WO2016165039A1 - Single-component thermoplastic polyacrylate shape-preserving coating composition - Google Patents

Single-component thermoplastic polyacrylate shape-preserving coating composition Download PDF

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Publication number
WO2016165039A1
WO2016165039A1 PCT/CN2015/000256 CN2015000256W WO2016165039A1 WO 2016165039 A1 WO2016165039 A1 WO 2016165039A1 CN 2015000256 W CN2015000256 W CN 2015000256W WO 2016165039 A1 WO2016165039 A1 WO 2016165039A1
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Prior art keywords
component
acrylate
coating composition
solvent
conformal coating
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PCT/CN2015/000256
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French (fr)
Chinese (zh)
Inventor
张廷珂
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上海佰奥聚新材料科技有限公司
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Priority to PCT/CN2015/000256 priority Critical patent/WO2016165039A1/en
Publication of WO2016165039A1 publication Critical patent/WO2016165039A1/en

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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
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the present invention relates to a coating composition, and more particularly to a one-component thermoplastic polyacrylate conformal coating composition having high adhesion while having high hardness and softness.
  • the core circuit board section One method that is widely used in practice is to apply a layer of conformal coating to the surface of the electronic component to form a protective barrier.
  • the conformal coating is a layer of protective material directly coated on the circuit board (PCB) of the soldered component.
  • the coating protective film formed after the coating layer is completely cured can enhance the moisture resistance and protection of the electronic circuit and components.
  • the protective film of the coating is also beneficial to improve the friction and solvent resistance of the circuit and components, and release the pressure caused by the cyclical changes in temperature, improve the stability of the electronic product, and prolong the service life of the electronic product.
  • conformal coating systems include systems such as silicones, polyacrylates, polyurethanes, synthetic rubbers, and epoxy resins.
  • polyacrylates are widely used in comparison with other systems due to the rich diversity of acrylate monomers used and the mature polymerization process, which can flexibly adjust the polymer polymers and systems.
  • thermoplastic polyacrylates are not only easy to apply, but also easy to remove and recoat on defective electronic components due to better solubility in solvent systems.
  • a single polyacrylate system is generally difficult to meet the requirements of some low-temperature use, and often has insufficient softness at low temperatures, and is easily brittle to lose the original protective properties.
  • the softness at low temperatures can be achieved by adjusting the glass transition temperature of the polyacrylate, it is easy to cause the viscosity to change at normal temperature and high temperature, and also loses the protective property.
  • protective coatings for electronic products are also required to maintain performance during temperature changes.
  • the two-component system has a certain life span, and often cannot be used beyond its fixed use time; and usually the requirements for the ratio are high, and the uncertainty in weighing tends to cause extreme performance. Great impact.
  • Ultraviolet curing systems require the use of an additional UV irradiation device, and in locations where light is not found, it is easy to cause incomplete curing and cause energy absorbing defects in the product. Therefore, if you can develop a single component and have a good fit It is imperative to maintain good softness at low temperatures and conformal coatings that are not tacky at high temperatures.
  • solvents are often used for different system requirements, such as methyl ethyl ketone and butyl acetate for acrylic acid systems; n-hexane, methyl cyclohexane for synthetic rubber; and toluene for silicone systems.
  • the role of the solvent in the conformal coating is to dilute and control the film formation. If the dilution is not well formed, the equipment will be blocked and unevenly constructed. The poor film formation will affect the final application. performance. Good solvents will have better dilution, faster drying speed and good uniform dense film formation. At the same time, after the formation of a dry film, if the defects of the construction are found, the solubility of the solvent system is often insufficient to achieve a good repair function.
  • the present invention aims to provide an environmentally friendly polyacrylate conformal shape which has high hardness and softness and high adhesion.
  • a coating composition comprising an acrylate polymer and an environmentally friendly, low toxicity, low odor organic solvent that dissolves the polyacrylate polymer.
  • thermoplastic polyacrylate conformal coating composition of the present invention comprises: a polyacrylate (first component) having a glass transition temperature higher than 40 ° C, or a polypolymer having a glass transition temperature higher than 40 ° C An acrylate (first component) and a polyacrylate (second component) acrylate polymer having a glass transition temperature below 20 °C. Wherein, the difference in glass transition temperature of the polyacrylate of the two components is 20-50 °C.
  • Weight ratio of polyacrylate (first component) having a glass transition temperature higher than 40 ° C to polyacrylate (second component) having a glass transition temperature lower than 20 ° C based on the total weight of the acrylate polymer It is from 100:0 to 2:1.
  • the thermoplastic polyacrylate conformal coating composition is a polyacrylate having a glass transition temperature of greater than 40 ° C (first component) and a glass transition temperature of less than 20 ° C.
  • An ester (second component) acrylate polymer When the weight ratio of the first component polyacrylate and the second component polyacrylate is higher than 20:1, the thermoplastic polyacrylate conformal coating composition of the present invention causes low temperature to become brittle The phenomenon of cracking; and when the weight ratio of the first component polyacrylate to the second component polyacrylate is less than 2:1, the thermoplastic polyacrylate conformal coating composition of the present invention exhibits a temperature-increasing phenomenon.
  • the weight ratio of the first component polyacrylate and the second component polyacrylate is from 20:1 to 3:1; preferably from 10:1 to 3:1; based on the total weight of the acrylate polymer; It is preferably from 5:1 to 3:1.
  • the acrylate polymer of the present invention comprises one or more nonionic acrylate monomers containing unsaturated double bonds and one or more ionic groups containing unsaturated double bonds.
  • the nonionic acrylate monomer containing an unsaturated double bond may be a single double bond (meth) acrylate such as methyl (meth) acrylate or ethyl (meth) acrylate, ( Methyl)butyl acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, sunflower (meth)acrylate, ( Dodecyl methacrylate, tetradecyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, cetyl (meth) acrylate, and Octadecyl (meth)acrylate; other (meth) acrylates such as isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)
  • the nonionic monomer of such a polymer may also contain 0-2% of a plurality of double bond monomers such as: tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Ethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butenediol di(meth)acrylate, di(meth)acrylic acid Polyalkyl glycol ester, hexadienoic acid ester, trimethylolpropyl tris(meth)acrylate, allyl (meth)acrylate, divinylbenzene, divinyltoluene, trivinylbenzene And divinylnaphthalene.
  • the ionic acrylate monomers include, but are not limited to, (meth)acrylic acid, itaconic acid, maleic anhydride, succinic acid, crotonic acid.
  • the nonionic acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isooctyl (meth)acrylate, styrene , vinyl acetate, or butyl maleate.
  • the ionic acrylate is (meth)acrylic acid, itaconic acid, maleic anhydride, or succinic acid or the like.
  • thermoplastic polyacrylate conformal coating composition system of the present invention further comprises a solvent system having strong solubility and low toxicity.
  • the solvent system of the present invention comprises a solvent of an alkyl ether.
  • the alkyl ether solvent has very good versatility and can be used for acrylic acid, synthetic rubber, polyurethane, and silicone systems, and has good dissolution and viscosity reduction effects in these systems.
  • the polyacrylate system and the silicone system the inventors have surprisingly found that both systems can solve the current RTV (room temperature curing) and two-component addition curing after using a solvent containing an alkyl ether. Incompatibility and lack of solubility encountered in repair and recoating.
  • the solvent of the alkyl ether can greatly improve the solubility; however, there is still a phenomenon of leakage coating during the spraying process. Therefore, it must be inspected after spraying and repaired with solvent.
  • Solvents commonly used in the prior art such as methyl ethyl ketone, toluene, and butyl acetate, tend to cause whitening of the paint film due to the inhomogeneity of solubility and volatilization rate, thereby seriously affecting the appearance of the paint. There may even be performance defects that result in defective products.
  • the alkyl ether solvent system provided by the present invention further contains a carbonate-based solvent.
  • the composition of the solvent system comprises a carbonate solvent and an ether solvent, and the content of the carbonate solvent is 10 to 90% by weight based on the total weight of the organic solvent, and the content of the ether solvent is 10 -90wt%.
  • the solvent of the carbonate includes, but is not limited to, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisooctyl carbonate;
  • the ether solvent includes but is not limited to Methyl tert-butyl, dibutyl ether, dipropyl ether, di-tert-butyl ether.
  • the organic solvent may further contain 0 to 20% by weight of an alcohol solvent such as ethanol, propanol, or tert-butanol or the like.
