Primer for polypropylene film coating organic silicon release agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of film coating, in particular to a primer for coating a polypropylene film with an organic silicon release agent, and a preparation method and application thereof.
Background
The film covering is one of the conventional post-printing processing techniques for paper printed matter, and is prepared by heating, pressurizing and adhering the plastic film coated with adhesive and the paper printed matter together. After the plastic film coated with the adhesive is rolled, the adhesive is easy to stretch and deform during use due to adhesion of the adhesive, so that the film coating effect is influenced, noise is generated, sound pollution is caused, and the like. The problems can be solved by coating the organic silicon release agent on the back surface of the plastic film coated with the adhesive. However, most of the plastic films commonly used for film coating are polypropylene materials, which belong to high-crystallinity materials, have low surface energy, no active group, weak boundary layers and poor interface wettability, so that the polypropylene materials are difficult to generate better bonding strength with the organosilicon release agent, and the polypropylene substrates are usually required to be subjected to modification treatment, such as flame and corona treatment, chemical treatment, surface grafting, low-temperature plasma surface modification and the like, so as to improve the bonding strength between the polypropylene materials and the organosilicon release agent.
The primer coating method is an effective method for improving the bonding strength between the organic silicon release agent and the polypropylene material. Compared with the method, the primer coating method has the advantages of simple preparation process, strong controllability, obvious effect, low cost and the like. However, the existing primer still has the defect of weak bonding strength in the aspect of improving the bonding strength between the organic silicon release agent and the polypropylene material, so that the organic silicon release agent still adheres to the bonding agent, and the film coating effect of the polypropylene is influenced.
Disclosure of Invention
The invention aims to provide a primer for coating a polypropylene film with an organic silicon release agent, and a preparation method and application thereof. The primer provided by the invention effectively improves the bonding strength between the organic silicon release agent and the polypropylene material.
In order to solve the technical problems, the invention provides a primer for coating a polypropylene film with an organic silicon release agent, which comprises the following components in parts by mass: 45-55 parts of trimethylsilyl ketoxime, 45-55 parts of allyl trimethoxy silane and 0.2-1 part of titanate.
Preferably, the primer for coating the polypropylene film with the silicone release agent comprises the following components in parts by mass: 48-52 parts of trimethylsilyl ketoxime, 48-52 parts of allyl trimethoxy silane and 0.4-0.8 part of titanate.
Preferably, the primer for coating the polypropylene film with the silicone release agent comprises the following components in parts by mass: 49-50 parts of trimethylsilyl ketoxime, 49-50 parts of allyl trimethoxy silane and 0.5-0.6 part of titanate.
Preferably, the titanate is tetrabutyl titanate, ethyl titanate, isopropyl titanate or isobutyl titanate.
The invention provides a preparation method of primer coating liquid for coating an organic silicon release agent on a polypropylene film, which comprises the following steps: mixing trimethylsilyl methyloxime, allyl trimethoxy silane and titanate to obtain the primer for coating the polypropylene film with the organic silicon release agent.
The invention also provides an application of the primer liquid for coating the polypropylene film with the organic silicon release agent, which is characterized in that the primer liquid for coating the polypropylene film with the organic silicon release agent is coated between the polypropylene film and the organic silicon release agent.
Preferably, the coating thickness of the primer for coating the polypropylene film with the organic silicon release agent is 1-2 μm.
