阅读说明：本技术 涂布于聚氯乙烯感压胶带的水性压克力压敏胶组合物 (Water-based acrylic pressure-sensitive adhesive composition coated on polyvinyl chloride pressure-sensitive adhesive tape ) 是由 李其政 段安华 蔡文洲 林士棉 王浩安 吕信谚 于 2020-05-14 设计创作，主要内容包括：本发明为一种水性压克力系压敏胶组合物,其可涂布于聚氯乙烯感压胶带,用以改善传统溶剂型压敏胶对于人体、环境与VOCs危害,其为一种环保型压敏胶,固含量约50～55％左右,对人体及自然环境相对友善。本发明水性压克力压敏胶以水作为溶剂,且不含壬基酚,对人体或是环境友善程度相对较溶剂型橡胶高很多；使用在聚氯乙烯压敏胶带上,能有效抑制熟成后小分子可塑剂转移到压敏胶上,避免造成相关物性较严重的衰退,使胶带能保持优良性能。(The invention relates to a water-based acrylic pressure-sensitive adhesive composition which can be coated on a polyvinyl chloride pressure-sensitive adhesive tape, is used for improving the harm of the traditional solvent-based pressure-sensitive adhesive to human bodies, environment and VOCs, is an environment-friendly pressure-sensitive adhesive, has the solid content of about 50-55 percent, and is relatively friendly to the human bodies and natural environment. The water-based acrylic pressure-sensitive adhesive takes water as a solvent, does not contain nonyl phenol, and has much higher degree of environmental friendliness to human bodies than solvent-based rubber; when the adhesive tape is used on a polyvinyl chloride pressure-sensitive adhesive tape, the transfer of a small molecular plasticizer to the pressure-sensitive adhesive after curing can be effectively inhibited, the serious decline of relevant physical properties is avoided, and the adhesive tape can keep excellent performance.)

1. The water-based acrylic pressure-sensitive adhesive composition coated on the polyvinyl chloride pressure-sensitive adhesive tape is characterized by comprising the following components in parts by weight: a water-based resin, the content range of which is 0.5 to 25 percent; a soft monomer, the content of which is 1-55%; and an anionic reactive emulsifier selected from polyoxyethylene alkyl ether ammonium sulfate and a nonionic emulsifier in an amount of 0.01 to 5%.

2. The aqueous acryl pressure-sensitive adhesive composition of claim 1, wherein the anionic reactive emulsifier is an environmentally friendly non-nonylphenol natural surfactant.

3. The aqueous acryl pressure-sensitive adhesive composition of claim 1 wherein the soft monomer is one or more selected from the group consisting of dibutyl maleate, dioctyl maleate, n-octyl acrylate, borneol acrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

4. The aqueous acryl pressure sensitive adhesive composition of claim 1, wherein the aqueous resin is one or more selected from the group consisting of C5 petroleum resin, terpene phenol resin, rosin resin and aqueous rubber.

5. The aqueous acryl pressure-sensitive adhesive composition according to claim 4, wherein the aqueous rubber is selected from natural rubber, styrene-butadiene rubber or natural latex.

6. The aqueous acryl pressure-sensitive adhesive composition of claim 2, wherein the soft monomer is included in an amount of 1 to 35%.

7. The aqueous acryl pressure-sensitive adhesive composition of claim 2, wherein the type of the aqueous resin is applicable in a range of 0.5 to 20%.

Technical Field

The invention relates to a water-based acrylic pressure-sensitive adhesive coated on a polyvinyl chloride pressure-sensitive adhesive tape, which is particularly assisted by using a water-based environment-friendly primer and a water-based environment-friendly pressure-sensitive adhesive which need to use related auxiliary agents.

Background

In the process of manufacturing the polyvinyl chloride pressure sensitive adhesive tape, Nonylphenol (NP) which pollutes the environment, also called nonylphenol, is used as a main raw material, and although nonylphenol is often used as one of raw materials for manufacturing Nonylphenol Polyoxyethylene Ethers (NPEO) due to the characteristics of high viscosity, high boiling point and low vapor pressure, in recent years, due to the fact that the nonylphenol is similar to estrogen (estrogen) in chemical structure and is considered to be one of environment hormones, the environmental awareness is raised, and the long-term contact is suspicious, so that the pollution of organisms and the environment is great, and therefore, the problem of the environmental hormones is solved.

Because the surface energy of the polyvinyl chloride film is high, if the rubber or the acrylic pressure-sensitive adhesive is directly coated, the adhesive will be degummed, so a layer of primer is coated before the aqueous acrylic glue is coated to be used as a medium for combining the polyvinyl chloride film and the rubber or the acrylic pressure-sensitive adhesive, so as to improve the adherence (Anchorage) of the pressure-sensitive adhesive to the polyvinyl chloride film.