  • the solvent system of the present invention is capable of well balancing the solubility and the rate of volatilization so that the repair becomes uniform. It has also been found in a particular embodiment of the invention that the mixed solvent system aids in the leveling of the spray process, such that automatic leveling occurs in the area where the leak is applied, thereby greatly reducing the repair process.
  • the one-component thermoplastic polyacrylate conformal coating composition of the present invention is contained in an amount of from 10 to 90% by weight based on the total weight of the coating composition, and from 10 to 90% by weight of the above organic Solvent system.
  • Another object of the present invention is to provide a process for preparing a thermoplastic polyacrylate conformal coating composition having high adhesion and having both hardness and softness by segmentally controlling the glass transition of the polymerization reactant. Temperature is used to achieve such a polymer system containing two or more constituents.
  • the glass transition temperature of the two or more constituents included includes a first component above 40 °C and a second component below 20 °C.
  • the polymerization system is a solution thermally initiated free radical polymerization. Suitable temperatures for the polymerization are from 60 ° C to 150 ° C, preferably from 60 ° C to 110 ° C. Different polymerization aids such as initiators, chain transfer agents are commonly employed in the polymerization process.
  • the initiator is an oil-soluble initiator including, but not limited to, benzoyl peroxide, tert-butyl peroxybenzoate, cumene peroxide, tert-butyl peroxyisophthalate, azobisisobutyronitrile, Tert-butyl hydroperoxide, or hydrogen peroxide.
  • Chain transfer agents include, but are not limited to, dodecyl mercaptan, methyl 3-mercaptopropionate, 3-mercaptopropionic acid, or ethanethiol, and the like.
  • the polymerization process of the acrylic monomer is continuous or semi-continuously added, and the rear stage is adjusted by adding a monomer having a lower glass transition temperature or a monomer having a high glass transition temperature in an intermediate process of adding the acrylic monomer.
  • the difference in glass transition temperature between the two components is 20-50 °C.
  • the glass transition temperature of the front stage is 50 ° C and the glass transition temperature of the latter stage is 25 ° C.
  • the glass transition temperature of the front stage is 15 ° C and the glass transition temperature of the latter stage is 45 ° C.
  • the "Glass transition temperature” or "Tg” value used in the present invention utilizes the Fox formula (TGFox, Bull. Am. Physics Soc., Vol. 1, No. 3, p. 123 ( 1956)) Calculated, ie, for calculating the Tg value of the copolymer of monomers M1 and M2:
  • 1/Tg (calculated value) w (M1) / Tg (M1) + w (M2) / Tg (M2)
  • Tg (calculated value) is the calculated glass transition temperature of the copolymer; w (M1) is the weight fraction of the monomer M1 in the copolymer; w (M2) is the weight fraction of the monomer M2 in the copolymer; Tg ( M1) is the glass transition temperature of the M1 homopolymer; Tg(M2) is the glass transition temperature of the M2 homopolymer; all temperatures are in °K.
  • the glass transition temperature of a homopolymer can be found, for example, in "Polymer Handbook", Handbook of Polymers (edited by J. Brandrup and E. H. Immergut, Interscience).
  • thermoplastic polyacrylate conformal coating system of the invention has high adhesion, hardness and softness, and is suitable for application of electronic circuit boards and electronic components of household appliances, consumer electronics, vehicles, precision instruments, aerospace and the like. protection.
  • the coating method can be airless spraying, brushing or automatic spraying.
  • the effective thickness of the coating is from 30 microns to 2 mm, preferably from 50 microns to 500 microns.
  • thermoplastic polyacrylate conformal coating composition of the present invention also has low toxicity, low odor, and high removal efficiency properties.
  • the coating composition can be widely used in household appliances, aerospace, transportation, medical electronics, communication equipment, consumer electronic equipment; in particular, it is used to protect electrical equipment, protect circuit boards from chemicals, vibration, moisture, Hazards under conditions such as smoke and high temperatures.
  • the raw materials used in the respective examples are commercially available raw materials, as follows,
  • the monomer mixture of 15 g of methyl methacrylate, 50 g of butyl acrylate and 0.5 g of methacrylic acid was continuously added dropwise to the reaction flask, while 0.65 g of TBPB was slowly added dropwise to the reaction flask to dissolve in 20 g of carbonic acid.
  • the solution of the methyl ester was added dropwise for 0.5 hours, and the reaction temperature was controlled at 90 ° C during the control.
  • GC gas chromatography
  • GC gas chromatography
  • GC gas chromatography
  • the copolymer obtained by polymerization in each of the above examples was used for film formation and hardening evaluation. The evaluation is carried out in accordance with the methods described below. In addition, the test ambient temperature was 25 ° C, 50% RH, unless otherwise stated.
  • the prepared sample was diluted to a solid content of 35%, and the polymer solution obtained above was uniformly scraped on a surface-clean glass plate using a 200 ⁇ m doctor blade, and dried at a constant temperature of 25 °C. Until the finger does not feel sticky, record the time from scratching the film to not sticking.
  • the test was performed using the cross-cut method, and the coated substrate was a glass plate, and the evaluation grade was sequentially weakened from 0 to 5.
  • Level 0 The cutting edge is completely smooth and there is no one falling off.
  • Level 1 There is a small amount of separation at the intersection of the incisions, but the cross-sectional area is affected by no more than 5%.
  • Level 2 The edge of the incision or the intersection has obvious shedding less than 5%, but the affected is obviously no more than 35%.
  • Level 3 The coating is peeled off along the edge of the cut, partially or completely with large fragments, or partially or completely on the different parts of the grid, significantly greater than 15%, but the affected is obviously no more than 35%.
  • Grade 4 The coating is peeled off along the edge of the cut, or some of the squares are partially or completely peeled off; more than 35%, but the affected is obviously no more than 65%.
  • Level 5 Severe shedding of more than 4 levels.
  • the sample was coated on a PC board, dried at 60 degrees for 2 hours, and then a 100 V DC voltage was applied to measure the insulation resistance value.
  • the same sample plate was prepared and then measured in a constant temperature and humidity vessel (85 degrees, 85% RH) with a DC voltage of 100V.
  • the prepared conformal coating was applied on a PC board with a coating thickness of 100 ⁇ m. After drying at room temperature, it was placed in a cooling cycle box for high and low temperature cycle test. The high temperature was set at 85 degrees and the low temperature was -5 degrees. . Each cycle test cycle is 24 hours and 10 cycles are tested. Record whether the low temperature coating becomes brittle or high temperature sticky during the cycle test. The test results are shown in the following table:

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Abstract

A single-component thermoplastic polyacrylate coating composition, based on the total weight of a coating composition, comprising: 10-90wt% of an acrylate polymer and 10-90wt% of an organic solvent, wherein the acrylate polymer contains polyacrylate, the glass-transition temperature of a first component of the polyacrylate being higher than 40°C, the glass-transition temperature of a second component of the polyacrylate being lower than 20°C, a difference between the glass-transition temperature of the first component and the glass-transition temperature of the second component being 20-50°C, the mass ratio of the first component to the second component being 100:0-2:1, and the organic solvent being a carbonate ester solvent, an ether solvent, and/or an alcohol solvent. The coating composition has the advantages of low toxicity, low odor and high adhesive force.

Description

单组分热塑性聚丙烯酸酯保形涂料组合物One-component thermoplastic polyacrylate conformal coating composition 技术领域Technical field
本发明涉及一种涂料组合物，尤其涉及一种具有高附着力、同时兼备高硬度和柔软度的单组分热塑性聚丙烯酸酯保形涂料组合物。The present invention relates to a coating composition, and more particularly to a one-component thermoplastic polyacrylate conformal coating composition having high adhesion while having high hardness and softness.
