WO2022183554A1 - 一种丙烯酸涂布镀氧化硅薄膜及其制造方法 - Google Patents

一种丙烯酸涂布镀氧化硅薄膜及其制造方法 Download PDF

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WO2022183554A1
WO2022183554A1 PCT/CN2021/083888 CN2021083888W WO2022183554A1 WO 2022183554 A1 WO2022183554 A1 WO 2022183554A1 CN 2021083888 W CN2021083888 W CN 2021083888W WO 2022183554 A1 WO2022183554 A1 WO 2022183554A1
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parts
silicon oxide
acrylic
emulsion
coated
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PCT/CN2021/083888
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English (en)
French (fr)
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冯亮
黎坛
王恩飞
李朝辉
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海南赛诺实业有限公司
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2502/00—Acrylic polymers

Definitions

  • the invention relates to the technical field of plated silicon oxide films, in particular to an acrylic coated silicon oxide plated film and a manufacturing method thereof.
  • Silicon oxide film is a high-barrier plastic film developed and produced at home and abroad in recent years. It is based on plastic film and is coated with a layer of silicon oxide with a thickness of several tens of nanometers by vacuum coating on its surface. membrane. The composition of this layer of silicon oxide film is amorphous SiO 2 . This layer of silicon oxide is very thin, has good transparency, and is very strongly bonded to the plastic film, so the retort resistance and bending resistance of the silicon-coated plastic film are both good. better. Because the thickness of the silicon oxide film is very thin, microwaves can pass through without being absorbed; the film is very dense, and the oxygen and moisture barrier properties are very good, making the performance of the silicon oxide film relatively better than that of the aluminized plastic film. The barrier performance of the silicon oxide plastic film is better than that of all plastic composite films, especially the fragrance retention of the silicon coated plastic film is also very good.
  • the silicon oxide film has the following excellent characteristics: excellent barrier properties, very good barrier properties to oxygen and water vapor; good temperature resistance, wide operating temperature range, and can transmit electromagnetic waves; excellent Chemical resistance, can be used for acid and alkali resistant packaging; good transparency; no environmental pollution, can be recycled after disposal, and has very little incineration residue.
  • the oxygen and water vapor transmission rate of the plated silicon oxide film is very small, and it is currently recognized as a transparent and high-barrier film with excellent balanced barrier properties.
  • the plated silicon oxide film cannot be directly applied to contents such as packaged food.
  • the present invention provides an acrylic-coated silicon oxide-plated film and a manufacturing method thereof.
  • the acrylic-coated silicon oxide-plated film of the present invention has high hardness, good wear resistance, and It has a high unsealing temperature, which is conducive to high temperature use and storage.
  • the invention provides an acrylic-coated silicon oxide-plated film, which comprises: a film substrate containing a silicon oxide-plated layer and a protective layer compounded on the surface of the silicon-oxide-plated layer;
  • the protective layer is an acrylic coating formed by coating the acrylic emulsion on the surface of the silicon oxide layer of the film substrate and drying it; the weight ratio of the raw materials contained in the acrylic emulsion is as follows:
  • the film substrate containing the silicon oxide plated layer is a silicon oxide plated biaxially oriented film with a thickness of 18-50 ⁇ m and an oxygen permeability of ⁇ 0.5 mL/m 2 .24hr.atm.
  • the thickness of the acrylic coated silicon oxide film is 19-52 ⁇ m; the solid content of the acrylic emulsion is 15.0-30.0%, and the gram weight of the acrylic coating is 0.5-2.0 g/m 2 .
  • the initiator is a peroxide-based initiator, preferably one or more of potassium persulfate, ammonium persulfate and sodium persulfate;
  • the chain transfer agent is ⁇ -methylstyrene linear bisulfite aggregates.
  • the emulsifier is one or more of dodecyl sulfate and styrene sulfonate, preferably sodium dodecyl sulfate and styrene sulfonic acid in a mixing mass ratio of 1:1 sodium.
  • the defoamer is a composite defoamer formed by mixing ethanol and octanol in a weight ratio of 1:2.
  • the pH adjusting agent is one or more of sodium bicarbonate and ammonia water, preferably ammonia water with a concentration of 25% to 30%.
  • the slip agent is an aqueous palm wax emulsion.
  • the release agent is one or more of synthetic silica and glass microbeads.
  • the present invention provides the manufacturing method of the acrylic coating silicon oxide film as described above, comprising the following steps:
  • emulsifier In another container, add 0.5-1.3 parts of emulsifier to 150-270 parts of soft water, stir at room temperature to obtain a second aqueous emulsifier solution, and then add 5-15 parts of methacrylic acid monomer, 20-25 parts of acrylamide monomer, 15-25 parts of hydroxypropyl methacrylate monomer, 0.1-0.2 part of initiator, 0.2-0.4 part of chain transfer agent, mixed and stirred to obtain shell structure monomer emulsion;
  • the present invention adopts an acrylic emulsion with a specific acrylic monomer and its raw material ratio, and coats it on the silicon oxide film to form an acrylic coating with a higher glass transition temperature, which can resist oxidation. Silicon coating for better protection.