The surface glue of the traditional polyvinyl chloride pressure-sensitive adhesive tape is mostly solvent type rubber pressure-sensitive adhesive, the solid content is about 15-35%, and the proportion of the solvent is quite high; volatile Organic Compounds (VOCs) are easy to damage in the coating process, which is not only harmful to human health, but also pollutes the surrounding natural environment.

Disclosure of Invention

In view of the above, the present invention provides an aqueous environment-friendly pressure sensitive adhesive, which is free of organic solution and nonyl phenol, so that it is friendly to human body and natural environment, and it is necessary to use a related auxiliary agent for assistance with the aqueous environment-friendly primer, and the auxiliary agent is used to increase dispersibility, wettability, coatability, etc. of the aqueous environment-friendly primer and the pressure sensitive adhesive, and deionized water is used to adjust the solid content of the aqueous environment-friendly glue of the polyvinyl chloride pressure sensitive adhesive tape, so as to control the coating thickness and uniformity well.

The optimal dosage range of the reactive emulsifier is 0.01-3%; the optimal using amount range of the soft monomer is 1-35%; the optimal dosage range of the cross-linking agent is 0.1-7%; the water-based resin comprises C5 petroleum resin, terpene phenol resin, rosin resin, water-based rubber (NR Latex (natural rubber), SBR Latex (styrene-butadiene rubber)), and the optimal amount is 0.5-20%. Thus, the method not only can meet the current environmental protection requirement, but also can meet the current customer requirement in the aspect of physical property.

The water-based environment-friendly pressure-sensitive adhesive is used for a Polyvinyl chloride pressure-sensitive adhesive tape, and the Polyvinyl chloride (PVC) material has the characteristics of softness, stretching, electric insulation, heat resistance and the like, so that the applicable industries are quite wide, such as: the pressure-sensitive adhesive tape may be used for wrapping, fixing, insulating, protecting, and even printing, and may be used in trade marks, etc. and has many applications.

The invention relates to an aqueous emulsion type acrylic modified pressure-sensitive adhesive for general packaging, which is prepared by using a common acrylic emulsion pressure-sensitive adhesive similar to the current industrial acrylic emulsion pressure-sensitive adhesive, using acrylic soft monomers, functional monomers, other alkene monomers and a reactive emulsifier as media, carrying out emulsion polymerization reaction on the reactive emulsifier and an emulsifier suitable for a system by using deionized water as a medium to prepare glue with narrow particle size distribution, and matching with aqueous resin and the like, so that the whole net structure is more compact, and the characteristics of plasticizer resistance, high temperature resistance, water resistance and the like can be achieved.

The anionic reaction type emulsifier Polyoxyethylene alkyl ether ammonium sulfate (Polyoxyethylene alkyl ether ammonium sulfate) is prepared from Nonylphenol (NP) which is similar to estrogen (estrogen) in chemical structure and is considered to be one of environmental hormones, so that the environmental pollution is high, unsaturated double bonds are contained in the structure in the free radical polymerization reaction and can directly react with monomers to bond, so that the structure of the pressure-sensitive adhesive is more stable, and the nonionic emulsifier is matched, so that the stability of the adhesive is improved, the narrow particle size distribution is realized, the water resistance, the weather resistance and the like of the resin are further improved, and the emulsifier with different carbon chains can be selected to be properly adjusted according to requirements, wherein the total amount is 0.01-5%, and the optimal amount is 0.01-3%.

The structural formula of the reactive emulsifier is shown in the formula I

The type of reactive emulsifier-polymer chain type is shown in FIG. 2

The soft monomer of the invention comprises dibutyl maleate, dioctyl maleate, n-octyl acrylate, borneol acrylate, cyclohexyl methacrylate, isobornyl methacrylate and the like, and the dosage range is 1-55% of the total amount of the monomer, and the optimal dosage range is 1-35%.

The water-based resin used in the present invention is commercially available in the form of terpene phenol resin, C5 petroleum resin, rosin resin, and water-based rubbers are classified into natural rubber and synthetic rubber; the water-based Terpene Phenolic Resin (for example, DRT TR series S.C%: 50-54), water-based C5 petroleum Resin (for example, C-5RESIN, for example, DRT DP series S.C%: 50-54), water-based rosin Resin (for example, Sichuan SUPER ESTER E series S.C (solid content): 50-54), water-based natural rubber (NRlatex, S.C%: 58-62), water-based synthetic rubber (SBR Latex, S.C%: 58-62), the total amount of the water-based Terpene Phenolic Resin (for example, DRT TR series S.C%: 50-54), the optimal amount of the water-based natural rubber (NRlatex, S.C%: 58-20), and the compatibility of each brand are different, and the water-based Resin needs to be compatible with the glue system of the self-body glue system to completely eliminate the fruit.