背景技术Background technique
众所周知，电子组件通常需要能够承受恶劣的操作环境，如那些应用在汽车和航空航天工业上的电子组件，由于受操作环境的影响，这些电子组件需要进行有效的保护，尤其是这些电子组件中比较核心的线路板部分。一个在实践中被广泛采用的方法是在电子组件表面涂覆一层保形涂料从而形成保护性阻挡层。该保形涂料是直接涂覆在焊接好的元件的线路板(PCB)上的一层保护材料，涂料层完全固化后形成的涂层保护膜可起到增强电子线路和元器件的防潮、防污能力，防止焊点和导体受到侵蚀；也可起到屏蔽和消除电磁干扰及防止线路短路的作用，从而提高线路板的绝缘性能。此外，涂层保护膜也有利于提高线路和元器件的耐摩擦和耐溶剂性能，并释放温度周期性变化所造成的压力，提高电子产品的稳定性、延长电子产品的使用寿命。It is well known that electronic components are often required to withstand harsh operating environments, such as those used in the automotive and aerospace industries. These electronic components need to be effectively protected due to the operating environment, especially in these electronic components. The core circuit board section. One method that is widely used in practice is to apply a layer of conformal coating to the surface of the electronic component to form a protective barrier. The conformal coating is a layer of protective material directly coated on the circuit board (PCB) of the soldered component. The coating protective film formed after the coating layer is completely cured can enhance the moisture resistance and protection of the electronic circuit and components. The ability to prevent solder joints and conductors from being eroded; it also acts to shield and eliminate electromagnetic interference and prevent short circuits, thereby improving the insulation performance of the board. In addition, the protective film of the coating is also beneficial to improve the friction and solvent resistance of the circuit and components, and release the pressure caused by the cyclical changes in temperature, improve the stability of the electronic product, and prolong the service life of the electronic product.
在本技术领域，基础的涂层保护膜已经被广泛应用于手机、电脑、汽车、电器等设备组件上，特别是应用于集成电路、印刷线路板和印刷电路板。一般说来，保形涂料体系包括有机硅、聚丙烯酸酯、聚氨酯、合成橡胶和环氧树脂等体系。其中，聚丙烯酸酯由于其所使用的丙烯酸酯单体的丰富多样性，以及成熟的聚合工艺能够对聚合物高分子和体系进行灵活的可调节性，得到了相对于其他体系的更广泛的应用。尤其是热塑性聚丙烯酸酯，不但具有易施工，而且由于在溶剂体系中较好的溶解度，也易于在造成有缺陷的电子组件上进行去除和重涂。但是，单一的聚丙烯酸酯体系通常比较难以满足一些低温使用的要求，往往在低温下柔软度不够，容易变脆从而失去原有的保护性能。虽然通过调节聚丙烯酸酯的玻璃化转变温度可以达到低温下柔软度，但是又容易导致常温和高温变粘，同样失去保护性能。由于电子产品在运输和保存过程中经常会遇到温度大幅变化的情形，因此，对电子产品的保护涂层也要求能够在温度变化的过程中能做到性能的保持。现有技术中有些通过双组分体系加入固化剂或者紫外固化的体系可以达到这一性能要求，如专利US20060047251和US5213875。但双组分的体系具有一定的寿命期限，经常是超过其固定的使用时间就无法继续使用；而且通常对配比的要求较高，称量上的不确定性往往会对产品的性能造成极大的影响。紫外固化体系则需要使用额外的紫外照射装置，而且在光线找不到的位置很容易导致固化不完全，对产品造成吸能缺陷。因此，如果能够开发一种单组分并且具有良好的适 用性，且能够在低温下保持良好的柔软度，而高温下又不发粘的保形涂料是刻不容缓的。In the technical field, basic protective coatings have been widely used in mobile phone, computer, automotive, electrical and other equipment components, especially in integrated circuits, printed circuit boards and printed circuit boards. In general, conformal coating systems include systems such as silicones, polyacrylates, polyurethanes, synthetic rubbers, and epoxy resins. Among them, polyacrylates are widely used in comparison with other systems due to the rich diversity of acrylate monomers used and the mature polymerization process, which can flexibly adjust the polymer polymers and systems. . In particular, thermoplastic polyacrylates are not only easy to apply, but also easy to remove and recoat on defective electronic components due to better solubility in solvent systems. However, a single polyacrylate system is generally difficult to meet the requirements of some low-temperature use, and often has insufficient softness at low temperatures, and is easily brittle to lose the original protective properties. Although the softness at low temperatures can be achieved by adjusting the glass transition temperature of the polyacrylate, it is easy to cause the viscosity to change at normal temperature and high temperature, and also loses the protective property. Since electronic products often encounter large temperature changes during transportation and storage, protective coatings for electronic products are also required to maintain performance during temperature changes. Some of the prior art can achieve this performance requirement by adding a curing agent or a UV-cured system through a two-component system, such as the patents US20060047251 and US5213875. However, the two-component system has a certain life span, and often cannot be used beyond its fixed use time; and usually the requirements for the ratio are high, and the uncertainty in weighing tends to cause extreme performance. Great impact. Ultraviolet curing systems require the use of an additional UV irradiation device, and in locations where light is not found, it is easy to cause incomplete curing and cause energy absorbing defects in the product. Therefore, if you can develop a single component and have a good fit It is imperative to maintain good softness at low temperatures and conformal coatings that are not tacky at high temperatures.
目前市售的保形涂料主要是单组份的溶剂型体系，这些溶剂型体系通常大多数含有大量有害溶剂，比如苯系溶剂(甲苯、二甲苯)、烷烃(正己烷)、酮类(丙酮、丁酮)、异丙醇等。并且，这些产品中的溶剂在使用后会挥发到空气中，从而会对环境和操作者造成一定的损害，严重时操作者会出现各种急性和慢性的不适状况。而且针对不同的体系的要求往往会使用不同种类的溶剂，比如丁酮、醋酸丁酯用于丙烯酸体系；正己烷、甲基环己烷由于合成橡胶；甲苯用于有机硅体系。通常溶剂在保形涂料中的作用是起到稀释和控制成膜，如果达不到很好地稀释作用会造成施工的设备的阻塞和施工不均匀，成膜不好就会影响到最后的应用性能。良好的溶剂会具有比较好的稀释性、较快的干燥速度和良好的均匀致密成膜性。同时，在形成干燥的膜后，如果发现施工的缺陷，往往由于溶剂体系的溶解度不够无法达到良好的修补功能，这点尤其体现在有机硅的体系中，目前还没有一种比较好的溶剂可以解决这个问题。根据现有的技术体系，目前还没有发现一种可以通用于不同体系，而且能够获得良好施工性能和成膜性能的溶剂体系。而且现有的体系中往往使用毒性较高的苯系物或脂溶性好的烷烃类溶剂，对操作者的环境的危害较大。因此，开发一种低气味、低毒和具有通用性和良好相容性的环保溶剂体系对于保形涂料是具有非常重要的意义。Currently, commercially available conformal coatings are mainly one-component solvent-based systems. Most of these solvent-based systems contain a large amount of harmful solvents such as benzene-based solvents (toluene, xylene), alkanes (n-hexane), and ketones (acetone). , butanone), isopropanol, and the like. Moreover, the solvents in these products will volatilize into the air after use, which will cause certain damage to the environment and the operator. In severe cases, the operator may experience various acute and chronic discomforts. Moreover, different kinds of solvents are often used for different system requirements, such as methyl ethyl ketone and butyl acetate for acrylic acid systems; n-hexane, methyl cyclohexane for synthetic rubber; and toluene for silicone systems. Usually, the role of the solvent in the conformal coating is to dilute and control the film formation. If the dilution is not well formed, the equipment will be blocked and unevenly constructed. The poor film formation will affect the final application. performance. Good solvents will have better dilution, faster drying speed and good uniform dense film formation. At the same time, after the formation of a dry film, if the defects of the construction are found, the solubility of the solvent system is often insufficient to achieve a good repair function. This is especially reflected in the silicone system. At present, there is no better solvent. solve this problem. According to the prior art system, a solvent system which can be used in different systems and which can obtain good workability and film forming properties has not been found. Moreover, in the existing system, a highly toxic benzene series or a fat-soluble alkane solvent is often used, which is harmful to the operator's environment. Therefore, the development of an environmentally friendly solvent system with low odor, low toxicity and versatility and good compatibility is very important for conformal coatings.
发明内容Summary of the invention
为了解决热塑性聚丙烯酸酯体系中的因温度变化导致的性能稳定性不好的技术问题，本发明旨在提供一种兼备高硬度和柔软度，并具有高附着力的环保型聚丙烯酸酯保形涂料组合物，该组合物包含丙烯酸酯聚合物，以及溶解该聚丙烯酸酯聚合物的环保、低毒、低气味的有机溶剂。In order to solve the technical problem that the performance stability due to temperature change in the thermoplastic polyacrylate system is not good, the present invention aims to provide an environmentally friendly polyacrylate conformal shape which has high hardness and softness and high adhesion. A coating composition comprising an acrylate polymer and an environmentally friendly, low toxicity, low odor organic solvent that dissolves the polyacrylate polymer.
