA hot melt adhesive and the existing conventional polyolefin hot melt adhesive, the adhesive material applicable to the invention is wider and has stronger adhesive property.

2. Low odor: compared with the traditional EVA hot melt adhesive, the EVA hot melt adhesive has less smoke, low smell and more environmental protection in a hot melt state.

3. Fast curing and good heat resistance: the curing time of the packaging hot melt adhesive is 1.0-2.5 seconds, and the heat resistance is suitable for automatic box sealing packaging of food industries such as cans, soy sauce and the like with special requirements on heat resistance.

The preparation method is simple, low in cost and suitable for large-scale production.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the embodiment of the present invention, the first and second substrates,

example 1

A novel high-heat-resistance quick-packaging hot melt adhesive comprises the following components in percentage by weight:

metallocene olefin Polymer 888040%

Alpha-olefin copolymer 8075%

Reinforced rubber segment polymer MD 16483%

Monomer resin D12512.5%

Tackifying resin HM-100020%

Fischer-Tropsch wax PX-10518%

10100.5 percent of antioxidant

1681% of antioxidant.

(3) heating the oil temperature of the reaction kettle to 160-170 ℃, adding 18% of Fischer-Tropsch wax PX-105, 0.5% of antioxidant 1010 and 1% of antioxidant 168, and continuously stirring until all the components are completely melted;

(4) the temperature of the reaction kettle oil is raised to 250 ℃ and kept, 40 percent of metallocene olefin polymer 8880, 5 percent of alpha-olefin copolymer 807 and 3 percent of reinforced rubber segment polymer MD1648 are added, and the mixture is stirred while being vacuumized until all the components are completely melted;

(5) setting the oil temperature of the reaction kettle at 200 ℃, respectively adding 12.5 percent of monomer resin D125 and 20 percent of tackifying resin HM-1000, and stirring while vacuumizing until all components are completely melted;

Example 2

metallocene olefin Polymer 888035%

Alpha-olefin copolymer 8078%

Reinforced rubber segment polymer MD 16485%

Monomer resin D12510.5%

Tackifying resin HM-100020%

Fischer-Tropsch wax PX-10520%

10100.5 percent of antioxidant

1681% of antioxidant.

(3) heating the oil temperature of the reaction kettle to 160-170 ℃, adding 20% of Fischer-Tropsch wax PX-105, 0.5% of antioxidant 1010 and 1% of antioxidant 168, and continuously stirring until all the components are completely melted;

(4) the temperature of the reaction kettle oil is raised to 250 ℃ and kept, 35 percent of metallocene olefin polymer 8880, 8 percent of alpha-olefin copolymer 807 and 5 percent of reinforced rubber segment polymer MD1648 are added, and the mixture is stirred while being vacuumized until all the components are completely melted;

(5) setting the oil temperature of the reaction kettle at 200 ℃, respectively adding 10.5 percent of monomer resin D125 and 20 percent of tackifying resin HM-1000, and stirring while vacuumizing until all components are completely melted;

Example 3

metallocene olefin Polymer 888035%

Alpha-olefin copolymer 8078%

Reinforced rubber segment polymer MD 16483%

Monomer resin D12510.5%

Tackifying resin HM-100020%

Fischer-Tropsch wax PX-10522%

10100.5% of antioxidant;

1681% of antioxidant

(3) heating the oil temperature of the reaction kettle to 160-170 ℃, adding 22% of Fischer-Tropsch wax PX-105, 0.5% of antioxidant 1010 and 1% of antioxidant 168, and continuously stirring until all the components are completely melted;

(4) the temperature of the reaction kettle oil is raised to 250 ℃ and kept, 35 percent of metallocene olefin polymer 8880, 8 percent of alpha-olefin copolymer 807 and 3 percent of reinforced rubber segment polymer MD1648 are added, and the mixture is stirred while being vacuumized until all the components are completely melted;