Drawings

FIG. 1 is a flow diagram of an aqueous acrylic manufacturing reaction of the present invention.

FIG. 2 is a schematic diagram of the type of reactive emulsifier-polymer chain type according to the present invention.

Detailed Description

Process for preparing aqueous acrylic glue

Referring to fig. 1, a flow diagram of an aqueous acrylic manufacturing reaction is fully disclosed.

Step 1, acrylic acid ester soft monomers, functional monomers and other vinyl monomers such as dibutyl maleate, dioctyl maleate, n-octyl acrylate, borneol acrylate, cyclohexyl methacrylate, isobornyl methacrylate and the like are used, the dosage range is 1-55% of the total amount of the monomers, the optimal dosage range is 1-35% and the dosage range of the reactive emulsifier is 0.01-3%, deionized water is used as a medium, and the pre-emulsification polymerization reaction is carried out by the reactive emulsifier and the emulsifier suitable for the system.

And 2, heating the reaction tank to the required temperature, adding an initiator (I), common water-soluble peroxides, such as Ammonium Persulfate (APS), potassium persulfate (KPS) and the like, to start the reaction, finishing the pre-emulsification monomer step, then using an initiator (II), common water-soluble peroxides, such as Ammonium Persulfate (APS), potassium persulfate (KPS) and the like, to start titration, and after the titration time is about three to five hours, carrying out isothermal reaction for one hour.

And 3, cooling and sequentially adding an oxidant (common oxides comprise TBHP, CHPO and the like) and a reducing agent (common oxides comprise SFS and vitamin C). The reaction is terminated mainly by oxidation-reduction.

And 4, adding a neutralizing agent, such as ammonia water. Mainly used for acid-base neutralization.

And 5, adding defoaming agents, such as Silicone defoaming agents and mineral oil defoaming agents which can be classified into two types. The effect of inhibiting the bubbles of the glue is mainly provided, and the foaming property of the glue is improved.

Step 6, adding a leveling agent, wherein the main function of the leveling agent can improve the flatness of glue when the glue is wet, and each large manufacturer of the product (such as BASF CYTEC and the like) has similar functional items

And 7, adding an antioxidant to mainly enhance the antioxidant effect, such as CIBA #1010, so as to obtain the water-based environment-friendly pressure-sensitive adhesive.

The old glue scale possibly existing in the reaction furnace or the slag with larger particles generated in the reaction is removed by shaving through a filtering mode, the whole coating surface is smooth, and the thickness is uniform.

Comparative test of aqueous environment-friendly pressure-sensitive adhesive

The novel water-based environment-friendly pressure-sensitive adhesive is matched with related materials to further perform various performance tests and evaluations on the polyvinyl chloride film; the following describes the influence of polyvinyl chloride pressure sensitive adhesive on the adhesion of polyvinyl chloride film after coating the polyvinyl chloride film with different components of aqueous environment-friendly primer, the coating method is that a No. 4 wire rod is coated with about 4.5 g/per Square Meter (SM) of wet adhesive thickness, the drying condition is 105 ℃ multiplied by 1 minute, then the polyvinyl chloride film is coated with the pressure sensitive adhesive, the thickness of the pressure sensitive adhesive for coating the polyvinyl chloride film is 20um, then the curing is carried out at 70 ℃ multiplied by 8 hours, the cured polyvinyl chloride film is taken out and placed at room temperature (23 ℃) and is tested and evaluated after 24 hours at room temperature, the evaluation method is that the polyvinyl chloride film is adhered to a steel plate, and the phenomena of degumming on the adhesive surface and residual adhesive on the back surface of the adhesive tape are observed. In addition, the evaluation methods of physical properties include adhesive force, back adhesive force, cohesive force, initial adhesive force, and the like.

Test method

One, adhesion (ASTM D-1000) test:

1. the sample was cut to 19mm width, pressed back and forth once per minute at 300mm per minute using a PSTC standard blanket cylinder to adhere the sample to a cleaned ASTM standard steel plate, and left to stand for 20 minutes to be tested.

2. And fixing the plate adhered with the sample on a tensile machine, zeroing and correcting the Load cell, and setting the stripping speed.

3. And after the time is up, the sample is turned back by 180 degrees, and then the adhesion detection is started.

Second, back adhesion (ASTM D-1000) test:

1. cutting the sample into a width of 19mm, and pressing back and forth once by using a PSTC standard rubber roller at the speed of 300mmmin to ensure that the sample is adhered to a cleaned ASTM standard steel plate; the same sample is pasted in the same way and is placed for 20 minutes to be tested.