  • the acrylic protective layer formed by the coating of the present invention has high hardness and good wear resistance, and at the same time, the unsealing temperature used for heat sealing is high, and it is not easy to stick together when used and stored at high temperature, which is beneficial to ensure that the packaged product is intact and convenient for the product. use.
  • the invention provides an acrylic-coated silicon oxide-plated film, which comprises: a film substrate containing a silicon oxide-plated layer and a protective layer compounded on the surface of the silicon-oxide-plated layer;
  • the protective layer is an acrylic coating formed by coating the acrylic emulsion on the surface of the silicon oxide layer of the film substrate and drying it; the weight ratio of the raw materials contained in the acrylic emulsion is as follows:
  • the invention provides an acrylic emulsion-coated silicon oxide film, which has high hardness, good wear resistance, and high unsealing temperature, which is favorable for high-temperature use and storage.
  • a silicon oxide-coated plastic film is used as the base material, the acrylic emulsion is uniformly coated on the silicon oxide-plated surface of the film base material, and dried to form an acrylic coating, so that the acrylic coating can be prepared.
  • Coated silicon oxide film is a film substrate containing a silicon oxide-coated layer (referred to as a silicon oxide-coated film), which is generally a silicon oxide-coated biaxially stretched film, and the biaxially stretched plastic resin is not particularly limited, including but Not limited to polypropylene (PP), polyethylene (PE), polyamide (PA), and the like.
  • the film substrate containing the silicon oxide-coated layer is a silicon oxide-coated BOPP film, and in other embodiments, a silicon oxide-coated BOPA film is used.
  • the present invention has no special limitation on the source of the silicon oxide-coated film, and its thickness can be 18-50 ⁇ m, preferably 20-40 ⁇ m; the oxygen transmission rate of the silicon-oxide-plated BOPP film is less than or equal to 0.5 mL/m 2 . 24hr.atm.
  • the surface of the silicon oxide layer of the film substrate is compounded with a coating formed by coating an acrylic emulsion, which can well protect the silicon oxide layer;
  • the acrylic emulsion mainly includes special types and proportions Additives such as acrylic monomers, soft water and emulsifiers.
  • the solid content (mass content) of the acrylic emulsion in the embodiment of the present invention is 15.0% to 30.0%; the ratio of monomer raw materials contained in the acrylic emulsion is: 5-15 parts of isobornyl methacrylate; 5-15 parts of ethyl acrylate 5-15 parts of n-butyl acrylate; 5-15 parts of isobutyl acrylate; 5-15 parts of methacrylic acid; 20-30 parts of acrylamide; 15-25 parts of hydroxypropyl methacrylate.
  • the proportion of monomers 10 parts of isobornyl methacrylate, 10 parts of ethyl acrylate, 10 parts of n-butyl acrylate, 10 parts of isobutyl acrylate; 10 parts of methacrylic acid, 25 parts of parts acrylamide, 20 parts hydroxypropyl methacrylate.
  • the proportion of monomers 13 parts of isobornyl methacrylate, 8 parts of ethyl acrylate, 9 parts of n-butyl acrylate, 8 parts of isobutyl acrylate; 15 parts of methacrylic acid, 25 parts of propylene amide, 22 parts of hydroxypropyl methacrylate.
  • the acrylic emulsion includes the following raw materials by mass: 300-570 parts of soft water; 0.2-0.4 parts of initiator; 1-2.5 parts of emulsifier; 2-4 parts of defoamer; 1-5 parts of pH regulator; 0.4-0.8 parts of chain transfer agent; 2-4 parts of slip agent; 0.3-3 parts of anti-blocking agent.
  • the acrylic emulsion contains a core-shell structure polymer; preferably obtained by the following preparation steps:
  • a flow pump can be used to add the shell structure monomer emulsion to the core structure emulsion, while maintaining the temperature of the mixed emulsion at 75-83° C., and the addition time is 1.5-2.0 hours;
  • the heating can be terminated immediately, the mixed emulsion can be naturally cooled to below 45°C, 2-4 parts of defoaming agent and 1-5 parts of pH regulator are added, and the pH value of the system is preferably adjusted to 6-8, cooled to room temperature;
  • the initiator can be a peroxide type initiator, preferably one or more of potassium persulfate, ammonium persulfate and sodium persulfate;
  • the chain transfer agent is ⁇ -methylstyrene Linear dimer (AMSD).
  • AMSD ⁇ -methylstyrene Linear dimer
  • emulsifier is preferably one or more of dodecyl sulfate and styrene sulfonate, more preferably sodium dodecyl sulfate (SDS) and sodium styrene sulfonate, and the mixing ratio can be 1:1.
  • the defoamer is a composite defoamer formed by mixing ethanol and octanol in a weight ratio of 1:2.
  • the pH adjusting agent is preferably one or more of sodium bicarbonate and ammonia water, more preferably ammonia water with a mass concentration of 25% to 30%, and ammonia water with a concentration of 28%.
  • the slip agent is preferably an aqueous palm wax emulsion;
  • the anti-sticking agent is preferably one or more of synthetic silica and glass microbeads, more preferably synthetic silica.
