CN114958247A - Medical green water-based heat-sealing adhesive and preparation method thereof - Google Patents
Medical green water-based heat-sealing adhesive and preparation method thereof Download PDFInfo
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- CN114958247A CN114958247A CN202210101173.7A CN202210101173A CN114958247A CN 114958247 A CN114958247 A CN 114958247A CN 202210101173 A CN202210101173 A CN 202210101173A CN 114958247 A CN114958247 A CN 114958247A
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- ethylene
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- acrylic acid
- based heat
- vinyl acetate
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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
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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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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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to C09J, in particular to a medical green water-based heat-sealing adhesive and a preparation method thereof. The preparation raw materials of the heat-seal adhesive comprise: biological wax, high molecular wax, rosin resin, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and neutralizer. After the ethylene-acrylic acid copolymer serving as an emulsifier reacts with the ethylene-vinyl acetate copolymer and is neutralized, the dispersion suspension property in water is promoted, and the water-based heat sealing adhesive is obtained and used for bonding medical packaging materials. When the ethylene-acrylic acid copolymer and the ethylene-vinyl acetate copolymer are simply added, the inventor finds that the stripping temperature is higher and the damage of the fibers of the dialyzing paper after stripping is caused, and the inventor finds that the proper stripping strength is kept during stripping by adopting the high-molecular wax with higher temperature while the reduction of the stripping temperature is promoted by adding the low-melting-point biological wax, so that the problem that the paper scraps are remained due to the difficulty in smooth stripping after subsequent heat sealing is avoided.
Description
Technical Field
The invention relates to C09J, in particular to a medical green water-based heat-sealing adhesive and a preparation method thereof.
Background
The medical sterilization package is generally composed of dialysis paper, such as Dupont Tyvek and the like, and a plastic film (or paper), wherein a heat-sealing adhesive is needed for bonding, and a water-based heat-sealing adhesive is generally adopted for the requirements of environmental protection and safety. However, in order to ensure the packaging effect, the consumption of the existing heat-sealing glue is large, and the air permeability is influenced.
CN108251016B provides a two-component-based general water-based heat sealing adhesive for medical instrument packaging and a preparation method thereof, and multiple polymer emulsions are adopted as main components to promote air permeability of dialysis paper and improve storage stability.
However, the existing heat-sealing glue has complex components, and if low-temperature heat sealing is required, acrylic emulsion is usually required to be prepared, and the existing water-based heat-sealing glue is difficult to realize good balance of heat-sealing strength and peeling residue while the process is complex.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a medical green water-based heat-sealing adhesive, which is prepared from the following raw materials: biological wax, high molecular wax, rosin resin, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and neutralizer.
As a preferable technical scheme, the preparation raw materials of the heat-seal adhesive comprise the following components in parts by weight: biological wax: 5-30 parts; polymer wax: 5-30 parts; rosin resin: 5-20 parts of a solvent; ethylene acrylic acid copolymer: 5-30 parts; ethylene-vinyl acetate polymer: 50-80 parts; and (4) neutralizing agent.
In a preferred embodiment of the present invention, the bio-wax has a melting point of 90 ℃ or lower, and the polymer wax has a softening point (ring and ball method) of 98 ℃ or higher.
Examples of biological waxes include, but are not limited to, beeswax, carnauba wax, soy wax, coconut wax such as DONGAO white beeswax, carnauba wax 8015-86-9, Jiaxin soy wax, Jiaxin coconut wax, and the like, wherein the melting points of beeswax, carnauba wax, soy wax, and coconut wax are all less than or equal to 90 deg.C, and the melting points are about 90 deg.C, 80-86 deg.C, 58-68 deg.C, and 40 deg.C, respectively. The biological wax is one or a mixture of more biological waxes, is not particularly limited, and only needs the melting point to be lower than the initial heat sealing temperature.
As examples of the polymer wax, there may be mentioned polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, etc., such as HONEWEIRER A-C6/6A, Jilin petrochemical LY95, Jilin petrochemical LY100, Jilin petrochemical LY105, Jilin petrochemical LY110, Tesheng PE wax, Jinlu JL-92, Jinlu JL-95, Trituo LRH-268, Trituo LRH-368, Trituo LRH-468, Trituo LRH-568, Thailand SCG LP0100P, etc., wherein the general softening point of the polyethylene wax is about 98 to 115 ℃.
