CN110713811B - Method for manufacturing high-elasticity pressure-sensitive adhesive for reflective film - Google Patents
Method for manufacturing high-elasticity pressure-sensitive adhesive for reflective film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
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Abstract
The invention relates to the technical field of pressure-sensitive adhesives for reflective films, in particular to a method for manufacturing a high-elasticity pressure-sensitive adhesive for reflective films, which comprises the following components in parts by weight: 100 parts of poly (methyl) acrylic acid copolymer, 1.5-10 parts of reactive liquid butadiene-acrylonitrile rubber, 0.1-0.8 part of epoxy cross-linking agent, 5-10 parts of expanded microspheres and 45-60 parts of organic solvent. The raw materials are selected as the components of the high-elasticity pressure-sensitive adhesive for the reflective film, the finally prepared pressure-sensitive adhesive has excellent elasticity, and the high-flexibility poly (methyl) acrylic acid copolymer and the air bags in the expansion microspheres can absorb certain energy after being impacted by the outside, so that the damage of the product is reduced; meanwhile, the poly (methyl) acrylic acid copolymer has excellent initial adhesion and cohesion, the product is guaranteed to have better constructability, only a little external pressure needs to be applied during use, the pressure-sensitive adhesive can be attached to the base material, and the poly (methyl) acrylic acid copolymer is not easy to drop and warp and has longer service life.
Description
Technical Field
The invention relates to a pressure-sensitive adhesive for a reflective film, in particular to a method for manufacturing a high-elasticity pressure-sensitive adhesive for a reflective film.
Background
The reflective film is widely used in people's social life as a reversible reflective film, and as the application of the reflective film is more and more mature, the reflective film is also applied in wider fields, for example, the reflective film is used in the aspects of guideboards, automobile license plates, guard rails, crash bars and the like in the transportation industry, and the surface of the reflective film is easily scratched and abraded in common application scenes. The existing reflective film generally comprises a plurality of polymer resin coatings, glass bead layers and pressure-sensitive adhesive layers, and the pressure-sensitive adhesive layers generally have relatively strong rigidity and relatively poor reboundable toughness, so that the reflective film is easy to scratch and crack after being impacted or rubbed, which is a main reason for the conditions of short service life and the like of the reflective film and also directly causes the condition of relatively high use cost of the reflective film.
In view of the above problems, it is highly desirable to improve the current state of pressure-sensitive adhesives on the market.
Disclosure of Invention
The invention provides a novel method for manufacturing a high-elasticity pressure-sensitive adhesive for a reflective film, aiming at the defects of poor reboundable toughness and the like of the pressure-sensitive adhesive layer for the reflective film in the prior art.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the preparation method of the high-elasticity pressure-sensitive adhesive for the reflective film comprises the following components in parts by weight:
100 parts of poly (meth) acrylic acid copolymer,
1.5 to 10 parts of reactive liquid nitrile butadiene rubber,
0.1 to 0.8 part of epoxy crosslinking agent,
5-10 parts of expanded microspheres,
45-60 parts of an organic solvent,
the organic solvent is one or a mixture of two of an ester solvent and a ketone solvent, and the preparation method comprises the following steps:
q1: at normal temperature, putting the organic solvent and the poly (methyl) acrylic acid copolymer in the weight ratio into a high-speed stirrer for pre-dispersion treatment, and stirring for 20-30 minutes at the stirring speed of 800-1500 r/min to obtain a dispersion A;
q2: adding the reactive liquid-state butadiene-acrylonitrile rubber and the expanded microspheres in the weight ratio into the dispersion liquid A, and continuously stirring for 30 minutes to obtain a dispersion liquid B;
q3: and adding the epoxy cross-linking agent in the weight ratio into the dispersion liquid B, and stirring for 15 minutes to obtain the high-elasticity pressure-sensitive adhesive for the reflective film.
