CN112760062B - Environment-friendly polyolefin hot melt adhesive for cigarettes and preparation method thereof - Google Patents
Environment-friendly polyolefin hot melt adhesive for cigarettes and preparation method thereof Download PDFInfo
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- CN112760062B CN112760062B CN202011563702.2A CN202011563702A CN112760062B CN 112760062 B CN112760062 B CN 112760062B CN 202011563702 A CN202011563702 A CN 202011563702A CN 112760062 B CN112760062 B CN 112760062B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an environment-friendly polyolefin hot melt adhesive for cigarettes and a preparation method thereof, belonging to the technical field of high polymer material synthesis. The composite material is mainly prepared from the following raw materials in percentage by weight: 20-40% of POP resin, 5-20% of modified resin, 5-15% of modifier, 20-50% of tackifying resin and 0.1-1% of antioxidant. And provides a preparation method. The hot melt adhesive disclosed by the invention is a hot melt adhesive with high safety, environmental protection, aging resistance, lasting adhesion, low density, low softening point, low viscosity and good sealing property, can be used in the field of high-speed box sealing and packaging in the cigarette industry and the food industry, is particularly suitable for the fields of novel sealing and packaging in the tobacco and food industry, and is suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to an environment-friendly polyolefin hot melt adhesive for cigarettes and a preparation method thereof.
Background
In recent years, with the increasing industrialization progress of China, the speed of a box sealing and packaging line is also increased. The packaging speed is improved from 10-30 boxes/min to 30-50 boxes/min at present, and even higher. Especially in the cigarette industry, food industry and other industries related to daily life consumption of people, the automatic packaging degree is faster. At the same time, the food industry and the cigarette industry (in particular the new tobacco) put new demands on the tightness of the hot-melt adhesive bond, which, in summary, is:
high safety and environmental protection: lower limits of hazardous substances, such as lead and arsenic contents below five parts per million, are required.
High aging resistance: the viscosity change rate of the colloid is not large after long-time use, the pipe is not easy to be blocked, and no coke substance is generated, so that the long-time continuous and efficient work of the box sealing and packaging machine is ensured.
High durable adhesion: the problems of glue failure and the like do not occur in the production, transportation, storage and use processes of the product, and the product quality is not influenced.
Fourthly, low density: under the same sizing condition and adhesion, the sizing amount is small, and the raw material cost is reduced.
Low viscosity: can match the basic conditions of high-speed operation of the box sealing and packaging machine.
Sixthly, low softening point: the low softening point hot melt adhesive is more beneficial to low-temperature sizing, and the energy-saving effect is better.
The sealing performance is good: the new technical requirements are mainly to reduce the continuous loss of flavor or liquid components in the novel tobacco and food package.
At present, the hot melt adhesive for packaging and sealing boxes still takes EVA as a main material and can meet the three items of the requirements including (i), (v) and (v). But the defects are obvious, because the EVA resin contains a large amount of ester groups, the melt viscosity of the resin is high, the content of the resin in the synthesis process of the hot melt adhesive is low, and finally the adhesive has poor aging resistance, short lasting adhesion, high density and poor sealing property.
To solve the above problems, polyolefin resins such as polyethylene have been used to prepare hot melt adhesives. Meets five items of the requirements of (I), (II), (III), (IV) and (V). However, compared with EVA, the content of the complex is obviously increased and cannot meet the requirement. And meanwhile, the problem is not solved well.
Therefore, the POP resin which is the lowest softening point in the polyolefin resin is selected, and the requirements of (i), (ii), (iii), (iv) and (iv) are difficult to meet while the problems of (i), (iii), (iv) and (iv) are well solved. This is because POP has a high melt viscosity and a low curing speed. In the prior art, all the seven technical requirements are difficult to meet.