首先，本发明的一个目的是提供一种具有高附着力、且兼备高硬度和柔软度的热塑性聚丙烯酸酯保形涂料组合物体系。其中，本发明所述的热塑性聚丙烯酸酯保形涂料组合物包含：含有玻璃化转变温度高于40℃的聚丙烯酸酯(第一组份)，或含有玻璃化转变温度高于40℃的聚丙烯酸酯(第一组份)和玻璃化转变温度低于20℃的聚丙烯酸酯(第二组份)的丙烯酸酯聚合物。其中，这两种组份的聚丙烯酸酯的玻璃化转变温度的差值在20-50℃。基于丙烯酸酯聚合物的总重，含有玻璃化转变温度高于40℃的聚丙烯酸酯(第一组份)与玻璃化转变温度低于20℃的聚丙烯酸酯(第二组份)的重量比例为100∶0-2∶1。First, it is an object of the present invention to provide a thermoplastic polyacrylate conformal coating composition system which has high adhesion and which combines high hardness and softness. Wherein the thermoplastic polyacrylate conformal coating composition of the present invention comprises: a polyacrylate (first component) having a glass transition temperature higher than 40 ° C, or a polypolymer having a glass transition temperature higher than 40 ° C An acrylate (first component) and a polyacrylate (second component) acrylate polymer having a glass transition temperature below 20 °C. Wherein, the difference in glass transition temperature of the polyacrylate of the two components is 20-50 °C. Weight ratio of polyacrylate (first component) having a glass transition temperature higher than 40 ° C to polyacrylate (second component) having a glass transition temperature lower than 20 ° C based on the total weight of the acrylate polymer It is from 100:0 to 2:1.
在本发明的优选实施例中，热塑性聚丙烯酸酯保形涂料组合物为含有玻璃化转变温度高于40℃的聚丙烯酸酯(第一组份)和玻璃化转变温度低于20℃的聚丙烯酸酯(第二组份)的丙烯酸酯聚合物。当第一组份聚丙烯酸酯和第二组份聚丙烯酸酯的重量比例高于20∶1时，本发明的热塑性聚丙烯酸酯保形涂料组合物会造成低温变脆开 裂现象；而当第一组份聚丙烯酸酯和第二组份聚丙烯酸酯的重量比例低于2∶1时，本发明的热塑性聚丙烯酸酯保形涂料组合物会出现升温发粘现象。In a preferred embodiment of the invention, the thermoplastic polyacrylate conformal coating composition is a polyacrylate having a glass transition temperature of greater than 40 ° C (first component) and a glass transition temperature of less than 20 ° C. An ester (second component) acrylate polymer. When the weight ratio of the first component polyacrylate and the second component polyacrylate is higher than 20:1, the thermoplastic polyacrylate conformal coating composition of the present invention causes low temperature to become brittle The phenomenon of cracking; and when the weight ratio of the first component polyacrylate to the second component polyacrylate is less than 2:1, the thermoplastic polyacrylate conformal coating composition of the present invention exhibits a temperature-increasing phenomenon.
优选地，基于丙烯酸酯聚合物的总重，第一组份聚丙烯酸酯和第二组份聚丙烯酸酯的重量比例为20∶1至3∶1；优选为10∶1至3∶1；更优选为5∶1至3∶1。Preferably, the weight ratio of the first component polyacrylate and the second component polyacrylate is from 20:1 to 3:1; preferably from 10:1 to 3:1; based on the total weight of the acrylate polymer; It is preferably from 5:1 to 3:1.
在本发明的具体实施例中，本发明所述的丙烯酸酯聚合物包含一种或几种含有不饱和双键的非离子丙烯酸酯单体和一种或几种含有不饱和双键的离子性丙烯酸酯单体，其中基于丙烯酸酯聚合物质量总重，非离子性丙烯酸酯单体含量在85-99.5wt％；离子性丙烯酸酯单体含量在0.5-15wt％。In a specific embodiment of the invention, the acrylate polymer of the present invention comprises one or more nonionic acrylate monomers containing unsaturated double bonds and one or more ionic groups containing unsaturated double bonds. An acrylate monomer in which the nonionic acrylate monomer content is from 85 to 99.5 wt% and the ionic acrylate monomer content is from 0.5 to 15 wt% based on the total mass of the acrylate polymer.
在本发明中，含有不饱和双键的非离子性丙烯酸酯单体可以是单个双键的(甲基)丙烯酸酯，如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸葵酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸油醇酯、(甲基)丙烯酸十六烷基酯、和(甲基)丙烯酸十八烷基酯；其它(甲基)丙烯酸酯如(甲基)丙烯酸异冰片酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸乙酰乙酸乙氧酯等；或烯基苯类单体，如：苯乙烯、2-甲基苯乙烯、4-甲基苯乙稀等；或醋酸乙烯酯、叔碳酸乙烯酯；或马来酸丁酯、琥珀酸酯、衣康酸酯。这种聚合物的非离子性单体也可以含有0-2％的多个双键的单体如：二(甲基)丙烯酸三丙二醇酯、二(甲基)丙烯酸二乙稀二醇酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸-1，6-己二醇酯、二(甲基)丙烯酸-1，3-丁烯二醇酯、二(甲基)丙烯酸聚烷基二醇酯、己二烯酞酸脂、三(甲基)丙烯酸三羟甲基丙酯、(甲基)丙烯酸烯丙酯、二乙烯基苯、二乙烯基甲苯、三乙烯基苯和二乙烯基萘。所述的离子性丙烯酸酯单体包括但不限于(甲基)丙烯酸、衣康酸、马来酸酐、琥珀酸、巴豆酸。In the present invention, the nonionic acrylate monomer containing an unsaturated double bond may be a single double bond (meth) acrylate such as methyl (meth) acrylate or ethyl (meth) acrylate, ( Methyl)butyl acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, sunflower (meth)acrylate, ( Dodecyl methacrylate, tetradecyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, cetyl (meth) acrylate, and Octadecyl (meth)acrylate; other (meth) acrylates such as isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid shrinkage a glyceride, acetoacetate (meth) acrylate, etc.; or an alkenyl benzene monomer such as styrene, 2-methylstyrene, 4-methylstyrene, or the like; or vinyl acetate, uncle Ethylene carbonate; or butyl maleate, succinate, itaconate. The nonionic monomer of such a polymer may also contain 0-2% of a plurality of double bond monomers such as: tripropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Ethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butenediol di(meth)acrylate, di(meth)acrylic acid Polyalkyl glycol ester, hexadienoic acid ester, trimethylolpropyl tris(meth)acrylate, allyl (meth)acrylate, divinylbenzene, divinyltoluene, trivinylbenzene And divinylnaphthalene. The ionic acrylate monomers include, but are not limited to, (meth)acrylic acid, itaconic acid, maleic anhydride, succinic acid, crotonic acid.
在本发明的优选实施方式中，非离子性丙烯酸酯为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异辛酯、苯乙烯、醋酸乙烯酯、或马来酸丁酯等。所述的离子性丙烯酸酯为(甲基)丙烯酸酸、衣康酸、马来酸酐、或琥珀酸等。In a preferred embodiment of the invention, the nonionic acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isooctyl (meth)acrylate, styrene , vinyl acetate, or butyl maleate. The ionic acrylate is (meth)acrylic acid, itaconic acid, maleic anhydride, or succinic acid or the like.