The invention provides a primer for coating a polypropylene film with an organic silicon release agent, which comprises the following components in parts by mass: 45-55 parts of trimethylsilyl ketoxime, 45-55 parts of allyl trimethoxy silane and 0.2-1 part of titanate. In the invention, organic functional groups in the allyl trimethoxy silane and the trimethylsilyl dimethylglyoxime have similar molecular structures with the polypropylene substrate, have good compatibility, and easily form stronger adhesive force with the surface of the polypropylene film through acting forces such as hydrogen bonds (hydroxyl in the trimethylsilyl dimethylglyoxime and hydrogen in the polypropylene form hydrogen bonds), dispersion force and the like; the allyl trimethoxy silane also contains 3 active functional groups (alkoxy groups) which are easy to hydrolyze, and can be hydrolyzed to form active Si-OH when being contacted with a trace amount of water in the air, and the Si-OH forms firm Si-O-Si bonds through self condensation or reaction with terminal hydroxyl in the organosilicon release agent, so that the adhesion between the organosilicon release agent and the polypropylene material can be effectively improved; meanwhile, the silyl group in the trimethylsilyl methyloxime and the organosilicon release agent have similar molecular structure parts (silicon groups), so the trimethylsilyl methyloxime and the organosilicon release agent also have good compatibility and are easy to form stronger adhesive force with the surface of the organosilicon release agent through the action forces of hydrogen bonds (the hydroxyl group in the trimethylsilyl methyloxime and the hydrogen in the polypropylene form hydrogen bonds), dispersion force and the like; in addition, because the trimethyl silicone oxime has stronger adhesive force with polypropylene and can be fused with allyl trimethoxy silane, and simultaneously the allyl trimethoxy silane can be fused with the organosilicon release agent, the adhesive property between the organosilicon release agent and the polypropylene material is effectively improved; and the titanate is used as an accelerant, so that the process can be accelerated. The experimental result shows that the primer for coating the polypropylene film with the organic silicon release agent is used for preparing the polypropylene film, the polypropylene film coated with the non-setting adhesive is separated from the organic silicon release agent and is adhered to the surface of a PET film, the peel strength of the polypropylene film is tested to be 1.95N/m, the peel strength is equivalent to that of the polypropylene film coated with the non-setting adhesive on a substrate and directly adhered to the surface of the PET film, and the peel strength is higher (0.75-1.13N/m) than that of the polypropylene film prepared by using the primer in the prior art, so that the primer for coating the polypropylene film with the organic silicon release agent effectively improves the bonding force of the polypropylene film and the organic silicon release agent, and the organic silicon release agent is prevented from being adhered by the non-setting adhesive; and the primer for coating the organic silicon release agent on the polypropylene film is quick to dry, can be dried within 20-50 s, does not need to use a solvent, and is an environment-friendly primer.
Detailed Description
The invention provides a primer for coating a polypropylene film with an organic silicon release agent, which comprises the following components in parts by mass: 45-55 parts of trimethylsilyl ketoxime, 45-55 parts of allyl trimethoxy silane and 0.2-1 part of titanate.
In the invention, the primer for coating the polypropylene film with the organic silicon release agent comprises, by weight, 45-55 parts of trimethylsilyl ketoxime, preferably 48-52 parts, and more preferably 49-50 parts. In the invention, the trimethylsilyl methyloxime is used as one of the main components of the primer solution, the organic functional group of the trimethylsilyl methyloxime has a similar molecular structure with a polypropylene substrate, has good compatibility and is easy to form strong adhesive force with the surface of a polypropylene film through acting forces such as hydrogen bonds, dispersion force and the like, and meanwhile, the trimethylsilyl methyloxime contains hydroxyl in molecules, so that the allyl trimethoxy silane can be promoted to effectively improve the adhesion between the organosilicon release agent and the polypropylene material.
In the present invention, the trimethylsilylketoxime has the structure shown in formula I:
the source of the trimethylsilyl methyloxime is not particularly limited in the present invention, and in the examples of the present invention, the trimethylsilyl methyloxime is obtained by self-production. In the present invention, the method for preparing trimethylsilylketoxime preferably comprises the steps of:
mixing 3-pentanone, trimethylsilyl cyanide, ionic liquid and ferroferric oxide, and carrying out addition reduction reaction to obtain trimethylsilyl ketoxime.
In the invention, the molar ratio of the 3-pentanone to the trimethylsilyl cyanide is preferably 1-1.2: 1, and more preferably 1.1-1.15: 1.
In the invention, the ionic liquid is choline chloride/urea eutectic ionic liquid. In the invention, the mol ratio of choline chloride to urea in the ionic liquid is preferably 1: 15-25, more preferably 1: 18-22, and most preferably 1: 20.
In the present invention, the preparation method of the ionic liquid preferably comprises the following steps:
and stirring the mixture of choline chloride and urea until the mixture is clear to obtain the ionic liquid.
In the present invention, the stirring is preferably performed in an air atmosphere. In the invention, the stirring temperature is preferably 95-105 ℃, more preferably 98-102 ℃, and most preferably 100 ℃; the heating rate of the invention for heating to the temperature required for stirring is not particularly limited, and any heating rate can be adopted. The stirring time and the rotating speed are not particularly limited, and the mixture is stirred until the mixture is clear to obtain colorless liquid.