As a preferable technical scheme of the invention, the weight ratio of the ethylene-acrylic acid copolymer to the ethylene-vinyl acetate copolymer is (5-30): (50-80), wherein the weight ratio of the polymer wax to the ethylene-acrylic acid copolymer is (5-30): (5-30).
Examples of the ethylene-acrylic acid copolymer include, but are not limited to, Korea SK EAA3004 (acrylic acid content: 9.7%, melt index: 8.5g/10min (190 ℃/2.16kg)), Dow's EAA3440 (melt index: 11g/10min (190 ℃/2.16kg), acrylic acid content: 9.7%), EAA3004 (melt index: 8.5g/10min (190 ℃/2.16kg), acrylic acid content: 9.7%), EAA1410 (melt index: 1.5g/10min (190 ℃/2.16kg), acrylic acid content: 9.7%), EAA 1321 (melt index: 2.6g/10min (190 ℃/2.16kg), acrylic acid content: 6.5%).
Preferably, the weight percentage of acrylic acid in the ethylene-acrylic acid copolymer is greater than or equal to 6%; more preferably, the weight percentage of acrylic acid in the ethylene-acrylic acid copolymer is 6-12%, and even more preferably 8-12%.
More preferably, the ethylene-acrylic acid copolymer has a melt index of 2 to 12g/10min (190 ℃/2.16kg), and still more preferably 6 to 12g/10min (190 ℃/2.16 kg).
Examples of the ethylene-vinyl acetate copolymer include, but are not limited to, U.S. DuPont 150 (melt finger: 43g/10min (190 ℃/2.16kg), vinyl acetate content: 32%), U.S. DuPont 40W (melt finger: 52g/10min (190 ℃/2.16kg), vinyl acetate content: 40%), U.S. DuPont 450 (melt finger: 8g/10min (190 ℃/2.16kg), vinyl acetate content: 18%), U.S. DuPont 460 (melt finger: 2.5g/10min (190 ℃/2.16kg), vinyl acetate content: 18%), U.S. DuPont 630, U.S. DuPont E418, U.S. DuPont E4260, U.S. DuPont 007S, U.S. DuPont 750 (melt finger: 7g/10min (190 ℃/2.16kg), vinyl acetate content: 9%), Japanese DuPont EV260, Japanese Sumitomo chemical F2021, Japanese Sumitomo chemical SV330, SV, Japanese Sumitomo chemical SV340, Japanese Sumitomo chemical SWA110, Japanese Sumitomo chemical SWA130, Japanese Sumitomo chemical SWA210, Japanese Sumitomo chemical SWA230, Japanese eastern Marine L-3388, Japanese eastern Cao 510, Japanese eastern Cao 630, Japanese Asahi chemical RF7830, Japanese Enoki card WSVA3010, Japanese Enoki card WSVA3020, Korean LGEA 19150.
Preferably, the weight percentage of the vinyl acetate in the ethylene-vinyl acetate copolymer is more than or equal to 7 percent; more preferably, the weight percentage of the vinyl acetate in the ethylene-vinyl acetate copolymer is 7-20%.
More preferably, the ethylene-vinyl acetate copolymer has a melt index of 2 to 12g/10min (190 ℃/2.16kg), and still more preferably 6 to 12g/10min (190 ℃/2.16 kg).
As a preferable technical solution of the present invention, the rosin resin is one or more selected from glycerol-modified rosin, pentaerythritol-modified rosin, and maleic rosin-modified resin. As a preferable technical scheme of the invention, the weight ratio of the rosin resin to the ethylene-acrylic acid copolymer is (5-20): (5-30).
As examples of the maleic acid rosin-modified resin, there can be mentioned Runlin rosin resin, Guangshi rosin resin 465654, Medium Vinegar rosin resin 422# (softening point (ring and ball method) ≥ 128 ℃ C., acid value ≤ 35mg KOH/g), Medium Vinegar resin 424# (softening point (ring and ball method) 136 ℃ C., acid value ≤ 30mg KOH/g), Delri chemical 4121 maleic acid rosin resin (softening point (ring and ball method) 100-. As a preferable technical scheme of the invention, the softening point of the maleic rosin modified resin is more than or equal to 128 ℃, and the acid value is less than or equal to 35mg KOH/g.