For example, Chinese patent CN103881618A discloses a fast packaging hot melt adhesive and a preparation method thereof: by adding a large amount of materials such as microcrystalline wax, polyethylene wax, paraffin wax, Fischer-Tropsch wax and the like in the process of synthesizing the hot melt adhesive, the viscosity is reduced and the curing speed is increased. Although the problems of high viscosity and low curing speed are solved, the bonding strength of the hot melt adhesive is obviously reduced along with the addition of a large amount of wax, and particularly, the surface of the hot melt adhesive is difficult to bond, even has no bonding strength. Most importantly, the phenomenon of adhesive failure is obviously increased, and the failure type is changed from the base material failure to the interface and adhesive layer failure, which shows that the cohesive strength and the adhesive property of the hot melt adhesive are obviously reduced.
Therefore, how to overcome the above technical problems and provide an environment-friendly polyolefin hot melt adhesive for cigarettes and a preparation method thereof are problems that need to be solved by technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides an environment-friendly polyolefin hot melt adhesive for cigarettes and a preparation method thereof.
The invention adopts the modified resin to solve the problems of high viscosity, slow curing speed and poor sealing property of POP. The modified resin is divided into two parts, namely polyolefin resin and polyisobutylene resin.
The polyolefin hot melt adhesive synthesized by using general thermoplastic materials such as polyethylene-propylene copolymer resin and the like as main resin has the advantages of high softening point, high melt viscosity and inapplicability. Although the softening point and the melt viscosity of the metallocene-catalyzed polyethylene-propylene copolymer resin are greatly reduced, the metallocene-catalyzed polyethylene-propylene copolymer resin still cannot be used as a main resin, but a polyolefin resin with the melt viscosity lower than that of the POP resin and the softening point slightly higher than that of the POP resin can be selected and used as a modified resin, so that the softening point is increased in a limited way, and the problem of overhigh melt viscosity caused by the overlarge addition amount of the POP resin can be reduced.
The metallocene catalyzed polyolefin resin is matched with POP resin, so that the hot melt adhesive with high aging resistance, low density, low viscosity, high bonding strength, safety and environmental protection can be synthesized. Compared with the POP resin used alone, the POP resin achieves the same melt viscosity, and the resin content can be 5-15% higher. I.e., increased permanent adhesion, decreased density, and a reduction in sizing by about 10%. However, the disadvantage is that the softening point rises to a different extent.
The polyisobutylene is used as the second component of the modified resin, can offset the increase of the softening point caused by adding the polyolefin modified resin, and has certain fluidity, adhesiveness and sealing property, so that the sealing effect after the whole is adhered is greatly improved, and all seven requirements mentioned in the background art are finally met.
In order to achieve the purpose, the invention adopts the following technical scheme:
an environment-friendly polyolefin hot melt adhesive for cigarettes is mainly prepared from the following raw materials in percentage by weight: 20-40% of POP resin, 5-20% of modified resin, 5-15% of modifier, 20-50% of tackifying resin and 0.1-1% of antioxidant.
Has the advantages that: the proportion is formed by adding modified resin and converting the typical technical scheme of common hot melt adhesive, and has universality.
Preferably: the composite material is mainly prepared from the following raw materials in percentage by weight: 20-40% of POP resin, 15-20% of modified resin, 10-15% of modifier, 29.8-39.8% of tackifying resin and 0.2% of antioxidant.
The beneficial effects are that: the optimized scheme balances the proportion of each component, particularly greatly reduces the upper limit of the content of the modifier, and enables the viscosity, the adhesive property, the density, the cohesive strength and the like to reach a balanced state.
Preferably: the POP resin is a copolymer of 1-octene and ethylene, and the density is 0.868-0.880 g/cm3。
And further: the physical and chemical properties of the copolymer of 1-octene and ethylene require that the melt viscosity at 175 ℃ is 6000-20000 mPa.s, and the melt index is 400-1200 g/10min under the conditions of 2.16kg and 190 ℃.
Has the advantages that: the setting of the technical indexes of the POP resin is the basis for preparing the hot melt adhesive with high safety, environmental protection, aging resistance, durable adhesion, low softening point and low viscosity.