2. And fixing the plate adhered with the sample on a tensile machine, zeroing and correcting the Load cell, and setting the stripping speed.

3. And after the time is up, the sample is turned back by 180 degrees, and then the back adhesion detection is started.

Thirdly, cohesion force (PSTC-7) test:

a detection instrument: the timer was hung at 50 ℃.

1. Cutting the sample into a width of 19mm, and pressing back and forth once by using a PSTC standard rubber roller at the speed of 300mmmin to ensure that the sample is adhered to a cleaned ASTM standard steel plate; cuts were made at 25mm to give a test area of 19 x 25(mm x mm).

After 2.20 minutes, the suspension was suspended on a suspension timer, and a 500g weight was suspended below the suspension to observe the state of the adhesive surface being damaged and the suspension time.

Initial adhesion (PSTC-6) test:

a detection instrument: the stainless steel ball conforms to the PSTC-6 standard ball rolling instrument, and the diameter of the stainless steel ball is 11 mm.

1. And (4) confirming whether the roller ball instrument is kept horizontal, wiping the stainless steel ball with acetone, and clamping with tweezers.

2. After the ball slides down the device from the slope to the sample, the distance from the bottom of the rolling ball instrument to the center of the ball is measured.

Examples

The first embodiment,

The invention uses the home-made general packaging unmodified/modified waterborne acrylic pressure-sensitive adhesive to carry out the relevant comparison test, and in addition, the pressure-sensitive adhesive before and after modification is subjected to relevant aging and detection, and the relevant physical property comparison is shown in the table I. The unmodified pressure-sensitive adhesive is coated on a PVC film coated with water-based primer, and a standard steel plate is pasted after drying, so that the phenomenon of degumming can be caused, and the related physical property detection can not be carried out. Coating the modified water-based acrylic pressure-sensitive adhesive on a PVC film coated with a water-based primer, drying the film, and then labeling a standard steel plate without degumming phenomenon, and performing related physical property detection before and after curing, wherein the modified water-based acrylic pressure-sensitive adhesive is the water-based acrylic pressure-sensitive adhesive coated on the polyvinyl chloride pressure-sensitive adhesive tape prepared by the invention; the preparation method of the unmodified water-based acrylic pressure-sensitive adhesive is the same as that of the water-based acrylic pressure-sensitive adhesive coated on the polyvinyl chloride pressure-sensitive adhesive tape, except that the emulsified monomer is not added.

TABLE I contrast test of unmodified/modified water-based acrylic pressure-sensitive adhesive for homemade common package

Example II,

The invention uses self-made modified waterborne acryl glue, matches with waterborne resin/waterborne rubber/cross linker with different concentrations, the following example is waterborne rosin ester, the adding proportion is 5 percent and 10 percent, after the relevant ripening detection, the relevant physical property comparison is shown in the table two.

TABLE II post-maturation assay with addition of waterborne rosin esters

Example III,

The invention uses self-made modified waterborne acryl glue, matches with waterborne resin/waterborne rubber with different concentrations, and the like, the following example is 5 percent waterborne rosin ester and waterborne rubber with different proportions, and the detection is carried out after the relevant ripening, and the relevant physical properties are compared and shown in the table III.

Third, detection after aging of adding waterborne rosin ester and waterborne rubber

Example four,

The invention uses self-made modified waterborne acryl glue, matches with waterborne resin/waterborne rubber with different concentrations, and the like, the following example is 10 percent waterborne rosin ester and waterborne rubber with different proportions, and the detection is carried out after the relevant ripening, and the relevant physical property comparison is shown in the table IV.

TABLE IV post-maturation assay with addition of aqueous rosin esters and aqueous rubbers

The invention uses INSTRON 5564 tension machine to strip the adhesive tape at a fixed speed, observes whether the adhesive surface is degummed and whether the adhesive tape back surface has the phenomenon of adhesive residue, and the slow stripping test speed (cmmin) is 30, and records the relevant adhesive force and back surface adhesive force data.

From the above table, it can be found that after the water-based environment-friendly primer is coated on the polyvinyl chloride film, the adhesive effect of various pressure-sensitive adhesive combinations is excellent, and no adhesive surface degumming or adhesive tape back surface residual adhesive phenomenon occurs no matter slow peeling or fast peeling; the pressure sensitive adhesive tapes using the aqueous environment friendly primers of comparative examples one, two, three and four were not sticky 5 times to cause the occurrence of the adhesive failure. The invention is water environmental protection surface glue, which is not containing organic solution and nonyl phenol, so it is friendly to human body and natural environment.

All of the features disclosed in this application can be implemented in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.