The neutralizing agent is not specifically limited, and examples include ammonia, diethanolamine, diethylamine, triethylamine, diethanolamine, triethanolamine, and the like, and the neutralizing agent is not specifically limited in specific amount, and only the residual acid after the reaction is neutralized.
The heat-sealing adhesive may further include additives, such as an antioxidant, a lubricant, a wetting agent, and the like, without being particularly limited.
The second aspect of the invention provides a preparation method of the medical green water-based heat-seal adhesive, which comprises the following steps: and melting the biological wax, the high-molecular wax, the rosin resin and the ethylene-vinyl acetate copolymer, adding the ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal adhesive.
As a preferable technical scheme, the preparation method of the medical green water-based heat-sealing adhesive comprises the following steps: heating biological wax, high-molecular wax, rosin resin and ethylene-vinyl acetate copolymer to 80-180 ℃, adding ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal adhesive.
The third aspect of the invention provides an emulsion, which comprises the medical green water-based heat-seal adhesive and water, wherein the solid content of the emulsion is 30-50 wt%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a heat-sealing adhesive, which is used for bonding medical packaging materials by using an aqueous heat-sealing adhesive which is obtained by using an ethylene-acrylic acid copolymer as an emulsifier to react with an ethylene-vinyl acetate copolymer and then neutralizing the ethylene-acrylic acid copolymer to promote the dispersion and suspension properties in water.
(2) When the ethylene-acrylic acid copolymer and the ethylene-vinyl acetate copolymer are simply added, the inventor finds that the stripping temperature is higher and the damage of the fibers of the dialyzing paper after stripping is caused, and the inventor finds that the proper stripping strength is kept during stripping by adopting the high-molecular wax with higher temperature while the reduction of the stripping temperature is promoted by adding the low-melting-point biological wax, so that the problem that the paper scraps are remained due to the difficulty in smooth stripping after subsequent heat sealing is avoided.
(3) The inventor also finds that when the biological wax and the polymer wax are used simultaneously, compared with the simple use of the biological wax, the storage and dilution stability of the aqueous heat-sealing glue are promoted, the spreading performance of subsequent coating is promoted to be improved, and the biological wax can be used for bonding various plastics (such as PET, PVC, PI, PE and the like)/paper and dialyzing paper.
(4) In addition, the inventor also finds that the low melting point and softening point of the biological wax and the high molecular wax relative to the heat sealing temperature can influence the permeation of the sterilizing gas, and the rosin resin, such as maleic rosin modified resin, is added to promote a certain micro-control structure after drying, promote ventilation and simultaneously reduce the invasion of cells and the like.
(5) Compared with the rosin resin with a high acid value, the inventor also finds that the rosin resin with a lower acid value, the ethylene-acrylic acid copolymer with a proper acid value and the ethylene-vinyl acetate copolymer are adopted to act together, so that the balance between a high polymer and a wax system is facilitated, the emulsion with better stability is obtained, and meanwhile, the damage to paper fibers in the stripping process is reduced.
Detailed Description
Examples
Example 1
The embodiment provides a water-based heat-seal adhesive, which comprises the following raw materials in parts by weight: 20 parts of bio-wax, down Yao and white beeswax; polymer wax, U.S. Honiville A-C6/6A: 20 parts of (1); rosin resin vesuvianite resin 422 #: 15 parts of (1); ethylene acrylic acid copolymer EAA 3004: 30 parts of (1); ethylene vinyl acetate polymer, U.S. dupont 460: 80 parts of a mixture; neutralizing agent diethanolamine.
The embodiment also provides a preparation method of the water-based heat-seal adhesive, which comprises the following steps: heating the biological wax, the high-molecular wax, the rosin resin and the ethylene-vinyl acetate copolymer to 160 ℃, adding the ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal adhesive.
Example 2
The embodiment provides a water-based heat-seal adhesive, which comprises the following raw materials in parts by weight: biological wax (carnauba wax and jiaxin soybean wax in a weight ratio of 1: 0.5): 15 parts of a mixture; three-way polymer wax LRH-468: 10 parts of (A); vinsol resin 424# among rosin resins: 15 parts of (1); ethylene acrylic acid copolymer EAA 3440: 20 parts of (1); ethylene vinyl acetate polymer dupont 450: 65 parts of (1); neutralizing agent diethanolamine.