After the stirring is completed, the present invention preferably cools the stirred product to room temperature to obtain the ionic liquid. . In the invention, the ionic liquid is still liquid at normal temperature. The cooling rate is not particularly limited in the present invention, and any cooling rate can be adopted.
In the invention, the mass ratio of the 3-pentanone to the ionic liquid is preferably 1: 1-10, more preferably 1: 3-7, and most preferably 1: 5-6. In the invention, the ionic liquid is used as a reaction medium, which is beneficial to the addition reduction reaction of 3-pentanone and trimethylsilyl cyanide.
In the invention, the mass ratio of the 3-pentanone to the ferroferric oxide is preferably 1: 0.01-0.12, and more preferably 1: 0.03-0.07. In the present invention, the ferroferric oxide functions as a catalyst.
In the invention, the particle size of the ferroferric oxide is preferably nano-scale. The source of the ferroferric oxide is not particularly limited, and the commercially available nano ferroferric oxide can be directly adopted. In the embodiment of the invention, the ferroferric oxide is sourced from Shanghai Merlin Biotechnology, Inc.
In the invention, the raw materials are preferably mixed in sequence by mixing 3-pentanone, ionic liquid and ferroferric oxide, heating to the temperature required by the addition reduction reaction, and then dropwise adding trimethylsilyl cyanide. In the invention, the dropping speed of the trimethyl silicon cyanide can ensure that the temperature of the addition reduction reaction is not changed.
In the invention, the temperature of the addition reduction reaction is preferably 20-50 ℃, and more preferably 30-40 ℃; the time of the addition reduction reaction is preferably 2-3 h, and more preferably 2.5 h; the time of the addition reduction reaction is preferably from the end of the dropwise addition of trimethylsilyl cyanide. In the process of addition reduction reaction, the carbonyl of 3-pentanone and the cyano of the trimethylsilyl cyanide are subjected to addition reduction to obtain the trimethylsilyl ketoxime.
After the addition reduction reaction is finished, the invention preferably makes the mixed solution obtained by the reaction stand and layer to obtain the upper layer liquid, namely the trimethylsilyl ketoxime.
In the invention, the standing time is preferably 1-2 h.
In the invention, the primer for coating the polypropylene film with the organic silicon release agent comprises, by weight, 45-55 parts of allyl trimethoxy silane, preferably 48-52 parts of allyl trimethoxy silane, and more preferably 49-50 parts of allyl trimethoxy silane. In the invention, the organic functional group in the allyltrimethoxysilane molecule has a similar molecular structure with the polypropylene substrate, has good compatibility, and is easy to form strong adhesive force with the surface of the polypropylene film through acting forces such as hydrogen bond, dispersion force and the like; meanwhile, the allyl trimethoxy silane molecule also contains 3 active functional groups (alkoxy groups) which are easy to hydrolyze, and can be hydrolyzed to form active Si-OH when being contacted with a trace amount of water in the air, and the Si-OH forms firm Si-O-Si bonds through self condensation or reaction with terminal hydroxyl groups in the organosilicon release agent, so that the adhesion between the organosilicon release agent and the polypropylene material can be effectively improved.
In the invention, the primer coating liquid for coating the silicone release agent on the polypropylene film comprises, by weight, 0.1-1 part of titanate, preferably 0.4-0.8 part, and more preferably 0.5-0.6 part. In the invention, the titanate is used as an accelerator to promote the bonding effect of trimethylsilyl ketoxime and allyl trimethoxy silane on the organic release agent and the polypropylene material.
In the present invention, the titanate is preferably tetrabutyl titanate, ethyl titanate, isopropyl titanate, or isobutyl titanate, more preferably tetrabutyl titanate. In the present invention, the aforementioned titanates have similar structures and can perform the same promoting effect.
The invention also provides a preparation method of the primer solution for coating the polypropylene film with the organic silicon release agent, which comprises the following steps: mixing trimethylsilyl methyloxime, allyl trimethoxy silane and titanate to obtain the primer for coating the polypropylene film with the organic silicon release agent.
The invention has no special limitation on the mixing sequence, the mixing temperature and the mixing mode of the trimethylsilyl ketoxime, the allyl trimethoxy silane and the titanate, and can uniformly mix the trimethylsilyl ketoxime, the allyl trimethoxy silane and the titanate.