  • the acrylic emulsion described in the embodiment of the present invention is coated on the silicon oxide-plated surface of the substrate, and the acrylic coating formed after drying is the protective layer on the surface of the silicon oxide-plated layer.
  • the thickness of the coating is 0.5-2.0 ⁇ m.
  • the gram weight can be 0.5 ⁇ 2.0g/m 2 .
  • the total thickness of the acrylic-coated silicon oxide-plated film is preferably 19-52 ⁇ m (for example, 20-45 ⁇ m); the unsealing temperature can be above 80°C.
  • Embodiments of the present invention provide the aforementioned method for manufacturing an acrylic-coated silicon oxide film, comprising the following steps:
  • the acrylic emulsion is coated on the surface of the silicon oxide-plated layer of the film substrate, and dried to form an acrylic coating to obtain an acrylic-coated silicon oxide-plated film.
  • the manufacturing method of the film of the present invention includes:
  • the amount of glue can be guaranteed to be 3-4g/m 2
  • the roll is wound, and placed at a temperature of 38°C for curing for 24 hours to obtain the acrylic-coated silicon oxide-plated film of the present invention.
  • the Tg (glass transition temperature) value of the emulsion is adjusted through the ratio of acrylic monomers, etc., and the Tg value of the emulsion is increased from conventional (generally lower than 60° C.) to 60-65° C.
  • the acrylic protective layer has higher hardness and better wear resistance, so as to achieve a better protection effect; at the same time, it also brings a higher unsealing temperature of the coating, which is beneficial to avoid the adhesion of the finished product due to high temperature during use.
  • the emulsifiers used are sodium lauryl sulfate and sodium styrene sulfonate, and the mixing ratio is 1:1; the defoamer is ethanol and octanol in a weight ratio of 1:2 The composite defoamer formed after mixing; the slip agent is water-based palm wax emulsion; the pH regulator is ammonia water with a concentration of 28%.
  • the addition time is 1.5 hours.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • emulsifier 1 part was added to 200 parts of soft water, stirred at room temperature to obtain an aqueous emulsifier solution, and then 12 parts of isobornyl methacrylate monomers, 15 parts of ethyl acrylate monomers, 8 part of n-butyl acrylate monomer, 10 parts of isobutyl acrylate monomer, 0.15 part of chain transfer agent ⁇ -methylstyrene linear dimer, mixed and stirred for 0.75 hours, and the stirring speed was controlled at 60 rpm.