Example 4

metallocene olefin Polymer 888045%

Alpha-olefin copolymer 8075%

Reinforced rubber segment polymer MD 16481%

Monomer resin D12515%

Tackifying resin HM-100015%

Fischer-Tropsch wax PX-10516%

Antioxidant 10101%;

1682% of antioxidant

(3) heating the oil temperature of the reaction kettle to 160-170 ℃, adding 16% of Fischer-Tropsch wax PX-105, 1% of antioxidant 1010 and 2% of antioxidant 168, and continuously stirring until all the components are completely melted;

(4) the temperature of the reaction kettle oil is raised to 250 ℃ and kept, 45 percent of metallocene olefin polymer 8880, 5 percent of alpha-olefin copolymer 807 and 1 percent of reinforced rubber segment polymer MD1648 are added, and the mixture is stirred while being vacuumized until all the components are completely melted;

(5) setting the oil temperature of the reaction kettle at 200 ℃, respectively adding 15% of monomer resin D125 and 15% of tackifying resin HM-1000, and stirring while vacuumizing until all components are completely melted;

Comparative example 1: conventional EVA type packaging hot melt adhesives are commercially available.

Comparative example 2: novel polyolefin packaging hot melt adhesive is sold in the market.

The products of example 1, example 2, example 3, example 4 and comparative example 1, comparative example 2 were selected and compared in six test items of Brookfield viscosity, softening point, curing time, hot-melt odor, adhesive property and heat resistance of the end-capped product.

The experimental method comprises the following steps:

1. brookfield viscosity test method: reference is made to GB/T2794-2013.

2. Softening point test method: reference is made to GB/T4507-2014.

3. Odor test method: reference is made to ASTM D4339-2001.

4. Curing time test method: and melting the glue, blade-coating the glue on one paperboard, then adhering the paperboard by using the other paperboard, timing from the completion of the adhesion, peeling from one end until the base material is broken, and recording the time, namely the curing time of the glue.

5. The adhesive property test method comprises the following steps: respectively selecting common corrugated paper, white cardboard, light oil ink paper and laminating paper, gluing, laminating, stripping after glue is solidified, and observing the bonding failure condition of the base material.

6. The method for testing the heat resistance of the box sealing finished product comprises the following steps:

(1): using a production line on the packaging hot melt adhesive to obtain a corresponding box-sealed packaging finished product;

(2): taking 1-3 packaged finished products, placing at 80 ℃ for 72 hours, taking out, and observing whether the bonding part bursts or not;

(3): during summer, the box-sealed packaged finished product is placed in a warehouse for 168 hours according to 10 stacked layers of 10 boxes, and whether the bonding part of the finished product bursts or not is observed;

(4): the tests (2) and (3) are both regarded as the heat resistance is qualified and the tests are passed.

The experimental results are as follows: see table 1 below for details

Table 1 heat energy glue experiment test results

Items of embodiment

Example 1

Example 2

Example 3

Example 4

Comparative example 1

Comparative example 2

Brookfield viscosity (cps/160 ℃ C.)

2000

2300

2100

1800

2050

1900

Softening Point (. degree. C.)

120

125

30

118

128

Curing time (S)

2

1.5

0.5

2

Hot melt smell (180 ℃ C.)

Small

Big (a)

Small

Adhesive property (whether material is broken)

Material crusher

Part of the base material can not be broken

Material crusher

Heat resistance of sealing box (whether burst open)

Does not explode

Bursting open

Does not explode

Bursting open

Therefore, the products in embodiments 1 to 4 of the present invention have moderate melt viscosity, good adhesion performance, wide applicable adhesion base material, fast curing, low odor, and good heat resistance, and have great advantages in the case sealing package of high-speed automatic production in the food industry, and particularly have unique advantages that are difficult to replace in the fields of cans, soy sauce, and the like having special requirements for heat resistance.

The hot melt adhesive is applied to the field of automatic carton sealing and packaging of products such as cans, soy sauce and the like in the food industry, but is not limited to the field and is also used as the automatic carton sealing and packaging of products such as beer, beverage and the like.