The invention also provides an application of the primer liquid for coating the polypropylene film with the organic silicon release agent, which is characterized in that the primer liquid for coating the polypropylene film with the organic silicon release agent is coated between the polypropylene film and the organic silicon release agent.
In the invention, the coating thickness of the primer liquid for coating the polypropylene film with the organic silicon release agent is preferably 1-2 μm.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing choline chloride and urea according to the molar ratio of 1:20 to obtain an ionic liquid raw material mixture; heating the ionic liquid raw material mixture to 100 ℃ in air, stirring at constant temperature until clear colorless liquid is formed, and cooling to room temperature to obtain ionic liquid;
mixing 100g of the ionic liquid, 100g of 3-pentanone and 2g of nano ferroferric oxide with the particle size, heating to 30 ℃, keeping the reaction temperature unchanged, and dropwise adding 100g of trimethyl silicon cyanide; after the dropwise addition, the reaction was continued for 2 hours, and after standing and layering, the lower layer liquid was discarded, and the upper layer liquid was collected to obtain 160g of a colorless liquid, i.e., trimethylsilylmethanone oxime, with a yield of 85%.
The trimethylsilyl ketoxime obtained in this example was subjected to nuclear magnetic resonance testing, the nuclear magnetic resonance testing results being as follows:
1H NMR(400MHz,CDCl3):δ(ppm)1.774-1.752(dd,4H),1.051-1.014(t,6H),0.237(s,9H),0.066(s,1H),;
13C NMR(400MHz,CDCl3):δ(ppm)94.7,34.4,22.9,3.3,2.6.MS(EI,m/z)187。
the nuclear magnetic resonance structure can determine that the product obtained in the embodiment has a structure shown in a formula I and is trimethylsilyl ketoxime.
The purity of trimethylsilyl ketoxime obtained in this example was measured by gas chromatography to obtain 98.3%.
49.9 parts by mass of trimethylsilyl ketoxime obtained in this example, 49.9 parts by mass of allyltrimethoxysilane, and 0.2 part by mass of tetrabutyl titanate were uniformly mixed at room temperature to obtain a primer solution.
Coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 50s, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying for later use; the organic silicon release agent is a commercially available general organic silicon release agent (a two-component organic silicon release agent produced by Shanghai silicon friend new material science and technology Co., Ltd.);
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.02N/m, and the noise is 3 decibels; the polypropylene film coated with the non-setting adhesive is stuck on the surface of a PET film, and the peel strength of the non-setting adhesive and the PET film is tested to obtain the result of 1.95N/m.
In the embodiment, the peel strength is tested by using the test method of the peel strength of the adhesive tape of GB/T2792-2014.
Example 2
Trimethylsilyl ketoxime was prepared according to the method described in example 1;
uniformly mixing 49.5 parts by mass of trimethylsilyl ketoxime obtained in the embodiment, 49.5 parts by mass of allyl trimethoxy silane and 1 part by mass of tetrabutyl titanate at room temperature to obtain a primer solution;
coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 30s, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying for later use; the silicone release agent is the same as the universal silicone release agent described in example 1;
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.04N/m, and the noise is 4 decibels; the polypropylene film coated with the adhesive sticker is attached to the surface of a PET film, and the peel strength of the adhesive sticker and the PET film is tested to obtain a result of 1.76N/m.
In the embodiment, the peel strength is tested by using the test method of the peel strength of the adhesive tape of GB/T2792-2014.
Example 3
Trimethylsilyl ketoxime was prepared according to the method described in example 1;
uniformly mixing 49.7 parts by mass of trimethylsilyl ketoxime obtained in the embodiment, 49.7 parts by mass of allyl trimethoxy silane and 0.6 part by mass of tetrabutyl titanate at room temperature to obtain a primer solution;
coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 25s, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying for later use; the silicone release agent is the same as the universal silicone release agent described in example 1;
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.03N/m, and the noise is 3 decibels; the polypropylene film coated with the non-setting adhesive is stuck on the surface of a PET film, and the peel strength of the non-setting adhesive and the PET film is tested to obtain the result of 1.95N/m.