Preferably: the modified resin is a mixture of polyolefin resin and polyisobutylene resin; the mass ratio of the polyolefin resin to the polyisobutylene resin is (1-2): 1.
preferably: the polyolefin resin is metallocene catalyzed polyethylene-propylene copolymer resin.
Further: the physical and chemical properties of the polyethylene-propylene copolymer resin are required to be solid at normal temperature, the melt viscosity at 150 ℃ is not higher than 20000mPa.s, and the ring-and-ball softening point is not higher than 110 ℃.
The beneficial effects are that: the function of the modified resin is to reduce the melt viscosity of the POP resin, balance the softening point and improve the sealing property.
Preferably: the modifier comprises one or more of Fischer-Tropsch wax, microcrystalline wax, polyethylene wax, paraffin, white oil and mineral oil;
wherein the ring-and-ball softening points of the Fischer-Tropsch wax, the microcrystalline wax, the polyethylene wax and the paraffin wax are 60-130 ℃.
Has the advantages that: the low softening point wax is primarily intended to balance the softening point of the hot melt adhesive, while having the effect of reducing the melt viscosity.
Preferably, the tackifying resin comprises one or more of rosin and derivatives thereof, terpene resin and derivatives thereof, and petroleum resin and derivatives thereof.
Further: hydrogenated derivatives of petroleum resins are selected, the ring and ball softening points of which are between 60 and 130 ℃.
Further, the petroleum resin is selected to be hydrogenated petroleum resin, and the ring and ball softening point is 80-110 ℃.
Further, the hydrogenated petroleum resin has a hydrogenation degree of more than 90%, and is more excellent in aging resistance.
Has the advantages that: the hydrogenated petroleum resin improves the integral aging resistance of the hot melt adhesive and reduces the softening point of the hot melt adhesive.
Preferably: antioxidants include antioxidant 1010 and/or BHT.
Further: BHT is also known as 2, 6-di-tert-butyl-p-cresol; the antioxidant 1010 is also known as pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Has the advantages that: the common antioxidant auxiliary agent in the hot melt adhesive technology has a synergistic effect when being used together.
The invention also provides a preparation method of the hot melt adhesive, which comprises the following steps:
(1) weighing the raw materials according to the weight ratio, placing the raw materials into a reactor, heating and stirring the raw materials at the stirring speed of 20-50 r/min, and heating the raw materials until the material temperature is kept at 95-105 ℃;
(2) heating to 140-160 ℃, stirring at a speed not lower than 100r/min, starting vacuum and reducing pressure, wherein the vacuum degree is not less than-0.08 MPa, reducing the pressure for 30-40 min, relieving the vacuum, cooling to 140-150 ℃, discharging, leveling, granulating and packaging.
According to the technical scheme, compared with the prior art, the invention discloses and provides the environment-friendly polyolefin hot melt adhesive for cigarettes and the preparation method thereof, and the technical effects are as follows:
aiming at the characteristics of high viscosity, low curing speed and poor sealing property in the prior POP technology, the modified resin is adopted to solve the problem. The modified resin meets the requirements of high aging resistance, low density, low melt viscosity, safety, environmental protection and the like, finally synthesizes the hot melt adhesive with high safety, environmental protection, high aging resistance, high lasting adhesion, low density, low softening point, low viscosity and good sealing property, can be used in the fields of high-speed box sealing and packaging in the cigarette industry, food industry and the like, is particularly suitable for the fields of novel sealing and packaging in the tobacco and food industry, has obvious improvement on the adhesion effect of materials difficult to adhere, such as cartons, soft package hardened tobacco packets and the like in the cigarette industry, and is suitable for popularization and application.
Detailed Description
The following will clearly and completely describe the technical solutions in 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 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.
The embodiment of the invention discloses an environment-friendly polyolefin hot melt adhesive for cigarettes and a preparation method thereof.
POP resins were purchased from Affinity (TM) GA 1950 polyofin Plastic (POP), Dow, USA.