  • the addition time is 1 hour.
  • Embodiments 1 to 3 correspond to Embodiments 1 to 3, respectively.
  • the oxygen transmission rate of the described silicon oxide BOPP film is less than or equal to 0.5mL/m 2 .24hr.atm.
  • Abrasion resistance corresponds to haze difference ⁇ H: the lower the value, the better the abrasion resistance.
  • the present invention provides a protective coating with high wear resistance and weather resistance and a method for manufacturing the coating film thereof.
  • the cloth is soft and not resistant to scratches.
  • the protective oxide coating is easily scratched due to scratches, resulting in poor overall barrier properties of the film.
  • the unsealing temperature of the acrylic acid is low.
  • the storage temperature exceeds a certain range, the surface of the film will stick together, resulting in damage to the product packaging and affecting the use of the product).
  • High and high temperature use and storage are not easy to adhere; at the same time, the printing performance of the film and its high transparency performance are guaranteed.

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Abstract

一种丙烯酸涂布镀氧化硅薄膜及其制造方法，该涂布薄膜包括：镀氧化硅薄膜基材和镀氧化硅层表面的保护层；保护层是由丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面形成的丙烯酸涂层；丙烯酸乳液的原料配比：5-15份甲基丙烯酸异冰片酯；5-15份丙烯酸乙酯；5-15份丙烯酸正丁酯；5-15份丙烯酸异丁酯；5-15份甲基丙烯酸；20-30份丙烯酰胺；15-25份甲基丙烯酸羟丙酯；0.2-0.4份引发剂；1-2.5份乳化剂；2-4份消泡剂；1-5份pH调节剂；0.4-0.8份链转移剂；2-4份滑爽剂；0.3-3份防粘剂；300-570份软水。该丙烯酸涂布镀氧化硅薄膜硬度高，耐磨性能好，且启封温度高。

Description

一种丙烯酸涂布镀氧化硅薄膜及其制造方法
本申请要求于2021年03月02日提交中国专利局、申请号为202110228838.6、发明名称为“一种丙烯酸涂布镀氧化硅薄膜及其制造方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及镀氧化硅薄膜技术领域，具体涉及一种丙烯酸涂布镀氧化硅薄膜及其制造方法。
背景技术
镀氧化硅薄膜是近年来国内外研制生产的高阻透性的塑料薄膜，是以塑料薄膜为基材，在其表面用真空镀膜的方法，镀上一层厚度为几十纳米的硅氧化物膜。该层硅氧化物膜成分为非晶体的SiO 2，这层硅氧化物很薄，透明性很好，与塑料薄膜粘合极牢，故镀硅塑料膜的耐蒸煮性和抗弯折性都较好。由于硅氧化物膜厚度很薄，微波可几乎不被吸收地透过；膜十分致密，阻氧、阻湿性能都非常好，使得镀氧化硅薄膜的性能相对优于镀铝塑料膜。镀硅氧化物塑料膜的阻隔性能又优于所有的塑料复合膜，尤其镀硅塑料膜的保香性也很好。
总体来说，镀氧化硅薄膜有如下优异特点：具有优异的阻透性，对氧和水蒸气的阻透性非常好；耐温性好，使用温度范围宽，而且可透过电磁波；优秀的耐药品性，可用于耐酸碱的包装；良好的透明性；无环境污染，废弃后可回收，焚烧残渣极少。