In the embodiment, the peel strength is tested by using the test method of the peel strength of the adhesive tape of GB/T2792-2014.
Example 4
Trimethylsilyl ketoxime was prepared according to the method described in example 1;
uniformly mixing 45 parts by mass of trimethylsilyl ketoxime obtained in the embodiment, 54 parts by mass of allyl trimethoxy silane and 1 part by mass of ethyl titanate at room temperature to obtain a primer solution;
coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 26s, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying for later use; the silicone release agent is the same as the universal silicone release agent described in example 1;
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.03N/m, and the noise is 3 decibels; the polypropylene film coated with the adhesive sticker is attached to the surface of a PET film, and the peel strength of the adhesive sticker and the PET film is tested to obtain the result of 1.92N/m.
In the embodiment, the peel strength is tested by using the test method of the peel strength of the adhesive tape of GB/T2792-2014.
Example 5
Trimethylsilyl ketoxime was prepared according to the method described in example 1;
uniformly mixing 52 parts by mass of trimethylsilyl ketoxime obtained in the embodiment, 47.2 parts by mass of allyl trimethoxy silane and 0.8 part by mass of isopropyl titanate at room temperature to obtain a primer solution;
coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 24s, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying for later use; the silicone release agent is the same as the universal silicone release agent described in example 1;
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.03N/m, and the noise is 3 decibels; the polypropylene film coated with the adhesive sticker is attached to the surface of a PET film, and the peel strength of the adhesive sticker and the PET film is tested to obtain the result of 1.94N/m.
In the embodiment, the peel strength is tested by using the test method of the peel strength of the adhesive tape of GB/T2792-2014.
Comparative example 1
The polypropylene film coated with the adhesive sticker was directly attached to the surface of the PET film, and the peel strength of the adhesive sticker and the PET film was measured to find that the peel strength was 1.84N/m.
Comparative example 2
Preparing primer liquid according to a method disclosed by the prior art of primer performance research for improving the bonding strength of a silicone rubber-polypropylene interface (Wangxiang et al, university of Hangzhou State academic newspaper, 7 months in 2017);
coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 7min, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying; the silicone release agent was the same as in example 1;
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.09N/m, and the noise is 5 decibels; the polypropylene film coated with the adhesive sticker is attached to the surface of a PET film, and the peel strength of the adhesive sticker and the PET film is tested to obtain a result of 1.13N/m.
Comparative example 3
Preparing primer solution according to a method disclosed by the research on the addition type silicone rubber/nylon interface bonding mechanism in the prior art (arbor and the like, rubber industry, 2014);
coating the primer solution on a polypropylene film in a thickness of 1-2 microns, drying after 11min, then coating an organic silicon release agent in a thickness of 1-2 microns, and drying; the silicone release agent was the same as in example 1;
covering the polypropylene film coated with the non-setting adhesive on an organic silicon release agent, contacting the non-setting adhesive with the organic silicon release agent, rolling, and aging at 40 ℃ for 7 days to obtain a polypropylene laminated film;
separating the polypropylene laminated film from the junction of the non-setting adhesive and the organic silicon release agent to obtain a polypropylene film coated with the non-setting adhesive, wherein the peel strength is 0.11N/m, and the noise is 6 decibels; the polypropylene film coated with the non-setting adhesive is pasted on the surface of a PET film, and the peel strength of the non-setting adhesive and the PET film is tested to obtain the result of 0.75N/m.
According to the records of the embodiments 1 to 3 and the comparative examples 1 to 3, the polypropylene film is prepared by the primer for coating the silicone release agent on the polypropylene film, the polypropylene film coated with the non-setting adhesive is separated from the silicone release agent, and is adhered to the surface of a PET film, the peel strength of the PET film is 1.76 to 1.95N/m, which is equivalent to the peel strength (1.84N/m) of the non-setting adhesive directly adhered to the surface of the PET film and is higher than the peel strength (0.75 to 1.13N/m) of the polypropylene film prepared by the primer in the prior art, so that the primer for coating the silicone release agent on the polypropylene film effectively improves the bonding force of the polypropylene film and the silicone release agent, and the non-setting adhesive is prevented from being adhered to the silicone release agent; and the primer prepared from the trimethylsilyl ketoxime is dried quickly, only needs 20-50 s, does not need a solvent, and is an environment-friendly primer.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.