另一方面，为了提高聚丙烯酸酯保形涂料组合物体系的溶解度，本发明所述热塑性聚丙烯酸酯保形涂料组合物体系还包含一种具有强溶解性、低毒性的溶剂体系。本发明所述的溶剂体系包含一种烷基醚类的溶剂。在实际应用中发明人发现On the other hand, in order to improve the solubility of the polyacrylate conformal coating composition system, the thermoplastic polyacrylate conformal coating composition system of the present invention further comprises a solvent system having strong solubility and low toxicity. The solvent system of the present invention comprises a solvent of an alkyl ether. Inventors found in practical applications
这种烷基醚类溶剂具有非常良好的通用性，既可以用于丙烯酸、合成橡胶、聚氨酯，也可以用于有机硅体系，在这些体系中都具有良好的溶解降粘作用。尤其对于聚丙烯酸酯体系和有机硅体系，发明人惊奇地发现，这两种体系在使用了含有烷基醚类的溶剂后，均可以解决目前RTV(室温固化)和双组分加成固化的修补和重涂遇到的不相容和溶解性不足的问题。对于组分热塑性的丙烯酸保形涂料体系来说，使用该烷基醚类的溶剂可以大大提高溶解度；但是，在喷涂过程中还是会有漏涂的现象发生， 因此，在喷涂过后必须进行检查并使用溶剂进行修补。现有技术中常用的溶剂如丁酮、甲苯、醋酸丁酯往往由于溶解度和挥发速率的不均一，经常会导致保形涂料出现漆膜发白的现象，从而严重的影响涂料的表观，有些甚至可能会出现性能的缺陷，造成产品的次品。The alkyl ether solvent has very good versatility and can be used for acrylic acid, synthetic rubber, polyurethane, and silicone systems, and has good dissolution and viscosity reduction effects in these systems. Especially for the polyacrylate system and the silicone system, the inventors have surprisingly found that both systems can solve the current RTV (room temperature curing) and two-component addition curing after using a solvent containing an alkyl ether. Incompatibility and lack of solubility encountered in repair and recoating. For the component thermoplastic thermoplastic conformal coating system, the solvent of the alkyl ether can greatly improve the solubility; however, there is still a phenomenon of leakage coating during the spraying process. Therefore, it must be inspected after spraying and repaired with solvent. Solvents commonly used in the prior art, such as methyl ethyl ketone, toluene, and butyl acetate, tend to cause whitening of the paint film due to the inhomogeneity of solubility and volatilization rate, thereby seriously affecting the appearance of the paint. There may even be performance defects that result in defective products.
为了解决上述问题，本发明提供的烷基醚溶剂体系还含有碳酸酯类溶剂。在本发明中，所述溶剂体系的组成包括一种碳酸酯类溶剂和一种醚类溶剂，基于有机溶剂的总重量，碳酸酯溶剂的含量在10-90wt％，醚类溶剂的含量在10-90wt％。所述的碳酸酯类的溶剂包括但不局限于碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、碳酸二异辛酯；所述的醚类溶剂包括但不局限于甲基叔丁基、二丁醚、二丙醚、二叔丁基醚。In order to solve the above problems, the alkyl ether solvent system provided by the present invention further contains a carbonate-based solvent. In the present invention, the composition of the solvent system comprises a carbonate solvent and an ether solvent, and the content of the carbonate solvent is 10 to 90% by weight based on the total weight of the organic solvent, and the content of the ether solvent is 10 -90wt%. The solvent of the carbonate includes, but is not limited to, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisooctyl carbonate; the ether solvent includes but is not limited to Methyl tert-butyl, dibutyl ether, dipropyl ether, di-tert-butyl ether.
在本发明的实施方式中，除这两种溶剂外，有机溶剂还可以含有0-20wt％的醇类溶剂如乙醇、丙醇、或叔丁醇等。In the embodiment of the present invention, in addition to the two solvents, the organic solvent may further contain 0 to 20% by weight of an alcohol solvent such as ethanol, propanol, or tert-butanol or the like.
本发明的溶剂体系能够很好的平衡溶解度和挥发速率，使得修补变得均一。在本发明的具体实施例中还发现该混合溶剂体系有助于喷涂过程的流平性，使得会发生漏涂地方自动流平，从而极大地减少了修补的工序。The solvent system of the present invention is capable of well balancing the solubility and the rate of volatilization so that the repair becomes uniform. It has also been found in a particular embodiment of the invention that the mixed solvent system aids in the leveling of the spray process, such that automatic leveling occurs in the area where the leak is applied, thereby greatly reducing the repair process.
在本发明中，本发明所述的单组分热塑性聚丙烯酸酯保形涂料组合物的含量为，基于涂料组合物总重量，10-90wt％丙烯酸酯聚合物，以及10-90wt％的上述有机溶剂体系。In the present invention, the one-component thermoplastic polyacrylate conformal coating composition of the present invention is contained in an amount of from 10 to 90% by weight based on the total weight of the coating composition, and from 10 to 90% by weight of the above organic Solvent system.
本发明的另一个目的是提供一种制备具有高附着力、且兼备硬度和柔软度的热塑性聚丙烯酸酯保形涂料组合物的方法，该制备方法是通过分段控制聚合反应物的玻璃化转变温度来实现这种含有两种或多种组成部分的聚合物体系。所包含的两种或多种组成部分的玻璃化转变温度，包括高于40℃的第一组成成份和低于20℃的第二组成成份。Another object of the present invention is to provide a process for preparing a thermoplastic polyacrylate conformal coating composition having high adhesion and having both hardness and softness by segmentally controlling the glass transition of the polymerization reactant. Temperature is used to achieve such a polymer system containing two or more constituents. The glass transition temperature of the two or more constituents included includes a first component above 40 °C and a second component below 20 °C.
所述的聚合体系为溶液热引发自由基聚合。所述的聚合反应的适宜温度范围为从60℃-150℃，优选范围从60℃-110℃。所述聚合过程普遍采用不同的合成辅助剂例如引发剂、链转移剂。所述的引发剂为油溶性引发剂包括但不限于如过氧化苯甲酰、苯甲酸过氧化叔丁酯、过氧化异丙苯、过氧化异辛酸叔丁酯、偶氮二异丁腈、叔丁基过氧化氢、或过氧化氢等。链转移剂包括但不限于如十二烷基硫醇、3-巯基丙酸甲酯、3-巯基丙酸、或乙硫醇等。The polymerization system is a solution thermally initiated free radical polymerization. Suitable temperatures for the polymerization are from 60 ° C to 150 ° C, preferably from 60 ° C to 110 ° C. Different polymerization aids such as initiators, chain transfer agents are commonly employed in the polymerization process. The initiator is an oil-soluble initiator including, but not limited to, benzoyl peroxide, tert-butyl peroxybenzoate, cumene peroxide, tert-butyl peroxyisophthalate, azobisisobutyronitrile, Tert-butyl hydroperoxide, or hydrogen peroxide. Chain transfer agents include, but are not limited to, dodecyl mercaptan, methyl 3-mercaptopropionate, 3-mercaptopropionic acid, or ethanethiol, and the like.
所述的聚合过程丙烯酸单体加料方式为连续或半连续加入，通过在丙烯酸单体加入的中间过程中加入玻璃化温度较低的丙烯酸单体或玻璃换转变温度高的单体来调节后段的与前段的玻璃化转变温度的差别。两种组分的玻璃换转变温度的差值为20-50℃。The polymerization process of the acrylic monomer is continuous or semi-continuously added, and the rear stage is adjusted by adding a monomer having a lower glass transition temperature or a monomer having a high glass transition temperature in an intermediate process of adding the acrylic monomer. The difference from the glass transition temperature of the front section. The difference in glass transition temperature between the two components is 20-50 °C.
在本发明的一个优选实施方案中，前段的玻璃化转变温度为50℃，后段的玻璃换转变温度为25℃。 In a preferred embodiment of the invention, the glass transition temperature of the front stage is 50 ° C and the glass transition temperature of the latter stage is 25 ° C.
在本发明的另一个优选实施方案中，前段的玻璃化转变温度为15℃，后段的玻璃换转变温度为45℃。In another preferred embodiment of the invention, the glass transition temperature of the front stage is 15 ° C and the glass transition temperature of the latter stage is 45 ° C.
本发明中所使用的“玻璃化转变温度(Glass transition temperature)”或“Tg”值是利用Fox公式(T.G.Fox，Bull.Am.Physics Soc.，第1卷，第3期，第123页(1956))计算的，即，对于计算单体M1和M2的共聚物的Tg值而言：The "Glass transition temperature" or "Tg" value used in the present invention utilizes the Fox formula (TGFox, Bull. Am. Physics Soc., Vol. 1, No. 3, p. 123 ( 1956)) Calculated, ie, for calculating the Tg value of the copolymer of monomers M1 and M2:
1/Tg(计算值)＝w(M1)/Tg(M1)+w(M2)/Tg(M2)1/Tg (calculated value) = w (M1) / Tg (M1) + w (M2) / Tg (M2)
其中，Tg(计算值)为计算的共聚物的玻璃化转变温度；w(M1)为共聚物中单体M1的重量分数；w(M2)为共聚物中单体M2的重量分数；Tg(M1)为M1均聚物的玻璃化转变温度；Tg(M2)为M2均聚物的玻璃化转变温度；所有的温度以°K计。均聚物的玻璃化转变温度可以在，例如，“Polymer Handbook”《聚合物手册》(J.Brandrup和E.H.Immergut编辑，Interscience出版)中找到。Wherein, Tg (calculated value) is the calculated glass transition temperature of the copolymer; w (M1) is the weight fraction of the monomer M1 in the copolymer; w (M2) is the weight fraction of the monomer M2 in the copolymer; Tg ( M1) is the glass transition temperature of the M1 homopolymer; Tg(M2) is the glass transition temperature of the M2 homopolymer; all temperatures are in °K. The glass transition temperature of a homopolymer can be found, for example, in "Polymer Handbook", Handbook of Polymers (edited by J. Brandrup and E. H. Immergut, Interscience).