Example 1
A preparation method of a hot melt adhesive comprises the following steps:
(1) adding raw materials (see table 1) into a container, heating and stirring at a stirring speed of 20r/min, and heating until the material temperature is kept at 95 ℃;
(2) heating to 140 deg.C after adding the raw materials, stirring at a speed of not less than 100r/min, starting vacuum, reducing the vacuum degree to not less than-0.08 MPa, reducing the pressure for 30min, removing the vacuum, cooling to 140 deg.C, discharging, leveling, granulating, and packaging.
Example 2
A preparation method of a hot melt adhesive comprises the following steps:
(1) adding the raw materials (see table 1) into a container according to the above raw material metering ratio, heating and stirring at a stirring speed of 30r/min until the material temperature is kept at 100 ℃;
(2) after the raw materials are added, heating to 150 ℃, stirring at a speed of not less than 100r/min, starting vacuum and reducing pressure, wherein the vacuum degree is not less than-0.08 MPa, reducing pressure for 35min, removing vacuum, cooling to 145 ℃, discharging, leveling, granulating and packaging.
Example 3
A preparation method of a hot melt adhesive comprises the following steps:
(1) adding the raw materials (see table 1) into a container according to the above raw material metering ratio, heating and stirring at a stirring speed of 50r/min until the material temperature is maintained at 105 ℃;
(2) after the raw materials are added, heating to 160 ℃, stirring at a speed of not less than 100r/min, starting vacuum and reducing pressure, wherein the vacuum degree is not less than-0.08 MPa, reducing pressure for 40min, removing vacuum, cooling to 150 ℃, discharging, leveling, granulating and packaging.
Comparative experiment
The hot melt adhesives were prepared according to the preparation methods of examples 1 to 3, respectively, using the raw materials shown in table 1.
Comparative examples 1 to 3 are typical polyolefin hot melt adhesives, POP hot melt adhesives and EVA hot melt adhesives (components are shown in Table 1), respectively.
TABLE 1 tables of compounding data for examples 1-3 and comparative examples
Experimental data: the basic performance tests and the computer experimental data are shown in table 2:
table 2 basic performance data and on-machine data of examples 1 to 3 and comparative examples 1 to 3
The results show that:
1. the results of comparing example 1 with comparative example 1 show that: the hot melt adhesive (comparative example 1) in which the main resin is a metallocene polyethylene-propylene copolymer resin is excellent in lowering the melt viscosity, but also has a significantly high softening point, and example 1 is low in the amount of application and superior in sealing and adhesion to comparative example 1.
2. The results of comparing example 2 with comparative example 2 show that: the modified resin has great effect of lowering the melt viscosity of POP resin and hot melt adhesive after modification, and the softening point is raised within a controllable range (raised by only 2 ℃). And meanwhile, the adhesive has excellent adhesiveness and sealing property.
3. Example 3 and comparative example 3 illustrate: the traditional EVA hot melt adhesive ratio (comparative example 3) is used, the addition amount of the modifier (oil and wax) is large, the bonding performance is reduced, and meanwhile, the heat aging resistance is poor due to the existence of the EVA resin.
By adopting the technical scheme of the embodiment of the invention, the characteristics of high aging resistance, low density, low melt viscosity, safety, environmental protection and the like of the modified resin are utilized, and other processes and raw materials are matched to finally synthesize the hot melt adhesive with high safety, environmental protection, high aging resistance, high lasting adhesion, low density, low softening point, low viscosity and good sealing property, so that the hot melt adhesive can be used in the fields of high-speed box sealing and packaging in the cigarette industry, the food industry and the like, is particularly suitable for the fields of novel tobacco, food industry sealing and packaging and the like, has obvious improvement on the bonding effect on materials difficult to bond, such as a carton, a soft package hardening cigarette packet and the like in the cigarette industry, and is suitable for popularization and application.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The environment-friendly polyolefin hot melt adhesive for cigarettes is characterized by mainly comprising the following raw materials in percentage by weight: 20-40% of POP resin, 15-20% of modified resin, 10-15% of modifier, 29.8-39.8% of tackifying resin and 0.2% of antioxidant;
the POP resin is a copolymer of 1-octene and ethylene, and the density is 0.868-0.880 g/cm 3;
the modified resin is a mixture of polyolefin resin and polyisobutylene resin; the mass ratio of the polyolefin resin to the polyisobutylene resin is (1-2): 1;
the polyolefin resin is metallocene catalyzed polyethylene-propylene copolymer resin.