The embodiment also provides a preparation method of the water-based heat-seal adhesive, which comprises the following steps: heating biological wax, high-molecular wax, rosin resin and ethylene-vinyl acetate copolymer to 160 ℃, adding the ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal glue.
Example 3
The embodiment provides a water-based heat-seal adhesive, which comprises the following raw materials in parts by weight: carnauba wax: 5 parts of a mixture; three-way polymer wax LRH-468: 5 parts of a mixture; vinsol resin 424# among rosin resins: 5 parts of a mixture; ethylene acrylic acid copolymer EAA 3440: 10 parts of (A); ethylene vinyl acetate polymer dupont 750: 50 parts of a mixture; neutralizing agent diethanolamine.
The embodiment also provides a preparation method of the water-based heat-seal adhesive, which comprises the following steps: heating the biological wax, the high-molecular wax, the rosin resin and the ethylene-vinyl acetate copolymer to 160 ℃, adding the ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal adhesive.
Example 4
The embodiment provides a water-based heat-seal adhesive, which comprises the following raw materials in parts by weight: biological wax (carnauba wax and jiaxin soybean wax in a weight ratio of 1: 0.5): 15 parts of (1); three-way polymer wax LRH-468: 2 parts of (1); vinsol resin 424# among rosin resins: 15 parts of (1); ethylene acrylic acid copolymer EAA 3440: 20 parts of (1); ethylene vinyl acetate polymer dupont 450: 65 parts of (1); neutralizing agent diethanolamine.
The embodiment also provides a preparation method of the water-based heat-seal adhesive, which comprises the following steps: heating the biological wax, the high-molecular wax, the rosin resin and the ethylene-vinyl acetate copolymer to 160 ℃, adding the ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal adhesive.
Example 5
The embodiment provides a water-based heat-seal adhesive, which comprises the following raw materials in parts by weight: biological wax (carnauba wax and jiaxin soybean wax in a weight ratio of 1: 0.5): 15 parts of (1); three-way polymer wax LRH-468: 10 parts of (A); rosin resin 4121 maleic rosin resin: 15 parts of (1); ethylene acrylic acid copolymer EAA 3440: 20 parts of (1); ethylene vinyl acetate polymer U.S. dupont 450: 65 parts of (1); neutralizing agent diethanolamine.
The embodiment also provides a preparation method of the water-based heat-seal adhesive, which comprises the following steps: heating the biological wax, the high-molecular wax, the rosin resin and the ethylene-vinyl acetate copolymer to 160 ℃, adding the ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal adhesive.
Evaluation of Performance
1. Heat seal strength: will be described in the embodimentsThe supplied heat-sealing glue is made into emulsion with the solid content of 40 percent, and the emulsion is coated on dialyzing paper and dried to obtain the dry glue with the coating weight of 2g/m 2 Post-wind, heat-seal PVC film, peel strength calculated according to ASTM F8806 as heat-seal strength, and heat-seal strength at seal-off temperature, where the seal-off temperature provided in examples 1-3 was found to be 95 ℃ and below, the seal-off temperature of example 1 was found to be 95 ℃ (3.06N/15mm), heat-seal strength (140 ℃): 6.08N/15mm, and the dialyzing paper was observed to be broken or have scraps left after being peeled off, and the results are shown in Table 1.
2. Air permeability: preparing the heat-seal adhesive provided by the embodiment into emulsion with the solid content of 40%, coating the emulsion on dialyzing paper, and drying to obtain the dry adhesive with the coating weight of 2g/m 2 And (3) post-rolling, namely, after the PET film is subjected to heat sealing at 140 ℃ and 4bar for 2s, calculating the air permeability according to ISO 5636-3, and obtaining the results shown in Table 1.
3. Diluting the heat-seal adhesive into emulsion with solid content of 40%, diluting the emulsion by 3-5 times, storing the emulsion for 24h, and observing whether layering, residue, flocculation and the like occur, wherein the results are shown in Table 1.
TABLE 1
4. And (3) performance testing: the heat-seal glues provided in the examples were made into 30-45% solids emulsions and tested as follows, with the results satisfying the properties in Table 2.