本发明所述的热塑性聚丙烯酸酯保形涂料体系具有高附着力、硬度和柔软度，其适用于家用电器、消费电子、交通工具、精密仪器、航空航天等电子线路板、电子元件的涂敷保护。涂敷方式可以是无气喷涂、刷涂或自动化喷涂。涂敷的有效厚度为30微米到2毫米，优选50微米到500微米。The thermoplastic polyacrylate conformal coating system of the invention has high adhesion, hardness and softness, and is suitable for application of electronic circuit boards and electronic components of household appliances, consumer electronics, vehicles, precision instruments, aerospace and the like. protection. The coating method can be airless spraying, brushing or automatic spraying. The effective thickness of the coating is from 30 microns to 2 mm, preferably from 50 microns to 500 microns.
本发明的热塑性聚丙烯酸酯保形涂料组合物还具有低毒、低气味、高去除效率性质。该涂料组合物可在家用电器、航空航天、交通运输、医疗电子、通讯设备、消费电子设备具有广泛的应用；尤其是用于保护电器设备，保护线路板免受化学物质、振动、湿气、烟雾和高温等条件下的危害。The thermoplastic polyacrylate conformal coating composition of the present invention also has low toxicity, low odor, and high removal efficiency properties. The coating composition can be widely used in household appliances, aerospace, transportation, medical electronics, communication equipment, consumer electronic equipment; in particular, it is used to protect electrical equipment, protect circuit boards from chemicals, vibration, moisture, Hazards under conditions such as smoke and high temperatures.
如果没有特殊说明，如本发明中所述，每个优选的解决方案和其他的优选解决方案相互结合，从而形成新的技术解决方案。由于篇幅有限，没有对组合技术进行详细说明，然而，所有通过相互结合的技术解决方案都应该认为已在本发明中进行的清晰的表述。Unless otherwise stated, as described in the present invention, each of the preferred solutions and other preferred solutions are combined to form a new technical solution. Due to the limited space, the combination technique is not described in detail, however, all technical solutions that are combined by each other should be considered as clear statements that have been made in the present invention.
下面的例子用以阐述本发明的过程和组成。这些例子有助于本领域技术人员了解本发明。但本发明不局限于这些例子。The following examples are presented to illustrate the process and composition of the present invention. These examples will help those skilled in the art to understand the present invention. However, the invention is not limited to these examples.
具体实施方式detailed description
各实施例中使用的原料为市售原料，具体如下，The raw materials used in the respective examples are commercially available raw materials, as follows,
简称Abbreviation 英文化学名English chemical name 中文化学名Chinese chemical name
MMAMMA Methyl MethacrylateMethyl Methacrylate 甲基丙烯酸甲酯Methyl methacrylate
BABA Butyl AcrylateButyl Acrylate 丙烯酸丁酯Butyl acrylate
STST StyreneStyrene 苯乙烯Styrene
(M)AA(M)AA (Meth)acrylic Acid(Meth)acrylic Acid (甲基)丙烯酸(Methacrylate
BMABMA Butyl MethacrylateButyl Methacrylate 甲基丙烯酸丁酯Butyl methacrylate
BPOBPO Benzoyl peroxideBenzoyl peroxide 过氧化苯甲酰Benzoyl peroxide
t-BPOt-BPO t-Butyl peroxy-2-ethylhexanoatet-Butyl peroxy-2-ethylhexanoate 过氧化异辛酸叔丁酯Tert-butyl peroxyoctanoate
TBPBTBPB t-Butyl peroxybenzoatet-Butyl peroxybenzoate 过氧化苯甲酸叔丁酯Tert-butyl peroxybenzoate
实施例1：Example 1:
氮气保护下，2升的反应瓶中加入碳酸二甲酯500克，加热到80℃，然后开始向反应瓶中滴加由200克甲基丙烯酸甲酯、200克甲基丙烯酸丁酯、18克甲基丙烯酸的单体混合液，同时向反应瓶缓慢滴加1.05克BPO溶解于10克碳酸二甲酯的溶液。当滴加到1.5小时，向上述单体混合液中加入60克丙烯酸丁酯，继续滴加0.5小时至滴加完毕，滴加过程中保持反应体系温度在80℃。然后继续保温2小时，并取样通过气相色谱(GC)检测反应液中未反应完的单体含量。之后每隔一小时取样一次测试未反应单体得含量，当GC检测丙烯酸酯单体含量低于0.1％时，加入荧光剂，搅拌均匀，冷却，过滤，得到透明的粘稠状液体。Under nitrogen protection, 500 g of dimethyl carbonate was added to a 2-liter reaction flask, heated to 80 ° C, and then 200 g of methyl methacrylate, 200 g of butyl methacrylate, and 18 g were added dropwise to the reaction flask. A monomer mixture of methacrylic acid was simultaneously added dropwise to the reaction flask with a solution of 1.05 g of BPO dissolved in 10 g of dimethyl carbonate. When dropwise addition was carried out for 1.5 hours, 60 g of butyl acrylate was added to the above monomer mixture, and dropwise addition was continued for 0.5 hour until the dropwise addition was completed, and the temperature of the reaction system was maintained at 80 ° C during the dropwise addition. Then, the incubation was continued for 2 hours, and sampling was carried out by gas chromatography (GC) to detect the content of unreacted monomers in the reaction solution. After that, the content of the unreacted monomer was sampled every hour. When the content of the acrylate monomer was less than 0.1% by GC, the fluorescent agent was added, stirred uniformly, cooled, and filtered to obtain a transparent viscous liquid.
实施例2：Example 2:
氮气保护下，2升的反应瓶中加入碳酸二甲酯420克，加热到80℃，然后开始向反应瓶中滴加由40克甲基丙烯酸甲酯、56.5克丙烯酸丁酯、8.5克甲基丙烯酸的单体混合液，同时向反应瓶缓慢滴加0.95克BPO溶解于15克碳酸二甲酯的溶液。当滴加到25分钟后，向单体混合液中加入285克甲基丙烯酸甲酯，继续滴加1.5小时至滴加完毕，滴加过程中保持反应体系温度在80℃。然后继续保温2小时，并取样通过气相色谱(GC)检测反应液中未反应完的单体含量。之后每隔一小时取样一次测试未反应单体得含量，当GC检测丙烯酸酯单体含量低于0.1％时，加入荧光剂，搅拌均匀，冷却，过滤，得到透明的粘稠状液体。Under nitrogen protection, 420 g of dimethyl carbonate was added to a 2-liter reaction flask, heated to 80 ° C, and then 40 g of methyl methacrylate, 56.5 g of butyl acrylate, and 8.5 g of methyl group were added dropwise to the reaction flask. A monomer mixture of acrylic acid was simultaneously slowly added dropwise to the reaction flask with a solution of 0.95 g of BPO dissolved in 15 g of dimethyl carbonate. After the dropwise addition for 25 minutes, 285 g of methyl methacrylate was added to the monomer mixture, and the dropwise addition was continued for 1.5 hours until the dropwise addition was completed, and the temperature of the reaction system was maintained at 80 ° C during the dropwise addition. Then, the incubation was continued for 2 hours, and sampling was carried out by gas chromatography (GC) to detect the content of unreacted monomers in the reaction solution. After that, the content of the unreacted monomer was sampled every hour. When the content of the acrylate monomer was less than 0.1% by GC, the fluorescent agent was added, stirred uniformly, cooled, and filtered to obtain a transparent viscous liquid.