其中，镀氧化硅薄膜对于氧及水蒸气的透过率非常小，是目前公认的平衡阻透性优良的透明高阻透性薄膜。但是，由于容易出现机械损伤等，镀氧化硅薄膜无法直接实际应用于包装食品等内容物。
发明内容
针对现有技术中存在的上述问题，本发明提供一种丙烯酸涂布镀氧化硅薄膜及其制造方法，本发明所述的丙烯酸涂布镀氧化硅薄膜具有较高硬度，耐磨性能好，并且具有较高的启封温度，利于高温使用、保存。
本发明提供一种丙烯酸涂布镀氧化硅薄膜，其包括：含有镀氧化硅层的薄膜基材和复合于镀氧化硅层表面的保护层；
所述保护层是由丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面、烘干后形成的丙烯酸涂层；所述丙烯酸乳液含有的原料重量配比如下：
5-15份 甲基丙烯酸异冰片酯；
5-15份 丙烯酸乙酯；
5-15份 丙烯酸正丁酯；
5-15份 丙烯酸异丁酯；
5-15份 甲基丙烯酸；
20-30份 丙烯酰胺；
15-25份 甲基丙烯酸羟丙酯；
0.2-0.4份 引发剂；
1-2.5份 乳化剂；
2-4份 消泡剂；
1-5份 pH调节剂；
0.4-0.8份 链转移剂；
2-4份 滑爽剂；
0.3-3份 防粘剂；
300-570份 软水。
优选地，所述含有镀氧化硅层的薄膜基材为镀氧化硅双向拉伸薄膜，厚度为18～50μm，氧气透过率≤0.5mL/m 2.24hr.atm。
优选地，所述丙烯酸涂布镀氧化硅薄膜的厚度为19～52μm；所述丙烯酸乳液的固含量为15.0％～30.0％，所述丙烯酸涂层克重0.5～2.0g/m 2。
优选地，所述引发剂为过氧化物类引发剂，优选为过硫酸钾、过硫酸铵和过硫酸钠中的一种或多种；所述链转移剂为α-甲基苯乙烯线性二聚体。
优选地，所述乳化剂为十二烷基硫酸盐和苯乙烯磺酸盐中的一种或多种，优选为混配质量比例为1:1的十二烷基硫酸钠和苯乙烯磺酸钠。
优选地，所述消泡剂为乙醇和辛醇按重量配比1：2混合后形成的复合消泡剂。
优选地，所述pH调节剂为碳酸氢钠和氨水中的一种或多种，优选为25％～30％浓度的氨水。
优选地，所述滑爽剂为水性棕榈蜡乳液。
优选地，所述防粘剂为合成二氧化硅和玻璃微珠中的一种或多种。
本发明提供如前文所述的丙烯酸涂布镀氧化硅薄膜的制造方法，包括以下步骤：
S1、将0.5-1.2份乳化剂加入到150-260份软水中，常温搅拌得到第一乳化剂水溶液，然后向第一乳化剂水溶液中加入5-15份甲基丙烯酸异冰片酯单体、5-15份丙烯酸乙酯单体、5-15份丙烯酸正丁酯单体、5-15份丙烯酸异丁酯单体、0.2-0.4份链转移剂，混合搅拌；之后通氮气保护升温到75-83℃，同时加入0.1-0.2份引发剂，保温反应，制得核结构乳液；
在另一容器中，将0.5-1.3份乳化剂加入到150-270份软水中，常温搅拌得到第二乳化剂水溶液，然后向第二乳化剂水溶液中加入5-15份甲基丙烯酸单体、20-25份丙烯酰胺单体、15-25份甲基丙烯酸羟丙酯单体、0.1-0.2份引发剂、0.2-0.4份链转移剂，混合搅拌，得到壳结构单体乳液；
S2、向所述核结构乳液中添加所述壳结构单体乳液，同时保持混合乳液温度75-83℃，添加时间1.5-2小时；降温，加入2-4份消泡剂和1-5份pH调节剂，调节乳液pH值到6-8，冷却至常温；再添加2-4份滑爽剂和0.3-3份防粘剂，搅拌，过滤得到丙烯酸乳液；
S3、将所述丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面，烘干形成丙烯酸涂层，得到丙烯酸涂布镀氧化硅薄膜。
与现有技术相比，本发明通过采用特定丙烯酸单体及其原料配比的丙烯酸乳液，将其在镀氧化硅薄膜上涂布，形成玻璃化转变温度较高的丙烯酸涂层，可对氧化硅镀层进行更好地保护。并且，本发明涂布形成的丙烯酸保护层的硬度较高，耐磨性能好，同时用于热封的启封温度高，高温使用保存不容易粘附在一起，利于保证包装产品完好无损，便于产品使用。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述 的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种丙烯酸涂布镀氧化硅薄膜，其包括：含有镀氧化硅层的薄膜基材和复合于镀氧化硅层表面的保护层；
所述保护层是由丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面、烘干后形成的丙烯酸涂层；所述丙烯酸乳液含有的原料重量配比如下：
5-15份 甲基丙烯酸异冰片酯；
5-15份 丙烯酸乙酯；
5-15份 丙烯酸正丁酯；
5-15份 丙烯酸异丁酯；
5-15份 甲基丙烯酸；
20-30份 丙烯酰胺；
15-25份 甲基丙烯酸羟丙酯；
0.2-0.4份 引发剂；
1-2.5份 乳化剂；
2-4份 消泡剂；
1-5份 pH调节剂；
0.4-0.8份 链转移剂；
2-4份 滑爽剂；
0.3-3份 防粘剂；
300-570份 软水。
本发明提供一种丙烯酸乳液涂布的镀氧化硅薄膜，其具有较高硬度，耐磨性能好，并且具有较高的启封温度，利于高温使用、保存。
本发明实施例是以镀氧化硅塑料薄膜为基材，在该薄膜基材的镀氧化硅面上均匀地涂布丙烯酸乳液，烘干形成丙烯酸涂层，即可制得所述的丙烯酸涂布镀氧化硅薄膜。其中，所包括的镀氧化硅塑料薄膜是含有镀氧化硅层的薄膜基材(简称镀氧化硅薄膜)，一般为镀氧化硅双向拉伸薄膜，双向拉伸的塑料树脂没有特殊限定，包括但不限于聚丙烯(PP)、聚乙烯(PE)、聚酰胺(PA) 等。一些实施例中，所述含有镀氧化硅层的薄膜基材为镀氧化硅BOPP薄膜，另一些实施例为镀氧化硅BOPA薄膜。本发明对所述的镀氧化硅薄膜的来源没有特殊限制，其厚度可为18～50μm、优选为20～40μm；所述的镀氧化硅BOPP薄膜的氧气透过率≤0.5mL/m 2.24hr.atm。
在本发明中，所述薄膜基材的镀氧化硅层表面复合有涂布丙烯酸乳液所形成的涂层，可很好地保护镀氧化硅层；所述的丙烯酸乳液主要包含特殊种类及配比的丙烯酸类单体、软水和乳化剂等添加剂。
本发明实施例所述丙烯酸乳液的固含量(质量含量)为15.0％～30.0％；其含有的单体原料配比为：5-15份甲基丙烯酸异冰片酯；5-15份丙烯酸乙酯；5-15份丙烯酸正丁酯；5-15份丙烯酸异丁酯；5-15份甲基丙烯酸；20-30份丙烯酰胺；15-25份甲基丙烯酸羟丙酯。在本发明的一些实施例中，单体配比：10份甲基丙烯酸异冰片酯，10份丙烯酸乙酯，10份丙烯酸正丁酯，10份丙烯酸异丁酯；10份甲基丙烯酸、25份丙烯酰胺、20份甲基丙烯酸羟丙酯。而另一些实施例中，单体配比：13份甲基丙烯酸异冰片酯，8份丙烯酸乙酯，9份丙烯酸正丁酯，8份丙烯酸异丁酯；15份甲基丙烯酸、25份丙烯酰胺、22份甲基丙烯酸羟丙酯。
并且，所述的丙烯酸乳液包括如下质量份的原料：300-570份软水；0.2-0.4份引发剂；1-2.5份乳化剂；2-4份消泡剂；1-5份PH调节剂；0.4-0.8份链转移剂；2-4份滑爽剂；0.3-3份防粘剂。
在本发明的具体实施例中，所述的丙烯酸乳液含有核壳结构聚合物；优选通过以下制备步骤获得：
(1)将0.5-1.2份乳化剂加入到盛有150-260份软水的容器中，常温搅拌得到第一乳化剂水溶液，然后向第一乳化剂水溶液中加入5-15份甲基丙烯酸异冰片酯单体、5-15份丙烯酸乙酯单体、5-15份丙烯酸正丁酯单体、5-15份丙烯酸异丁酯单体、0.2-0.4份链转移剂，混合搅拌0.5小时-1.0小时，搅拌速度可控制在60-80转/分钟；
(2)混合搅拌完成后，通氮气保护升温到75-83℃，同时加入0.1-0.2份引发剂，保温反应1h-1.5h，制得核结构乳液；
(3)在另一容器中，将0.5-1.3份乳化剂加入到150-270份软水中，常温搅拌得到第二乳化剂水溶液，然后向第二乳化剂水溶液中加入5-15份甲基丙烯酸单体、20-25份丙烯酰胺单体、15-25份甲基丙烯酸羟丙酯单体、0.1-0.2份引发剂、0.2-0.4份链转移剂，混合搅拌0.5小时-1.0小时，搅拌速度可控制在60-80转/分钟，得到壳结构单体乳液；
(4)可使用流量泵，向所述核结构乳液中添加所述壳结构单体乳液，同时保持混合乳液温度75-83℃，添加时间1.5-2.0小时；
(5)添加完成后，可立即结束加热，使混合乳液自然降温到45℃以下，加入2-4份消泡剂和1-5份pH调节剂，优选调节体系pH值到6-8，冷却至常温；
(6)再添加2-4份滑爽剂和0.3-3份防粘剂(优选为0.3～1.5质量份)，搅拌均匀，优选使用200目过滤网过滤后，即可得到本发明实施例使用的丙烯酸乳液。
其中，所述的引发剂可为过氧化物类引发剂，优选为过硫酸钾、过硫酸铵和过硫酸钠中的一种或多种；所述的链转移剂为α-甲基苯乙烯线性二聚体(AMSD)。所述的乳化剂优选为十二烷基硫酸盐和苯乙烯磺酸盐中的一种或多种，更优选为十二烷基硫酸钠(SDS)和苯乙烯磺酸钠，混配比例可为1:1。作为优选，所述的消泡剂为乙醇和辛醇按重量配比1：2混合后形成的复合消泡剂。
并且，所述的pH调节剂优选为碳酸氢钠和氨水中的一种或多种，更优选为25％～30％质量浓度的氨水，进一步为浓度28％的氨水。所述的滑爽剂优选为水性棕榈蜡乳液；所述的防粘剂优选为合成二氧化硅和玻璃微珠中的一种或多种，更优选为合成二氧化硅。
本发明实施例所述的丙烯酸乳液涂布于基材的镀氧化硅表面、烘干后形成的丙烯酸涂层，即为镀氧化硅层表面的保护层，涂层厚度0.5～2.0μm，涂层克重可为0.5～2.0g/m 2。此外，所述的丙烯酸涂布镀氧化硅薄膜的总厚度优选为19～52μm(例如20～45μm)；启封温度可在80℃以上。
本发明实施例提供了如前文所述的丙烯酸涂布镀氧化硅薄膜的制造方法，包括以下步骤：
提供前文所述原料及配比的丙烯酸乳液；
将所述丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面，烘干形成丙烯酸涂层，得到丙烯酸涂布镀氧化硅薄膜。
具体地，本发明所述的薄膜的制造方法包括：
将镀氧化硅基材薄膜放卷，采用逆转辊吻式涂布方式，在基材的镀氧化硅面上均匀的涂布上一层乳液，上胶量可保证在3～4g/m 2，经烘箱90-110℃烘干2s-5s后，收卷，放置到38℃的温度下固化24小时，即可制得本发明所述的一种丙烯酸涂布的镀氧化硅薄膜。
本发明实施例通过丙烯酸单体的配比等，调节乳液Tg(玻璃化转变温度)值，把乳液Tg值从常规(一般低于60℃)升高到60-65℃，使得涂布后的丙烯酸保护层硬度较大，耐磨性能更好，从而达到更好的保护效果；同时也带来的涂层启封温度更高，有利于避免成品在使用过程中因高温而产生的粘连现象。
为了进一步理解本申请，下面结合实施例对本申请提供的丙烯酸涂布镀氧化硅薄膜及其制造方法进行具体地描述。但是应当理解，这些实施例是在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制，本发明的保护范围也不限于下述的实施例。