Other compounds which do not affect the physical and chemical properties of the hot melt adhesive can be added into the hot melt adhesive, and the other compounds comprise pigments for increasing the color, fluorescent agents, any compounds for covering the odor, ultraviolet absorbers and the like. Additives to these compounds are well known to those skilled in the art.

In conclusion, the metallocene olefin polymer is selected as the main component of the novel high-heat-resistance quick-packaging hot melt adhesive, and simultaneously the alpha-olefin copolymer with good compatibility and the reinforced rubber chain polymer are compounded to form the composite matrix component, so that the good adhesive property and high and low temperature resistance of the composite matrix component are ensured; the application of a proper amount of Fischer-Tropsch wax reduces the wiredrawing property and the melt viscosity of the composite matrix component, and improves the fluidity and the curing speed of the hot melt adhesive; the use of a suitable tackifying resin provides higher peel strength to the hot melt adhesive itself and sufficient assurance that the hot melt adhesive will produce good bonding to the packaging substrates. The invention has the advantages of strong adhesive property, low odor, quick curing and good heat resistance, and the preparation method is simple, has lower cost and is suitable for large-scale production.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims

1. The novel high-heat-resistance quick-packaging hot melt adhesive is characterized by comprising the following components in percentage by weight:

35-50% of metallocene olefin polymer

2 to 10% of an alpha-olefin copolymer

1-8% of reinforced rubber chain segment polymer

30-55% of tackifying resin

15-25% of Fischer-Tropsch wax

1-5% of an antioxidant;

2. The novel high-heat-resistance quick-packaging hot melt adhesive as claimed in claim 1, which comprises the following components in percentage by weight:

35-45% of metallocene olefin polymer

5 to 8% of an alpha-olefin copolymer

1-5% of reinforced rubber chain segment polymer

30-40% of tackifying resin

15-22% of Fischer-Tropsch wax

1-3% of antioxidant.

3. The novel high heat-resistant fast packaging hot melt adhesive as claimed in claim 1, wherein the metallocene olefin polymer is preferably a copolymer of low crystallinity propylene and ethylene, density: and (2) carrying out high speed fruit harvest at 0.855-0.871 g/cm, MFR: 400-800 g/10 min.

4. The novel high heat-resistant fast-packaging hot melt adhesive as claimed in claim 1, wherein the α -olefin copolymer is preferably a novel olefin copolymer obtained by silane-grafting or anhydride-modifying an amorphous poly- α -olefin copolymer polymerized by the ziegler process.

5. The novel high heat-resistant fast-packaging hot melt adhesive as claimed in claim 1, wherein the tackifying resin is preferably any one or a mixture of hydrogenated or semi-hydrogenated C5 petroleum resin, C5/C9 petroleum resin, terpene resin with color less than No. 3 in melt Gardner color, terpene styrene resin and hydrogenated rosin ester;

the softening point of the tackifying resin by a ring and ball method is 100-120 ℃.

6. The novel high heat-resistant fast-packaging hot melt adhesive as claimed in claim 1, wherein the fischer-tropsch wax is preferably any one of fischer-tropsch wax PX-105 or fischer-tropsch wax PX-100.

7. The novel high-heat-resistance quick-packaging hot melt adhesive as claimed in claim 1, wherein the antioxidant is preferably one or a mixture of two of antioxidant 1010 and antioxidant 168.

8. The novel high-heat-resistance quick packaging hot melt adhesive as claimed in claim 1, wherein the Brookfield viscosity of the hot melt adhesive is as follows: 1800 +/-500/160 ℃, softening point: 125 +/-10 ℃, and the curing time is as follows: 1.5-2.5 s.

9. The preparation method of the novel high-heat-resistance quick-packaging hot melt adhesive according to any one of claims 1 to 8, characterized in that the specific preparation method of the hot melt adhesive comprises the following steps: