WO2021208508A1 - 一种用于纸盒包装行业的胶膜及其制备方法 - Google Patents

一种用于纸盒包装行业的胶膜及其制备方法 Download PDF

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WO2021208508A1
WO2021208508A1 PCT/CN2020/140463 CN2020140463W WO2021208508A1 WO 2021208508 A1 WO2021208508 A1 WO 2021208508A1 CN 2020140463 W CN2020140463 W CN 2020140463W WO 2021208508 A1 WO2021208508 A1 WO 2021208508A1
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parts
adhesive film
antioxidant
combination
temperature
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French (fr)
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何建雄
杨博
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何建雄
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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention belongs to the field of hot melt adhesives, and relates to an adhesive film, in particular to an adhesive film used in the carton packaging industry and a preparation method thereof.
  • TPU Thermoplastic Polyurethane
  • PVC polyvinyl chloride material
  • TPU has excellent physical properties, such as abrasion resistance and resilience better than ordinary polyurethane and PVC, and aging resistance is better than rubber. It can be said that it is the most ideal material to replace PVC and PU.
  • Polyurethane glue is a glue containing urethane and isocyanate groups in the molecular chain. Because it contains strong polar isocyanate and urethane groups, it has high reactivity and can be cured at room temperature. , Plastic, wood, fabric, leather and other materials have excellent adhesive properties. The main chain of polyurethane is very flexible, and its biggest feature is its resistance to shock, vibration and bending fatigue, high peel strength, especially excellent low temperature resistance, and it stands out among the existing glues. Polyurethane glue has simple process, can be cured at room temperature and heating, and has little effect of thermal stress when different materials are glued. It has a wide range of applications in various fields.
  • CN 105542701 A discloses the formula of a new type of polyurethane glue and a preparation method thereof. After the reaction is carried out by adding diisocyanate and polyether diol into a low-temperature and normal-pressure reactor, the reacted mixture is added to high-temperature and normal pressure. The reaction kettle is used to react to produce a new type of polyurethane glue.
  • the polyurethane glue can be applied to make pressure-sensitive adhesives, and can also be used to foam and make foam pressure-sensitive adhesives.
  • the beneficial effects of the present invention are: no Solvents exist, the environmental impact is small, the process is easy to control, the reaction time is short, and there is no need to add expensive combustion devices that are likely to cause safety hazards.
  • the polyurethane glue provided has a lower bonding strength to metal.
  • CN 106398623 A discloses a water-based polyurethane glue
  • the water-based polyurethane glue contains the following components by weight: 40-60% solid content of 80-120 parts of water-based polyurethane dispersion, 0.05-0.8 parts of defoamer, wetting and dispersing 0.1-1.0 parts of agent, 0.1-0.7 parts of pH value regulator, 0.3-1.0 parts of thickener, 0.01-0.8 parts of bactericide.
  • the water-based polyurethane glue of the present invention is prepared into a one-component water-based polyurethane glue by using medium-crystalline water-based polyurethane, matched with suitable pH value regulators, thickeners and other ingredients, which has excellent aging resistance and high temperature resistance and stable storage It has the characteristics of high performance, no organic volatile matter volatilization, and simple use process.
  • the invention also discloses a preparation method of the water-based polyurethane glue.
  • the polyurethane glue provided has a lower bonding strength to metal.
  • white glue is mostly used for carton packaging.
  • white glue has defects such as weak adhesion and transparent capacity. Hot melt glue is relatively rarely used in carton packaging.
  • the present invention provides an adhesive film used in the carton packaging industry and a preparation method thereof.
  • the corrugated paper and the liner board play a physical and chemical bonding role at the same time, and the overall strength of the bonded carton is enhanced, and the carton is not easy to deform and crack.
  • the present invention adopts the following technical solutions:
  • One of the objectives of the present invention is to provide an adhesive film for the carton packaging industry.
  • the raw materials of the adhesive film include hexamethylene diisocyanate, polyether polyol, chain extender, catalyst, plasticizer, and tackifier. Resins, fillers and additives.
  • the raw materials of the adhesive film in parts by weight include:
  • the weight parts of hexamethylene diisocyanate can be 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts or 79 parts, etc.
  • the weight parts of the polyether polyol can be 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts or 59 parts, etc.
  • the weight parts of the chain extender can be 11 parts, 12 parts, 13 parts, 14 parts, 15 parts , 16 parts, 17 parts, 18 parts or 19 parts, etc.
  • the weight parts of the catalyst can be 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, etc.
  • the weight parts of the plasticizer can be 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, etc.
  • the weight parts of the tackifying resin can be 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts , 18 parts or 19 parts, etc.
  • the weight parts of the filler can be 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts or 29 parts, etc.
  • the weight parts of the additives can be 1.5 Parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, etc., but are not limited to the listed values, and other unlisted values in the above numerical ranges are also applicable.
  • the raw materials of the adhesive film in parts by weight include:
  • the degree of polymerization of the polyether polyol is 3000-5000, such as 3000, 3500, 4000, 4500 or 5000, etc., but it is not limited to the listed values, and the range of values is not listed elsewhere. The values also apply.
  • the chain extender includes any one or a combination of at least two of 1,4-butanediol, 1,6-hexanediol, diethylene glycol or diethylaminoethanol, Typical but non-limiting examples of the combination are: the combination of 1,4-butanediol and 1,6-hexanediol, the combination of 1,6-hexanediol and diethylene glycol, the combination of diethylene glycol and diethylaminoethanol , A combination of diethylaminoethanol and 1,4-butanediol or a combination of 1,4-butanediol, 1,6-hexanediol and diethylene glycol, etc.
  • the catalyst includes any one or a combination of at least two of stannous chloride, stannous octoate, hydroxytrimethyltin or dibutyltin dilaurate, a typical but non-limiting example of the combination There are: a combination of stannous chloride and stannous octoate, a combination of stannous octoate and hydroxytrimethyltin, a combination of hydroxytrimethyltin and dibutyltin dilaurate or stannous chloride, stannous octoate and Combinations of hydroxytrimethyltin, etc.
  • the plasticizer includes any one or a combination of at least two of dibutyl phthalate, diisononyl phthalate or dioctyl phthalate, Typical but non-limiting examples of the combination are: the combination of dibutyl phthalate and diisononyl phthalate, the combination of diisononyl phthalate and dioctyl phthalate, The combination of dioctyl phthalate and dibutyl phthalate or the combination of dibutyl phthalate, diisononyl phthalate and dioctyl phthalate, etc.
  • the tackifying resin includes rosin resin and/or terpene resin.
  • the filler includes aluminum oxide and/or silicon dioxide.
  • the auxiliary agent includes an antioxidant and a flame retardant.
  • the flame retardant includes any one or a combination of at least two of red phosphorus capsules, APP or MCA.
  • Typical but non-limiting examples of the combination include: a combination of red phosphorus capsules and APP, APP and MCA The combination of red phosphorus capsules and MCA or the combination of red phosphorus capsules, APP and MCA, etc.
  • the antioxidant includes any one or a combination of at least two of antioxidant 1010, antioxidant 1076, or antioxidant 168.
  • a typical but non-limiting example of the combination is: antioxidant 1010 Combination with antioxidant 1076, combination of antioxidant 1076 and antioxidant 168, combination of antioxidant 168 and antioxidant 1010, or combination of antioxidant 1010, antioxidant 1076 and antioxidant 168.
  • the weight part of the flame retardant is 0.5 to 2.5 parts, such as 0.6 part, 0.8 part, 1.0 part, 1.2 part, 1.5 part, 1.8 part, 2.2 part or 2.4 part, etc., but it is not limited to the listed ones. Numerical value, other unlisted values in this numerical range are also applicable.
  • the weight of the antioxidant is 0.5 to 2.5 parts, such as 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.2 parts or 2.4 parts, etc., but is not limited to those listed Numerical value, other unlisted values in this numerical range are also applicable.
  • a plasticizer and a tackifying resin are added to the hot-melt adhesive, and the two have a synergistic effect, which not only increases the viscosity of the hot-melt adhesive, but also reduces its softening temperature, and enhances the resistance of the hot-melt adhesive after film formation. Tensile strength.
  • the second objective of the present invention is to provide a method for preparing the above-mentioned adhesive film used in the carton packaging industry.
  • the preparation method includes the following steps:
  • step (1) The raw materials in step (1) are pumped and injected into a twin-screw extruder, and the twin-screw extruder is used for reaction and underwater granulation to obtain hot melt adhesive particles for preparing the adhesive film.
  • the temperature during vacuum dehydration in step (1) is 60-80°C, such as 60°C, 63°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C or 80°C, etc., but not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the stirring rate in step (1) is 300-1000r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min or 1000r/min min, etc., but not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the pressure during vacuum dehydration in step (1) is -0.3 ⁇ -0.1kPa, such as -0.3kPa, -0.28kPa, -0.25kPa, -0.23kPa, -0.2kPa, -0.18kPa, -0.15kPa , -0.13kPa or -0.1kPa, etc., but not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the temperature of the feeding section of the twin-screw extruder in step (2) is 110-120°C, such as 112°C, 115°C, 118°C, or 120°C; the temperature of the mixing section is 130-120°C.
  • 150°C such as 132°C, 135°C, 138°C, 140°C, 143°C, 145°C or 148°C, etc.
  • the temperature of the extrusion section is 170 ⁇ 180°C, such as 172°C, 175°C, 178°C or 180°C, etc.
  • the temperature of the machine head is 150-160°C, such as 153°C, 155°C, 158°C or 160°C, etc., but not limited to the listed values, and other unlisted values within the above-mentioned ranges are also applicable.
  • the present invention has at least the following beneficial effects:
  • the present invention provides an adhesive film used in the carton packaging industry and a preparation method thereof.
  • the hot-melt adhesive film has a good bonding force with wet objects, has strong penetrating power, and is simultaneously formed between the corrugated paper and the liner board. To physical and chemical bonding, the overall strength of the bonded carton is enhanced, and the carton is not easy to deform and crack;
  • the softening temperature of the hot melt adhesive provided by the present invention is lower than 100°C, and the viscosity can reach 150,000 mPa ⁇ s when tested at 180°C, and the adhesive film has good performance at -20-60°C.
  • Fig. 1 is a graph of the relationship between the tensile strength of the adhesive film and the temperature in a specific embodiment of the present invention.
  • This embodiment provides a method for preparing an adhesive film used in the carton packaging industry.
  • the preparation method includes the following steps:
  • step (1) Pumping and injecting the raw materials in step (1) into a twin-screw extruder, using the twin-screw extruder to react and underwater pelletizing, to obtain hot melt adhesive particles for preparing the adhesive film;
  • the temperature of the feeding section of the twin-screw extruder is 110°C
  • the temperature of the mixing section is 130°C
  • the temperature of the extrusion section is 170°C
  • the temperature of the die head is 150°C;
  • step (3) The hot-melt adhesive particles obtained in step (2) are heated at 100° C. for 10 s to melt, and then coated on the carton to be adhered, and the adhesive film is obtained after cooling.
  • This embodiment provides a method for preparing an adhesive film used in the carton packaging industry.
  • the preparation method includes the following steps:
  • step (1) Pumping and injecting the raw materials in step (1) into a twin-screw extruder, using the twin-screw extruder to react and underwater pelletizing, to obtain hot melt adhesive particles for preparing the adhesive film;
  • the feeding section temperature of the twin-screw extruder is 120°C
  • the mixing section temperature is 150°C
  • the extrusion section temperature is 180°C
  • the die temperature is 160°C;
  • step (3) The hot-melt adhesive particles obtained in step (2) are heated at 100° C. for 10 s to melt, and then coated on the carton to be adhered, and the adhesive film is obtained after cooling.
  • This embodiment provides a method for preparing an adhesive film used in the carton packaging industry.
  • the preparation method includes the following steps:
  • step (1) Pumping and injecting the raw materials in step (1) into a twin-screw extruder, using the twin-screw extruder to react and underwater pelletizing, to obtain hot melt adhesive particles for preparing the adhesive film;
  • the feeding section temperature of the twin-screw extruder is 115°C
  • the mixing section temperature is 140°C
  • the extrusion section temperature is 175°C
  • the die temperature is 155°C;
  • step (3) The hot-melt adhesive particles obtained in step (2) are heated at 100° C. for 10 s to melt, and then coated on the carton to be adhered, and the adhesive film is obtained after cooling.
  • This embodiment provides a method for preparing an adhesive film used in the carton packaging industry.
  • the preparation method includes the following steps:
  • step (1) Pumping and injecting the raw materials in step (1) into a twin-screw extruder, using the twin-screw extruder to react and underwater pelletizing, to obtain hot melt adhesive particles for preparing the adhesive film;
  • the feeding section temperature of the twin-screw extruder is 115°C
  • the mixing section temperature is 140°C
  • the extrusion section temperature is 175°C
  • the die temperature is 155°C;
  • step (3) The hot-melt adhesive particles obtained in step (2) are heated at 100° C. for 10 s to melt, and then coated on the carton to be adhered, and the adhesive film is obtained after cooling.
  • This embodiment provides a method for preparing an adhesive film used in the carton packaging industry.
  • the preparation method includes the following steps:
  • step (1) Pumping and injecting the raw materials in step (1) into a twin-screw extruder, using the twin-screw extruder to react and underwater pelletizing, to obtain hot melt adhesive particles for preparing the adhesive film;
  • the feeding section temperature of the twin-screw extruder is 115°C
  • the mixing section temperature is 140°C
  • the extrusion section temperature is 175°C
  • the die temperature is 155°C;
  • step (3) The hot-melt adhesive particles obtained in step (2) are heated at 100° C. for 10 s to melt, and then coated on the carton to be adhered, and the adhesive film is obtained after cooling.
  • Example 1 82 108350 3.5
  • Example 2 97 149770 4.2
  • Example 3 90 112020 3.6
  • Example 4 95 135730 3.9
  • Example 5 93 140960 3.7 Comparative example 1 125 102530 1.2 Comparative example 2 119 71370 3.0
  • the hot melt adhesive prepared in Examples 1-5 of the present application has a low softening point, high viscosity, and excellent tensile strength after bonding.
  • the tensile strength of the above-mentioned adhesive film was tested at different temperatures in the range of -30-80°C, and it was found that the above-mentioned adhesive film had good performance at -20-60°C. And in the process of making the adhesive film, it was also found that the hot melt adhesive has the best viscosity when the paper surface processing temperature is 45-60°C. Comparative Example 1 added a plasticizer, and Comparative Example 2 did not add a tackifying resin, resulting in Comparative Examples 1 and 2 inferior to Example 5 in all aspects of performance.

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  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

一种用于纸盒包装行业的胶膜及其制备方法，其特征在于，所述胶膜的原料包括六亚甲基二异氰酸酯、聚醚多元醇、扩链剂、催化剂、增塑剂、增粘树脂、填料以及助剂。所述热熔胶膜与湿物有很好的结合力，渗透力强，在瓦楞纸和衬纸板间同时起到物理及化学的粘合作用，粘合后的纸箱整体强度增强，纸箱不易变形与开裂。

Description

一种用于纸盒包装行业的胶膜及其制备方法
本公开基于申请号为202010298506.0，申请日为2020年04月16日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明属于热熔胶领域，涉及一种胶膜，尤其涉及一种用于纸盒包装行业的胶膜及其制备方法。
背景技术
热塑性聚氨酯(TPU)是一种新型的有机高分子合成材料，其各项性能优异，可以代替橡胶、软性聚氯乙烯材料PVC。TPU具有优异的物理性能，例如耐磨性，回弹力都好过普通聚氨酯和PVC，耐老化性优于橡胶，可以说是替代PVC和PU的最理想的材料。
聚氨酯胶水是分子链中含有氨酯基和异氰酸酯基的胶水，由于含有强极性的异氰酸酯和氨基甲酸酯基，具有很高的反应性，能够室温固化，因而对金属、橡胶、玻璃、陶瓷、塑料、木材、织物、皮革等多种材料都有优良的胶粘性能。聚氨酯的主链柔性很好，其最大特点是耐受冲击震动和弯曲疲劳，剥离强度很高，特别是耐低温性能极其优异，在现有的胶水中独占鳌头。聚氨酯胶水工艺简便，室温和加热均能固化，不同材料胶粘时热应力影响小，在各个领域都有广泛的应用。
CN 105542701 A公开了一种新型聚氨酯胶水的配方及其制备方法,通过将二异氰酸酯以及聚醚二元醇添加进低温常压反应釜实施反应后，在将反应后的混合物料添加进高温常压反应釜实施反应，制成新型的聚氨酯胶水，所述的聚 氨酯胶水实现了可以实施涂布制作压敏胶，还可以用来发泡，制作泡棉压敏胶；本发明有益效果为：完全不存在溶剂，环境影响小，工艺易于控制，反应时间短，无需加配价格昂贵且容易造成安全隐患的燃烧装置，由于不存在溶剂，同时排除了烘干过程中由于溶剂和高温存在而带来的安全风险，相对保障了作业人员的生命财产安全。但是该技术方案中，提供的聚氨酯胶水对于金属的粘接强度较低。
CN 106398623 A公开了一种水性聚氨酯胶水，所述水性聚氨酯胶水包含以下重量份的成分：40～60％固含量的水性聚氨酯分散体80～120份、消泡剂0.05～0.8份、润湿分散剂0.1～1.0份、pH值调节剂0.1～0.7份、增稠剂0.3～1.0份、杀菌剂0.01～0.8份。本发明的水性聚氨酯胶水，通过使用中等结晶性的水性聚氨酯，搭配合适的pH值调节剂、增稠剂等成分，制备成单组份水性聚氨酯胶水，其具有耐老化耐高温性能优、贮存稳定性高、无有机挥发物挥发、使用工艺简单等特点。同时，本发明还公开了所述水性聚氨酯胶水的制备方法。但是该技术方案中，提供的聚氨酯胶水对于金属的粘接强度同样较低。
现有技术中，纸盒包装多用白胶水，然而白胶水存在粘合不牢固、容量透胶等缺陷，热熔胶早纸盒包装中的使用还相对较少。
发明内容
针对现有技术中存在的技术问题，本发明提供一种用于纸盒包装行业的胶膜及其制备方法，所述热熔胶膜与湿物有很好的结合力，渗透力强，在瓦楞纸和衬纸板间同时起到物理及化学的粘合作用，粘合后的纸箱整体强度增强，纸箱不易变形与开裂。
为达上述目的，本发明采用以下技术方案：
本发明目的之一在于提供一种用于纸盒包装行业的胶膜，所述胶膜的原料 包括六亚甲基二异氰酸酯、聚醚多元醇、扩链剂、催化剂、增塑剂、增粘树脂、填料以及助剂。
作为本发明优选的技术方案，按照重量份计所述胶膜的原料包括：
Figure PCTCN2020140463-appb-000001
其中，六亚甲基二异氰酸酯的重量份可以是71份、72份、73份、74份、75份、76份、77份、78份或79份等，聚醚多元醇的重量份可以是51份、52份、53份、54份、55份、56份、57份、58份或59份等，扩链剂的重量份可以是11份、12份、13份、14份、15份、16份、17份、18份或19份等，催化剂的重量份可以是1.5份、2份、2.5份、3份、3.5份、4份或4.5份等，增塑剂的重量份可以是1.5份、2份、2.5份、3份、3.5份、4份或4.5份等，增粘树脂的重量份可以是11份、12份、13份、14份、15份、16份、17份、18份或19份等，填料的重量份可以是21份、22份、23份、24份、25份、26份、27份、28份或29份等，助剂的重量份可以是1.5份、2份、2.5份、3份、3.5份、4份或4.5份等，但并不仅限于所列举的数值，上述各数值范围其他未列举的数值同样适用。
作为本发明优选的技术方案，按照重量份计所述胶膜的原料包括：
Figure PCTCN2020140463-appb-000002
作为本发明优选的技术方案，所述聚醚多元醇的聚合度为3000～5000，如3000、3500、4000、4500或5000等，但并不仅限于所列举的数值，该数值范围其他未列举的数值同样适用。
作为本发明优选的技术方案，所述扩链剂包括1,4-丁二醇、1,6-己二醇、二甘醇或二乙氨基乙醇中的任意一种或至少两种的组合，所述组合典型但非限制性实例有：1,4-丁二醇和1,6-己二醇的组合、1,6-己二醇和二甘醇的组合、二甘醇和二乙氨基乙醇的组合、二乙氨基乙醇和1,4-丁二醇的组合或1,4-丁二醇、1,6-己二醇和二甘醇的组合等。
优选地，所述催化剂包括氯化亚锡、辛酸亚锡、羟基三甲基锡或二丁基二月桂酸锡中的任意一种或至少两种的组合，所述组合典型但非限制性实例有：氯化亚锡和辛酸亚锡的组合、辛酸亚锡和羟基三甲基锡的组合、羟基三甲基锡和二丁基二月桂酸锡的组合或氯化亚锡、辛酸亚锡和羟基三甲基锡的组合等。
作为本发明优选的技术方案，所述增塑剂包括邻苯二甲酸二丁酯、邻苯二甲酸二异壬酯或邻苯二甲酸二辛酯中的任意一种或至少两种的组合，所述组合典型但非限制性实例有：邻苯二甲酸二丁酯和邻苯二甲酸二异壬酯的组合、邻 苯二甲酸二异壬酯和邻苯二甲酸二辛酯的组合、邻苯二甲酸二辛酯和邻苯二甲酸二丁酯的组合或苯二甲酸二丁酯、邻苯二甲酸二异壬酯和邻苯二甲酸二辛酯的组合等。
优选地，所述增粘树脂包括松香树脂和/或萜烯树脂。
优选地，所述填料包括三氧化二铝和/或二氧化硅。
作为本发明优选的技术方案，所述助剂包括抗氧剂和阻燃剂。
优选地，所述阻燃剂包括红磷胶囊、APP或MCA中的任意一种或至少两种的组合，所述组合典型但非限制性实例有：红磷胶囊和APP的组合、APP和MCA的组合、红磷胶囊和MCA的组合或红磷胶囊、APP和MCA的组合等。
优选地，所述抗氧剂包括抗氧剂1010、抗氧剂1076或抗氧剂168中的任意一种或至少两种的组合，所述组合典型但非限制性实例有：抗氧剂1010和抗氧剂1076的组合、抗氧剂1076和抗氧剂168的组合、抗氧剂168和抗氧剂1010的组合或抗氧剂1010、抗氧剂1076和抗氧剂168的组合。
优选地，所述阻燃剂的重量份为0.5～2.5份，如0.6份、0.8份、1.0份、1.2份、1.5份、1.8份、2.2份或2.4份等，但并不仅限于所列举的数值，该数值范围其他未列举的数值同样适用。
优选地，所述抗氧剂的重量份为0.5～2.5份，如0.6份、0.8份、1.0份、1.2份、1.5份、1.8份、2.2份或2.4份等，但并不仅限于所列举的数值，该数值范围其他未列举的数值同样适用。
本发明中，在热熔胶中加入增塑剂与增粘树脂，二者产生协同作用，不仅增加了热熔胶的粘度，同时降低了其软化温度，增强了热熔胶成膜后的抗拉强度。
本发明目的之二在于提供一种上述用于纸盒包装行业的胶膜的制备方法， 所述制备方法包括以下步骤：
(1)按照配比将六甲基二异氰酸酯加入到A储料罐中，聚醚多元醇加入到B储料罐中，扩链剂、催化剂、增塑剂、增粘树脂、填料以及助剂加入到C储料罐中，在搅拌条件下，真空脱水；
(2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒。
作为本发明优选的技术方案，步骤(1)所述真空脱水时的温度为60～80℃，如60℃、63℃、65℃、68℃、70℃、72℃、75℃、78℃或80℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(1)所述搅拌的速率为300～1000r/min，如300r/min、400r/min、500r/min、600r/min、700r/min、800r/min、900r/min或1000r/min等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(1)所述真空脱水时的压力为-0.3～-0.1kPa，如-0.3kPa、-0.28kPa、-0.25kPa、-0.23kPa、-0.2kPa、-0.18kPa、-0.15kPa、-0.13kPa或-0.1kPa等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本发明优选的技术方案，步骤(2)所述双螺杆挤出机的喂料段温度为110～120℃，如112℃、115℃、118℃或120℃等；混合段温度为130～150℃，如132℃、135℃、138℃、140℃、143℃、145℃或148℃等；挤出段温度为170～180℃，如172℃、175℃、178℃或180℃等；机头温度为150～160℃，如153℃、155℃、158℃或160℃等，但并不仅限于所列举的数值，上述各数值范围内其他未列举的数值同样适用。
与现有技术方案相比，本发明至少具有以下有益效果：
(1)本发明提供一种用于纸盒包装行业的胶膜及其制备方法，所述热熔胶膜与湿物有很好的结合力，渗透力强，在瓦楞纸和衬纸板间同时起到物理及化学的粘合作用，粘合后的纸箱整体强度增强，纸箱不易变形与开裂；
(2)本发明提供的热熔胶的软化温度低于100℃，且粘度在180℃下测试可达150000mPa·s，胶膜在-20-60℃之间均有良好的性能。
附图说明
图1是本发明具体实施方式中胶膜的抗拉强度与温度的关系曲线图。
下面对本发明进一步详细说明。但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
实施例1
本实施例提供一种用于纸盒包装行业的胶膜的制备方法，所述制备方法包括以下步骤：
(1)按照配比将70份六甲基二异氰酸酯加入到A储料罐中，50份PPG3000加入到B储料罐中，10份1,4-丁二醇、1份氯化亚锡、1份邻苯二甲酸二丁酯、10份松香树脂、20份二氧化硅、0.5份抗氧剂1010以及0.5份红磷胶囊加入到C储料罐中，在300r/min的搅拌条件下，60℃以及-0.3kPa下真空脱水；
(2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒；
所述双螺杆挤出机的喂料段温度为110℃，混合段温度为130℃，挤出段温度为170℃，机头温度为150℃；
(3)将步骤(2)得到的热熔胶颗粒在100℃下加热10s至熔融后涂覆于纸盒粘结除，冷却后得到胶膜。
实施例2
本实施例提供一种用于纸盒包装行业的胶膜的制备方法，所述制备方法包括以下步骤：
(1)按照配比将80份六甲基二异氰酸酯加入到A储料罐中，60份PPG5000加入到B储料罐中，20份1,6-己二醇、5份辛酸亚锡、5份邻苯二甲酸二异壬酯、20份萜烯树脂、30份二氧化硅、2.5份抗氧剂1076以及2.5份MCA加入到C储料罐中，在1000r/min的搅拌条件下，80℃以及-0.1kPa下真空脱水；
(2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒；
所述双螺杆挤出机的喂料段温度为120℃，混合段温度为150℃，挤出段温度为180℃，机头温度为160℃；
(3)将步骤(2)得到的热熔胶颗粒在100℃下加热10s至熔融后涂覆于纸盒粘结除，冷却后得到胶膜。
实施例3
本实施例提供一种用于纸盒包装行业的胶膜的制备方法，所述制备方法包括以下步骤：
(1)按照配比将72份六甲基二异氰酸酯加入到A储料罐中，55份PPG4000加入到B储料罐中，12份二甘醇、2份羟基三甲基锡、2份邻苯二甲酸二辛酯、12份松香树脂、25份二氧化硅、1份抗氧剂168以及1份APP加入到C储料罐 中，在500r/min的搅拌条件下，70℃以及-0.2kPa下真空脱水；
(2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒；
所述双螺杆挤出机的喂料段温度为115℃，混合段温度为140℃，挤出段温度为175℃，机头温度为155℃；
(3)将步骤(2)得到的热熔胶颗粒在100℃下加热10s至熔融后涂覆于纸盒粘结除，冷却后得到胶膜。
实施例4
本实施例提供一种用于纸盒包装行业的胶膜的制备方法，所述制备方法包括以下步骤：
(1)按照配比将78份六甲基二异氰酸酯加入到A储料罐中，58份PPG4000加入到B储料罐中，15份二乙氨基乙醇、3份二丁基二月桂酸锡、3份邻苯二甲酸二辛酯、18份松香树脂、28份二氧化硅、1.5份抗氧剂168以及1.5份APP加入到C储料罐中，在500r/min的搅拌条件下，70℃以及-0.2kPa下真空脱水；
(2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒；
所述双螺杆挤出机的喂料段温度为115℃，混合段温度为140℃，挤出段温度为175℃，机头温度为155℃；
(3)将步骤(2)得到的热熔胶颗粒在100℃下加热10s至熔融后涂覆于纸盒粘结除，冷却后得到胶膜。
实施例5
本实施例提供一种用于纸盒包装行业的胶膜的制备方法，所述制备方法包 括以下步骤：
(1)按照配比将75份六甲基二异氰酸酯加入到A储料罐中，56份PPG4000加入到B储料罐中，16份二乙氨基乙醇、2.5份二丁基二月桂酸锡、2.5份邻苯二甲酸二辛酯、15份松香树脂、26份二氧化硅、1份抗氧剂168以及1.5份APP加入到C储料罐中，在500r/min的搅拌条件下，70℃以及-0.2kPa下真空脱水；
(2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒；
所述双螺杆挤出机的喂料段温度为115℃，混合段温度为140℃，挤出段温度为175℃，机头温度为155℃；
(3)将步骤(2)得到的热熔胶颗粒在100℃下加热10s至熔融后涂覆于纸盒粘结除，冷却后得到胶膜。
对比例1
本对比例除了不加入增塑剂而换为等质量的增粘树脂外，其余条件均与实施例5相同。
对比例2
本对比例除了不加入增粘树脂而换为等质量的增塑剂外，其余条件均与实施例5相同。
将实施例1-5以及对比例1-2得到的热熔胶颗粒的软化温度、软化后(180℃)的粘度，胶膜(厚度0.5mm)的抗拉强度进行测试结果如表1所示。
表1
  软化温度/℃ 粘度/mPa·s 抗拉强度/MPa
实施例1 82 108350 3.5
实施例2 97 149770 4.2
实施例3 90 112020 3.6
实施例4 95 135730 3.9
实施例5 93 140960 3.7
对比例1 125 102530 1.2
对比例2 119 71370 3.0
通过表1的测试结果可以看出，本申请实施例1-5制备得到热熔胶的软化点较低，且粘度高，粘结后的抗拉强度优异。在-30-80℃范围内的不同温度下对上述胶膜的抗拉强度进行测试发现，上述胶膜在-20-60℃之间均有良好的性能。且在胶膜制作过程中，还发现当纸面加工温度在45～60℃时，热熔胶具有最佳粘度。对比例1为添加增塑剂，而对比例2未添加增粘树脂，导致对比例1和2的各方面性能均差于实施例5。
申请人声明，本发明通过上述实施例来说明本发明的详细结构特征，但本发明并不局限于上述详细结构特征，即不意味着本发明必须依赖上述详细结构特征才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用部件的等效替换以及辅助部件的增加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征， 在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

  1. 一种用于纸盒包装行业的胶膜，其特征在于，所述胶膜的原料包括六亚甲基二异氰酸酯、聚醚多元醇、扩链剂、催化剂、增塑剂、增粘树脂、填料以及助剂。
  2. 根据权利要求1所述的胶膜，其特征在于，按照重量份计所述胶膜的原料包括：
    Figure PCTCN2020140463-appb-100001
  3. 根据权利要求1或2所述的胶膜，其特征在于，按照重量份计所述胶膜的原料包括：
    Figure PCTCN2020140463-appb-100002
    Figure PCTCN2020140463-appb-100003
  4. 根据权利要求1-3任一项所述的胶膜，其特征在于，所述聚醚多元醇的聚合度为3000～5000。
  5. 根据权利要求1-4任一项所述的胶膜，其特征在于，所述扩链剂包括1,4-丁二醇、1,6-己二醇、二甘醇或二乙氨基乙醇中的任意一种或至少两种的组合；
    优选地，所述催化剂包括氯化亚锡、辛酸亚锡、羟基三甲基锡或二丁基二月桂酸锡中的任意一种或至少两种的组合。
  6. 根据权利要求1-5任一项所述的胶膜，其特征在于，所述增塑剂包括邻苯二甲酸二丁酯、邻苯二甲酸二异壬酯或邻苯二甲酸二辛酯中的任意一种或至少两种的组合；
    优选地，所述增粘树脂包括松香树脂和/或萜烯树脂；
    优选地，所述填料包括三氧化二铝和/或二氧化硅。
  7. 根据权利要求1-6任一项所述的胶膜，其特征在于，所述助剂包括抗氧剂和阻燃剂；
    优选地，所述阻燃剂包括红磷胶囊、APP或MCA中的任意一种或至少两种的组合；
    优选地，所述抗氧剂包括抗氧剂1010、抗氧剂1076或抗氧剂168中的任意一种或至少两种的组合；
    优选地，所述阻燃剂的重量份为0.5～2.5份；
    优选地，所述抗氧剂的重量份为0.5～2.5份。
  8. 根据权利要求1-7任一项所述的胶膜的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)按照配比将六甲基二异氰酸酯加入到A储料罐中，聚醚多元醇加入 到B储料罐中，扩链剂、催化剂、增塑剂、增粘树脂、填料以及助剂加入到C储料罐中，在搅拌条件下，真空脱水；
    (2)将步骤(1)中的原料抽注到双螺杆挤出机中，利用双螺杆挤出机反应、水下造粒，得到制备所述胶膜的热熔胶颗粒。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤(1)所述真空脱水时的温度为60～80℃；
    优选地，步骤(1)所述搅拌的速率为300～1000r/min；
    优选地，步骤(1)所述真空脱水时的压力为-0.3～-0.1kPa；
  10. 根据权利要求8所述的制备方法，其特征在于，步骤(2)所述双螺杆挤出机的喂料段温度为110～120℃，混合段温度为130～150℃，挤出段温度为170～180℃，机头温度为150～160℃。
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