以下实施例中，所使用的乳化剂为十二烷基硫酸钠和苯乙烯磺酸钠，混配比例为1：1；所述的消泡剂为乙醇和辛醇按重量配比1：2混合后形成的复合消泡剂；所述的滑爽剂为水性棕榈蜡乳液；所述的PH调节剂为28％浓度的氨水。
实施例一：
(1)将0.8份乳化剂加入到230份软水中，常温搅拌得到乳化剂水溶液，然后向该乳化剂水溶液中加入10份甲基丙烯酸异冰片酯单体、10份丙烯酸乙酯单体、10份丙烯酸正丁酯单体、10份丙烯酸异丁酯单体、0.2份链转移剂α-甲基苯乙烯线性二聚体，混合搅拌0.5小时，搅拌速度控制在60转/分钟。
(2)混合搅拌完成后，通氮气保护升温到75℃，同时加入0.15份引发剂过硫酸钠，保温反应1h，制得核结构乳液。
(3)在另一容器中，将1份乳化剂加入到250份软水中，常温搅拌得到乳化剂水溶液，然后向该乳化剂水溶液中加入10份甲基丙烯酸单体、25份丙烯酰 胺单体、20份甲基丙烯酸羟丙酯单体、0.15份引发剂过硫酸钠、0.3份链转移剂α-甲基苯乙烯线性二聚体，混合搅拌0.5小时，搅拌速度控制在60转/分钟，得到壳结构单体乳液。
(4)使用流量泵向所述核结构乳液中添加壳结构单体乳液，同时保持乳液温度75℃，添加时间1.5小时。
(5)添加完成后，立即结束加热，使乳液自然降温到45℃以下，加入2份消泡剂和1.5份PH调节剂，调节乳液PH值到6.5，冷却至常温。
(6)再添加2份滑爽剂和0.3份防粘剂合成二氧化硅，搅拌均匀，使用200目过滤网过滤后，即可得到固含量为16.7％的丙烯酸乳液。
(7)将20μm的镀氧化硅BOPP薄膜放卷，采用逆转辊吻式涂布方式，在基材的镀氧化硅面上均匀的涂布上述乳液，上胶量保证在4g/m 2，经烘箱105℃烘干3s后，收卷，放置到38℃的温度下固化24小时，即可制得厚度20.5μm的一种丙烯酸涂布的镀氧化硅BOPP薄膜。
实施例二：
(1)将1份乳化剂加入到200份软水中，常温搅拌得到乳化剂水溶液，然后向该乳化剂水溶液中加入12份甲基丙烯酸异冰片酯单体、15份丙烯酸乙酯单体、8份丙烯酸正丁酯单体、10份丙烯酸异丁酯单体、0.15份链转移剂α-甲基苯乙烯线性二聚体，混合搅拌0.75小时，搅拌速度控制在60转/分钟。
(2)混合搅拌完成后，通氮气保护升温到78℃，同时加入0.15份引发剂过硫酸铵，保温反应1.5小时，制得核结构乳液。
(3)在另一容器中，将1.3份乳化剂加入到200份软水中，常温搅拌得到乳化剂水溶液，然后向该乳化剂水溶液中加入15份甲基丙烯酸单体、20份丙烯酰胺单体、18份甲基丙烯酸羟丙酯单体、0.3份引发剂过硫酸铵、0.3份链转移剂α-甲基苯乙烯线性二聚体，混合搅拌0.5小时，搅拌速度控制在60转/分钟，得到壳结构单体乳液。
(4)使用流量泵向所述核结构乳液中添加壳结构单体乳液，同时保持乳液温度80℃，添加时间1小时。
(5)添加完成后，立即结束加热，使乳液自然降温到45℃以下，加入3份消泡剂和2.5份PH调节剂，调节乳液PH值到7.5，冷却至常温。
(6)再添加1.5份滑爽剂和0.3份防粘剂合成二氧化硅，搅拌均匀，使用200目过滤网过滤后，即可得到固含量为20.1％的丙烯酸乳液。
(7)将25μm的镀氧化硅BOPP薄膜放卷，采用逆转辊吻式涂布方式，在基材的镀氧化硅面上均匀的涂布上述乳液，上胶量保证在4g/m 2，经烘箱110℃烘干3s后，收卷，放置到38℃的温度下固化24小时，即可制得厚度25.6μm的一种丙烯酸涂布的镀氧化硅BOPP薄膜。
实施例三：
(1)将0.9份乳化剂加入到180份软水中，常温搅拌得到乳化剂水溶液，然后向该乳化剂水溶液中加入13份甲基丙烯酸异冰片酯单体、8份丙烯酸乙酯单体、9份丙烯酸正丁酯单体、8份丙烯酸异丁酯单体、0.2份链转移剂α-甲基苯乙烯线性二聚体，混合搅拌0.5小时，搅拌速度控制在80转/分钟。
(2)混合搅拌完成后，通氮气保护升温到82℃，同时加入0.15份引发剂过硫酸铵，保温反应1.2小时，制得核结构乳液。
(3)在另一容器中，将1.2份乳化剂加入到200份软水中，常温搅拌得到乳化剂水溶液，然后向该乳化剂水溶液中加入15份甲基丙烯酸单体、25份丙烯酰胺单体、22份甲基丙烯酸羟丙酯单体、0.2份引发剂过硫酸铵、0.25份链转移剂α-甲基苯乙烯线性二聚体，混合搅拌0.75小时，搅拌速度控制在75转/分钟，得到壳结构单体乳液。
(4)使用流量泵向所述核结构乳液中添加壳结构单体乳液，同时保持乳液温度80℃，添加时间2小时。
(5)添加完成后，立即结束加热，使乳液自然降温到45℃以下，加入4份消泡剂和4份PH调节剂，调节乳液PH值到7.8，冷却至常温。
(6)再添加1.5份滑爽剂，0.5份防粘剂合成二氧化硅，搅拌均匀，使用200目过滤网过滤后，即可得到固含量为21.3％的丙烯酸乳液。
(7)将28μm的镀氧化硅BOPP薄膜放卷，采用逆转辊吻式涂布方式，在基材的镀氧化硅面上均匀的涂布上述乳液，上胶量保证在3g/m 2，经烘箱95℃ 烘干4s后，收卷，放置到38℃的温度下固化24小时，即可制得厚度28.5μm的一种丙烯酸涂布的镀氧化硅BOPP薄膜。
对本发明以上实施例制得的丙烯酸涂布镀氧化硅薄膜进行性能测试，结果如下：
表1 实施例中丙烯酸涂布镀氧化硅薄膜的性能
Figure PCTCN2021083888-appb-000001
注：Tg/粘度在标准试验条件下测得。耐磨性ΔH：数值越低，耐磨性能越好。实施例1至实施例3分别对应实施例一至实施例三。