TABLE 2
Claims (10)
1. The medical green water-based heat-sealing adhesive is characterized by comprising the following raw materials:
biological wax, high molecular wax, rosin resin, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and neutralizer.
2. The medical green water-based heat-seal adhesive as claimed in claim 1, wherein the biological wax is a biological wax with a melting point of 90 ℃ or lower, and the polymer wax is a polymer wax with a softening point of 98 ℃ or higher.
3. The medical green water-based heat-seal adhesive according to claim 1, wherein the weight ratio of the biological wax to the polymer wax is (5-30): (5-30).
4. The medical green water-based heat-seal adhesive as claimed in claim 1, wherein the weight ratio of the ethylene-acrylic acid copolymer to the ethylene-vinyl acetate copolymer is (5-30): (50-80), wherein the weight ratio of the polymer wax to the ethylene-acrylic acid copolymer is (5-30): (5-30).
5. The medical green water-based heat-seal adhesive as claimed in claim 4, wherein the weight percentage of acrylic acid in the ethylene-acrylic acid copolymer is greater than or equal to 6%.
6. The medical green water-based heat-seal adhesive as claimed in claim 5, wherein the weight percentage of acrylic acid in the ethylene-acrylic acid copolymer is 6-12%.
7. The medical green water-based heat-seal adhesive as claimed in claim 1, wherein the weight percentage of vinyl acetate in the ethylene-vinyl acetate copolymer is greater than or equal to 7%.
8. The medical green water-based heat-seal adhesive according to any one of claims 1 to 7, wherein the rosin resin is one or more selected from glycerol-modified rosin, pentaerythritol-modified rosin and maleic rosin-modified resin.
9. The preparation method of the medical green water-based heat-sealing adhesive according to any one of claims 1 to 8, characterized by comprising the following steps: heating and mixing biological wax, high-molecular wax, rosin resin and ethylene-vinyl acetate copolymer, adding ethylene-acrylic acid copolymer for reaction, and adding a neutralizer for neutralization to obtain the heat-seal glue.
10. An emulsion comprising the green colored water-based heat-sealable adhesive for medical use according to any one of claims 1 to 8 and water, wherein the emulsion has a solid content of 30 to 50 wt%.
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| CN202210101173.7A CN114958247A (en) | 2022-01-27 | 2022-01-27 | Medical green water-based heat-sealing adhesive and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247428A (en) * | 1979-08-16 | 1981-01-27 | The Goodyear Tire & Rubber Company | Adhesive for polyesters and polyolefins |
| CN101289599A (en) * | 2008-06-04 | 2008-10-22 | 金尔昇 | Process for dispersing hot-melt adhesive fillers |
| CN107057636A (en) * | 2017-06-06 | 2017-08-18 | 王京赫 | A kind of PUR and preparation method thereof |
| CN108587521A (en) * | 2018-04-20 | 2018-09-28 | 无锡市健鼎包装技术有限公司 | A kind of medical dialyzing paper aqueous coating heat-seal adhesive and its coating process |
| CN109321171A (en) * | 2018-09-26 | 2019-02-12 | 上海乘鹰新材料有限公司 | Aqueous medical dialyzing paper heat-seal adhesive of one kind and preparation method thereof |
-
2022
- 2022-01-27 CN CN202210101173.7A patent/CN114958247A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247428A (en) * | 1979-08-16 | 1981-01-27 | The Goodyear Tire & Rubber Company | Adhesive for polyesters and polyolefins |
| CN101289599A (en) * | 2008-06-04 | 2008-10-22 | 金尔昇 | Process for dispersing hot-melt adhesive fillers |
| CN107057636A (en) * | 2017-06-06 | 2017-08-18 | 王京赫 | A kind of PUR and preparation method thereof |
| CN108587521A (en) * | 2018-04-20 | 2018-09-28 | 无锡市健鼎包装技术有限公司 | A kind of medical dialyzing paper aqueous coating heat-seal adhesive and its coating process |
| CN109321171A (en) * | 2018-09-26 | 2019-02-12 | 上海乘鹰新材料有限公司 | Aqueous medical dialyzing paper heat-seal adhesive of one kind and preparation method thereof |
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