实施例3：Example 3:
氮气保护下，2升的反应瓶中加入丁醚180克，碳酸二甲酯150克，加热到90℃，然后开始向反应瓶中滴加由120克甲基丙烯酸甲酯、250克甲基丙烯酸丁酯、5克甲基丙烯酸的单体混合液，同时向反应瓶缓慢滴加0.65克TBPB溶解于20克碳酸二甲酯的溶液，控制滴加时间为1.5小时。然后继续向反应瓶中滴加由15克甲基丙烯酸甲酯、50克丙烯酸丁酯、0.5克甲基丙烯酸的单体混合液，同时向反应瓶缓慢滴加0.65克TBPB溶解于20克碳酸二甲酯的溶液，滴加时间为0.5小时，控制过程中控制反应温度在90℃。同时向反应瓶缓慢滴加0.15克TBPB溶解于5克碳酸二甲酯的溶液，滴加完毕，继续保温2小时，并取样通过气相色谱(GC)检测反应液中未反应完的单体含量。当GC检测丙烯酸酯单体含量低于0.1％时，加入荧光剂，搅拌均匀，冷却，过滤，得到透明的粘稠状液体。 Under nitrogen protection, 180 g of dibutyl ether and 150 g of dimethyl carbonate were added to a 2-liter reaction flask, heated to 90 ° C, and then 120 g of methyl methacrylate and 250 g of methacrylic acid were added dropwise to the reaction flask. A monomer mixture of butyl ester and 5 g of methacrylic acid was simultaneously added dropwise to the reaction flask with a solution of 0.65 g of TBPB dissolved in 20 g of dimethyl carbonate, and the dropping time was controlled to be 1.5 hours. Then, the monomer mixture of 15 g of methyl methacrylate, 50 g of butyl acrylate and 0.5 g of methacrylic acid was continuously added dropwise to the reaction flask, while 0.65 g of TBPB was slowly added dropwise to the reaction flask to dissolve in 20 g of carbonic acid. The solution of the methyl ester was added dropwise for 0.5 hours, and the reaction temperature was controlled at 90 ° C during the control. At the same time, a solution of 0.15 g of TBPB dissolved in 5 g of dimethyl carbonate was slowly added dropwise to the reaction flask, and the addition was continued, the incubation was continued for 2 hours, and sampling was carried out by gas chromatography (GC) to detect the unreacted monomer content in the reaction solution. When the GC detects that the acrylate monomer content is less than 0.1%, the fluorescer is added, stirred uniformly, cooled, and filtered to obtain a transparent viscous liquid.
实施例4：Example 4:
氮气保护下，2升的反应瓶中加入碳酸二甲酯450克，加热到85℃，然后开始向反应瓶中滴加由260克甲基丙烯酸甲酯、132克甲基丙烯酸丁酯、8克甲基丙烯酸的单体混合液，同时向反应瓶缓慢滴加0.55克t-BPO溶解于10克碳酸二甲酯的溶液。滴加过程中反应体系维持在反应温度85度，当360克单体混合液滴加进反应瓶后，向单体混合液中加入12克丙烯酸异辛酯，20分钟滴加完毕，滴加过程中保持温度在85℃。然后继续保温2小时，并取样通过气相色谱(GC)检测反应液中未反应完的单体含量。当GC检测丙烯酸酯单体含量低于0.1％时，加入荧光剂，搅拌均匀，冷却，过滤，得到透明的粘稠状液体。Under nitrogen protection, add 450 grams of dimethyl carbonate to a 2 liter reaction flask, heat to 85 ° C, and then start adding 260 grams of methyl methacrylate, 132 grams of butyl methacrylate, 8 grams to the reaction flask. A monomer mixture of methacrylic acid was simultaneously added dropwise to the reaction flask with a solution of 0.55 g of t-BPO dissolved in 10 g of dimethyl carbonate. During the dropwise addition, the reaction system was maintained at a reaction temperature of 85 °C. When 360 g of monomer mixed droplets were added to the reaction flask, 12 g of isooctyl acrylate was added to the monomer mixture, and the addition was completed in 20 minutes. The temperature was maintained at 85 °C. Then, the incubation was continued for 2 hours, and sampling was carried out by gas chromatography (GC) to detect the content of unreacted monomers in the reaction solution. When the GC detects that the acrylate monomer content is less than 0.1%, the fluorescer is added, stirred uniformly, cooled, and filtered to obtain a transparent viscous liquid.
比较例1：Comparative Example 1:
氮气保护下，2升的反应瓶中加入醋酸丁酯500克，加热到100℃，然后开始向反应瓶中滴加由260克甲基丙烯酸甲酯、120克丙烯酸丁酯、20克甲基丙烯酸的单体混合液，同时向反应瓶缓慢滴加0.85克TBPB溶解于15克醋酸丁酯的溶液。滴加时间为2小时，滴加过程中反应体系保持温度在100℃。滴加完毕，然后继续保温2小时，并取样通过气相色谱(GC)检测反应液中未反应完的单体含量。当GC检测丙烯酸酯单体含量低于0.1％时，加入荧光剂，搅拌均匀，冷却，过滤，得到透明的粘稠状液体。Under nitrogen protection, 500 g of butyl acetate was added to a 2-liter reaction flask, heated to 100 ° C, and then 260 g of methyl methacrylate, 120 g of butyl acrylate, and 20 g of methacrylic acid were added dropwise to the reaction flask. The monomer mixture was slowly added dropwise to the reaction flask with a solution of 0.85 g of TBPB dissolved in 15 g of butyl acetate. The dropping time was 2 hours, and the reaction system was kept at a temperature of 100 ° C during the dropwise addition. After the dropwise addition was completed, the temperature was further maintained for 2 hours, and sampling was carried out by gas chromatography (GC) to measure the content of unreacted monomers in the reaction liquid. When the GC detects that the acrylate monomer content is less than 0.1%, the fluorescer is added, stirred uniformly, cooled, and filtered to obtain a transparent viscous liquid.
比较例2：Comparative Example 2:
氮气保护下，2升的反应瓶中加入醋酸丁酯500克，加热到90℃，然后开始向反应瓶中滴加由100克甲基丙烯酸甲酯、220克丙烯酸乙酯、80克甲基丙烯酸丁酯的单体混合液，同时向反应瓶缓慢滴加1.1克BPO溶解于10克醋酸丁酯的溶液。滴加时间为2小时，滴加过程中反应体系保持温度在90℃。然后继续保温2小时，并取样通过气相色谱(GC)检测反应液中未反应完的单体含量。当GC检测丙烯酸酯单体含量低于0.1％时，加入荧光剂，搅拌均匀，冷却，过滤，得到透明的粘稠状液体。Under nitrogen protection, 500 g of butyl acetate was added to a 2-liter reaction flask, heated to 90 ° C, and then 100 g of methyl methacrylate, 220 g of ethyl acrylate, and 80 g of methacrylic acid were added dropwise to the reaction flask. A monomer mixture of butyl ester was simultaneously added dropwise to the reaction flask with a solution of 1.1 g of BPO dissolved in 10 g of butyl acetate. The dropping time was 2 hours, and the reaction system was kept at a temperature of 90 ° C during the dropwise addition. Then, the incubation was continued for 2 hours, and sampling was carried out by gas chromatography (GC) to detect the content of unreacted monomers in the reaction solution. When the GC detects that the acrylate monomer content is less than 0.1%, the fluorescer is added, stirred uniformly, cooled, and filtered to obtain a transparent viscous liquid.
使用以上各实施例中聚合得到的共聚物进行成膜，硬化评价。评价按照下述的方法尽心。另外，在没有特别说明的情况下，测试环境温度为25℃，50％RH。The copolymer obtained by polymerization in each of the above examples was used for film formation and hardening evaluation. The evaluation is carried out in accordance with the methods described below. In addition, the test ambient temperature was 25 ° C, 50% RH, unless otherwise stated.
(1)指干速度(1) refers to the dry speed
将所制备的样品稀释至35％的固体含量，使用200微米的刮膜器，将以上所得的聚合物溶液均匀的刮涂在表面洁净的玻璃板上，在25℃恒温下干燥。直到手指感觉不到发粘，记录从刮膜到不发粘所需的时间。The prepared sample was diluted to a solid content of 35%, and the polymer solution obtained above was uniformly scraped on a surface-clean glass plate using a 200 μm doctor blade, and dried at a constant temperature of 25 °C. Until the finger does not feel sticky, record the time from scratching the film to not sticking.
(2)附着力测试(2) Adhesion test
根据GB/T9286-88标准，使用划格法进行测试，涂敷基材为玻璃板，评价等级由0-5依次减弱。 According to the GB/T9286-88 standard, the test was performed using the cross-cut method, and the coated substrate was a glass plate, and the evaluation grade was sequentially weakened from 0 to 5.