另外，采用常规丙烯酸乳液涂布后与本申请的性能对比如下：
表2 本发明产品的性能对比
Figure PCTCN2021083888-appb-000002
注：所述的镀氧化硅BOPP薄膜的氧气透过率≤0.5mL/m 2.24hr.atm。耐磨性对应雾度差ΔH：数值越低，耐磨性能越好。
针对镀氧化硅薄膜无法直接用于包装，需要保护涂层等问题，本发明提供了一种高耐磨性、耐候性的保护涂层及其涂布薄膜的制造方法，相比常规丙烯 酸(涂布偏软，不耐刮花，在使用过程中容易因刮花造成保护的镀氧化物层刮伤，造成薄膜整体阻隔性变差；同时该丙烯酸启封温度较低，在使用过程中如果长时间储存时温度超出一定范围，薄膜表面就有粘附在一起的情况发生，造成产品包装的破损，影响产品使用)，本发明包含的丙烯酸涂布后硬度更大，耐磨性能好，且启封温度高，高温使用保存不容易粘附；同时保证薄膜的印刷性能以及其高透明性能。
以上所述仅是本发明的优选实施方式，应当指出，对于使本技术领域的专业技术人员，在不脱离本发明技术原理的前提下，是能够实现对这些实施例的多种修改的，而这些修改也应视为本发明应该保护的范围。

Claims (10)

  1. 一种丙烯酸涂布镀氧化硅薄膜，其特征在于，包括：含有镀氧化硅层的薄膜基材和涂覆于镀氧化硅层表面的保护层；
    所述保护层是由丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面、烘干后形成的丙烯酸涂层；所述丙烯酸乳液含有的原料重量配比如下：
    5-15份甲基丙烯酸异冰片酯；
    5-15份丙烯酸乙酯；
    5-15份丙烯酸正丁酯；
    5-15份丙烯酸异丁酯；
    5-15份甲基丙烯酸；
    20-30份丙烯酰胺；
    15-25份甲基丙烯酸羟丙酯；
    0.2-0.4份引发剂；
    1-2.5份乳化剂；
    2-4份消泡剂；
    1-5份pH调节剂；
    0.4-0.8份链转移剂；
    2-4份滑爽剂；
    0.3-3份防粘剂；
    300-570份软水。
  2. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述含有镀氧化硅层的薄膜基材为镀氧化硅双向拉伸薄膜，厚度为18～50μm，氧气透过率≤0.5mL/m 2.24hr.atm。
  3. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述丙烯酸涂布镀氧化硅薄膜的厚度为19～52μm；所述丙烯酸乳液的固含量为15.0％～30.0％，所述丙烯酸涂层克重0.5～2.0g/m 2。
  4. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述引发剂为过氧化物类引发剂，优选为过硫酸钾、过硫酸铵和过硫酸钠中的一种 或多种；所述链转移剂为α-甲基苯乙烯线性二聚体。
  5. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述乳化剂为十二烷基硫酸盐和苯乙烯磺酸盐中的一种或多种，优选为混配质量比例为1:1的十二烷基硫酸钠和苯乙烯磺酸钠。
  6. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述消泡剂为乙醇和辛醇按重量配比1：2混合后形成的复合消泡剂。
  7. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述pH调节剂为碳酸氢钠和氨水中的一种或多种，优选为25％～30％浓度的氨水。
  8. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述滑爽剂为水性棕榈蜡乳液。
  9. 根据权利要求1所述的丙烯酸涂布镀氧化硅薄膜，其特征在于，所述防粘剂为合成二氧化硅和玻璃微珠中的一种或多种。
  10. 如权利要求1-9任一项所述的丙烯酸涂布镀氧化硅薄膜的制造方法，包括以下步骤：
    S1、将0.5-1.2份乳化剂加入到150-260份软水中，常温搅拌得到第一乳化剂水溶液，然后向第一乳化剂水溶液中加入5-15份甲基丙烯酸异冰片酯单体、5-15份丙烯酸乙酯单体、5-15份丙烯酸正丁酯单体、5-15份丙烯酸异丁酯单体、0.2-0.4份链转移剂，混合搅拌；之后通氮气保护升温到75-83℃，同时加入0.1-0.2份引发剂，保温反应，制得核结构乳液；
    在另一容器中，将0.5-1.3份乳化剂加入到150-270份软水中，常温搅拌得到第二乳化剂水溶液，然后向第二乳化剂水溶液中加入5-15份甲基丙烯酸单体、20-25份丙烯酰胺单体、15-25份甲基丙烯酸羟丙酯单体、0.1-0.2份引发剂、0.2-0.4份链转移剂，混合搅拌，得到壳结构单体乳液；
    S2、向所述核结构乳液中添加所述壳结构单体乳液，同时保持混合乳液温度75-83℃，添加时间1.5-2小时；降温，加入2-4份消泡剂和1-5份pH调节剂，调节乳液pH值到6-8，冷却至常温；再添加2-4份滑爽剂和0.3-3份防粘剂，搅拌，过滤得到丙烯酸乳液；
    S3、将所述丙烯酸乳液涂布于薄膜基材的镀氧化硅层表面，烘干形成丙烯酸涂层，得到丙烯酸涂布镀氧化硅薄膜。
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