2. The hot melt adhesive of claim 1, wherein the modifier comprises one or more of a mixture of Fischer-Tropsch wax, microcrystalline wax, polyethylene wax, paraffin wax, white oil, and mineral oil;
wherein the ring-and-ball softening points of the Fischer-Tropsch wax, the microcrystalline wax, the polyethylene wax and the paraffin wax are 60-130 ℃.
3. The hot melt adhesive of claim 1, wherein the tackifying resin comprises a mixture of one or more of rosin and derivatives thereof, terpene resin and derivatives thereof, and petroleum resin and derivatives thereof.
4. The hot melt adhesive of claim 1, wherein the antioxidant comprises antioxidant 1010 and/or BHT.
5. A preparation method of a hot melt adhesive is characterized by comprising the following steps:
(1) weighing the raw materials according to any one of claims 1 to 4, placing the raw materials in a reactor, heating and stirring the raw materials at a stirring speed of 20 to 50r/min, and heating the raw materials until the material temperature is kept between 95 and 105 ℃;
(2) heating to 140-160 ℃, stirring at a speed not lower than 100r/min, starting vacuum and reducing pressure, reducing the vacuum degree to be not less than-0.08 MPa, relieving the vacuum after reducing the pressure for 30-40 min, discharging after cooling to 140-150 ℃, leveling, granulating and packaging.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113322034B (en) * | 2021-06-08 | 2022-04-26 | 北京长润化工有限公司 | Hot melt adhesive for filter stick and preparation method and application thereof |
| CN115247039B (en) * | 2022-05-13 | 2023-10-31 | 上海路嘉胶粘剂有限公司 | Quick-drying cigarette hot melt adhesive with good weather resistance and preparation process thereof |
| CN115044333B (en) * | 2022-07-27 | 2023-07-07 | 北京长润化工有限公司 | Hot melt adhesive for packaging and preparation method and application thereof |
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|---|---|---|---|---|
| CA2203450A1 (en) * | 1996-04-24 | 1997-10-24 | Darryl A. Godfrey | Polyethylene based hot melt adhesive |
| JP2011195711A (en) * | 2010-03-19 | 2011-10-06 | Toyo Adl Corp | Hot melt type adhesive composition and laminate using the same |
| CN103881618A (en) * | 2014-03-13 | 2014-06-25 | 广州泰晟生物科技有限公司 | Rapid packing hot melt adhesive and preparation method thereof |
| CN107257833A (en) * | 2015-01-23 | 2017-10-17 | 波士胶公司 | Metallocene-polyolefin base low activation temperature seals hot-melt adhesive |
| CN108219711A (en) * | 2018-01-18 | 2018-06-29 | 广州景翊粘合剂有限公司 | A kind of air filter polypropylene thermal melten gel and its preparation method and application |
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2020
- 2020-12-25 CN CN202011563702.2A patent/CN112760062B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2203450A1 (en) * | 1996-04-24 | 1997-10-24 | Darryl A. Godfrey | Polyethylene based hot melt adhesive |
| JP2011195711A (en) * | 2010-03-19 | 2011-10-06 | Toyo Adl Corp | Hot melt type adhesive composition and laminate using the same |
| CN103881618A (en) * | 2014-03-13 | 2014-06-25 | 广州泰晟生物科技有限公司 | Rapid packing hot melt adhesive and preparation method thereof |
| CN107257833A (en) * | 2015-01-23 | 2017-10-17 | 波士胶公司 | Metallocene-polyolefin base low activation temperature seals hot-melt adhesive |
| CN108219711A (en) * | 2018-01-18 | 2018-06-29 | 广州景翊粘合剂有限公司 | A kind of air filter polypropylene thermal melten gel and its preparation method and application |
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