0级：切割边缘完全平滑，无一格脱落。Level 0: The cutting edge is completely smooth and there is no one falling off.
1级：切***叉处有少许薄片分离，但划格区域受影响明显不大于5％。Level 1: There is a small amount of separation at the intersection of the incisions, but the cross-sectional area is affected by no more than 5%.
2级：切口边缘或交叉口有明显脱落大于5％，但受影响明显不大于35％。Level 2: The edge of the incision or the intersection has obvious shedding less than 5%, but the affected is obviously no more than 35%.
3级：涂层沿切割边缘，部分或全部以大碎片脱落，或在格子不同部位上，部分或全部脱落，明显大于15％，但受影响明显不大于35％。Level 3: The coating is peeled off along the edge of the cut, partially or completely with large fragments, or partially or completely on the different parts of the grid, significantly greater than 15%, but the affected is obviously no more than 35%.
4级：涂层沿切割边缘，大碎片剥落，或一些方格部分或全部脱落明显；大于35％，但受影响明显不大于65％。Grade 4: The coating is peeled off along the edge of the cut, or some of the squares are partially or completely peeled off; more than 35%, but the affected is obviously no more than 65%.
5级：大于4级的严重脱落。Level 5: Severe shedding of more than 4 levels.
(3)绝缘电阻和高温高湿电阻(3) Insulation resistance and high temperature and high humidity resistance
将样品涂敷在PC板上，在60度下干燥2小时，然后外加100V直流电压测定绝缘电阻值。The sample was coated on a PC board, dried at 60 degrees for 2 hours, and then a 100 V DC voltage was applied to measure the insulation resistance value.
制备同样的样品板，然后在恒温恒湿器皿(85度，85％RH)中，外加100V直流电压进行测定。The same sample plate was prepared and then measured in a constant temperature and humidity vessel (85 degrees, 85% RH) with a DC voltage of 100V.
(4)高低温循环测试(4) High and low temperature cycle test
将所制备的保形涂料刮涂在PC板上，涂层厚度在100微米，室温充分干燥后，放入冷却循环箱中进行高低温循环测试，设定高温为85度，低温为-5度。每个循环测试周期为24小时，测试10个循环。记录循环测试过程中是否出现低温涂层变脆脱落或高温发粘现象。测试结果如下表所示：The prepared conformal coating was applied on a PC board with a coating thickness of 100 μm. After drying at room temperature, it was placed in a cooling cycle box for high and low temperature cycle test. The high temperature was set at 85 degrees and the low temperature was -5 degrees. . Each cycle test cycle is 24 hours and 10 cycles are tested. Record whether the low temperature coating becomes brittle or high temperature sticky during the cycle test. The test results are shown in the following table:
Figure PCTCN2015000256-appb-000001
Figure PCTCN2015000256-appb-000001
以上所述仅为本发明的一些较佳的实施例，并不用以限制本发明。凡在本发明所述的原则之内，所作的任何修改、等同替换、改进等，都应包含在本发明之内。 The above is only some of the preferred embodiments of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the principles of the invention are intended to be included in the invention.

Claims (10)

  1. 一种单组分热塑性聚丙烯酸酯保形涂料组合物，基于保形涂料组合物总重，包含：10-90wt％丙烯酸酯聚合物和10-90wt％的有机溶剂；A one-component thermoplastic polyacrylate conformal coating composition comprising, based on the total weight of the conformal coating composition, from 10 to 90% by weight of an acrylate polymer and from 10 to 90% by weight of an organic solvent;
    其中，所述丙烯酸酯聚合物含有玻璃化转变温度高于40℃的第一组份和玻璃化转变温度低于20℃的第二组份的聚丙烯酸酯，所述第一组分与第二组分的玻璃化转变温度的差值在20-50℃；所述第一组分和第二组分的质量比为100∶0-2∶1；Wherein the acrylate polymer comprises a first component having a glass transition temperature higher than 40 ° C and a second component polyacrylate having a glass transition temperature lower than 20 ° C, the first component and the second component The difference in glass transition temperature of the component is 20-50 ° C; the mass ratio of the first component to the second component is 100:0-2:1;
    所述有机溶剂为碳酸酯类溶剂，醚类溶剂和/或醇类溶剂。The organic solvent is a carbonate solvent, an ether solvent, and/or an alcohol solvent.
  2. 如权利要求1所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，所述丙烯酸酯聚合物含有一种或几种非离子性丙烯酸酯单体和一种或几种离子性丙烯酸酯单体；基于聚合物干重，所述非离子性丙烯酸酯单体含量在85-99.5wt％；所述离子性丙烯酸酯单体含量在0.5-15wt％。The one-component thermoplastic polyacrylate conformal coating composition of claim 1 wherein said acrylate polymer comprises one or more nonionic acrylate monomers and one or more ionic acrylics The ester monomer; the nonionic acrylate monomer content is from 85 to 99.5 wt% based on the dry weight of the polymer; and the ionic acrylate monomer content is from 0.5 to 15 wt%.
  3. 如权利要求1所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，基于丙烯酸酯聚合物的总重，所述第一组分和第二组分的质量比为20∶1-3∶1。The one-component thermoplastic polyacrylate conformal coating composition according to claim 1, wherein the mass ratio of the first component to the second component is 20:1 based on the total weight of the acrylate polymer. 3:1.
  4. 如权利要求3所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，所述第一组分和第二组分的质量比为10∶1-3∶1。The one-component thermoplastic polyacrylate conformal coating composition according to claim 3, wherein the mass ratio of the first component to the second component is from 10:1 to 3:1.
  5. 如权利要求4所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，所述第一组分和第二组分的质量比为5∶1-3∶1。The one-component thermoplastic polyacrylate conformal coating composition according to claim 4, wherein the mass ratio of the first component to the second component is from 5:1 to 3:1.
  6. 如权利要求2所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，所述的非离子性丙烯酸酯为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异辛酯、苯乙烯、醋酸乙烯酯、或马来酸丁酯。The one-component thermoplastic polyacrylate conformal coating composition according to claim 2, wherein said nonionic acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, (methyl) ) butyl acrylate, isooctyl (meth) acrylate, styrene, vinyl acetate, or butyl maleate.
  7. 如权利要求2所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，所述的离子性丙烯酸酯为(甲基)丙烯酸酸、衣康酸、马来酸酐、或琥珀酸。The one-component thermoplastic polyacrylate conformal coating composition according to claim 2, wherein the ionic acrylate is (meth)acrylic acid, itaconic acid, maleic anhydride, or succinic acid.
  8. 如权利要求1-7任一所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，所述碳酸酯类溶剂为碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、或碳酸二异辛酯；所述醚类溶剂为甲基叔丁基、二丁醚、二丙醚、或二叔丁基醚；所述醇类溶剂为乙醇、丙醇、或叔丁醇。The one-component thermoplastic polyacrylate conformal coating composition according to any one of claims 1 to 7, wherein the carbonate-based solvent is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and carbonic acid. Butyl ester or diisooctyl carbonate; the ether solvent is methyl t-butyl, dibutyl ether, dipropyl ether or di-tert-butyl ether; the alcohol solvent is ethanol, propanol or uncle Butanol.
  9. 如权利要求8所述的单组分热塑性聚丙烯酸酯保形涂料组合物，其中，基于有机溶 剂的总重量，所述碳酸酯类溶剂为10-90wt％，醚类溶剂为10-90wt％，所述醇类溶剂为0-20wt％A one-component thermoplastic polyacrylate conformal coating composition according to claim 8 wherein the organic solvent is based on The total weight of the agent, the carbonate solvent is 10-90% by weight, the ether solvent is 10-90% by weight, and the alcohol solvent is 0-20% by weight.
  10. 一种制备如权利要求1-9所述的单组分热塑性聚丙烯酸酯保形涂料组合物的方法，通过自由基聚合，在聚合过程中通过改变丙烯酸酯单体的组成来控制两组成部分的玻璃换转变温度。 A process for the preparation of a one-component thermoplastic polyacrylate conformal coating composition according to claims 1-9, by means of free radical polymerization, by controlling the composition of the acrylate monomer during the polymerization to control the two components Glass changeover temperature.
PCT/CN2015/000256 2015-04-13 2015-04-13 Single-component thermoplastic polyacrylate shape-preserving coating composition WO2016165039A1 (en)

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