The raw materials are selected as the components of the high-elasticity pressure-sensitive adhesive for the reflective film, so that the finally prepared product has excellent impact resistance and rebound elasticity, and also has excellent initial adhesion and retention, the product can be constructed under different climatic environments and can be better attached to the surface of a base material for use, and the service life of the reflective film is prolonged.
In the step Q1, the stirring speed is 800-1500 r/min, the stirring time is 20-30 min, so that the poly (meth) acrylic acid copolymer is dispersed in the organic solvent under high-speed stirring to form a uniform and stable solution, if the stirring speed exceeds 1500r/min, the friction between the poly (meth) acrylic acid copolymer molecular chain and the stirring shaft is too large due to too fast stirring speed, so that heat is generated and the stability of the poly (meth) acrylic acid copolymer is affected, if the stirring speed is lower than 800r/min, the phenomenon of non-uniform dispersion is easily caused due to too low stirring speed, and the stirring time is controlled to be 20-30 min, so that the volatilization of the solvent in the stirring process is reduced to the greatest extent and the stirring uniformity is ensured.
In the step Q2, the reactive liquid butadiene-acrylonitrile rubber and the expanded microspheres are added into the dispersion liquid A and stirred for 30 minutes, so that the expanded microspheres can be wetted by the poly (methyl) acrylic acid copolymer more fully, and meanwhile, the molecular chains of the reactive liquid butadiene-acrylonitrile rubber can be mixed and wound with the molecular chains of the poly (methyl) acrylic acid copolymer, so that the finally prepared product is more excellent in stability and workability.
In the step Q3, an epoxy cross-linking agent is added to be fully and uniformly mixed with the dispersion liquid B, and the epoxy cross-linking agent is added in the last step to avoid that the reactive groups on the epoxy cross-linking agent and the reactive groups on the poly (meth) acrylic acid copolymer and the reactive liquid butadiene-acrylonitrile rubber are contacted too early to generate chemical reaction, so that the application property and the stability of the product are influenced.
The high-elasticity pressure-sensitive adhesive for the reflective film prepared by the steps has excellent impact resilience, initial adhesion and retention force, and can ensure better stability and constructability in different climatic environments, so the defects of the existing pressure-sensitive adhesive are greatly improved, and the manufacturing process is simple.
Preferably, in the above method for manufacturing a high-elasticity pressure-sensitive adhesive for a reflective film, the poly (meth) acrylic acid copolymer comprises the following components in parts by weight:
4-8 parts of butadiene, namely butadiene,
20-30 parts of methyl acrylate,
50-65 parts of acrylic acid-2-ethyl ester,
8-14 parts of vinyl acetate, and the like,
0.8 to 1.5 parts of itaconic acid,
0.8 to 2.5 parts of tert-butyl peroxybenzoate,
200 to 320 parts of ethyl acetate,
50-80 parts of toluene,
the manufacturing method comprises the following steps:
s1: mixing and stirring butadiene, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene at room temperature to prepare a mixture I;
s2: mixing and stirring methyl acrylate, acrylic acid-2-ethyl ester, vinyl acetate, itaconic acid and tert-butyl peroxybenzoate according to the weight ratio to prepare a mixture II;
s3: taking 70% of the total weight of the tert-butyl peroxybenzoate, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene, mixing and stirring to prepare a mixture III;
s4: putting the mixture I into a reaction container provided with a stirrer, a heater, a condenser and a nitrogen inlet pipe, opening the nitrogen inlet pipe and introducing nitrogen, and simultaneously opening the stirrer to stir the mixture I for 15-30 minutes;
s5: closing the nitrogen inlet pipe, stopping inputting nitrogen, opening the heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 10-15 minutes when the temperature in the reaction container is increased to 100-120 ℃;
s6: dropping the mixture II into a reaction container, uniformly dropping the mixture II within 100-150 minutes, keeping the temperature in the reaction container after the dropping is finished, and continuously reacting for 120-180 minutes;
s7: dropping the mixture III into the reaction container, uniformly dropping the mixture in 40-90 minutes, keeping the temperature in the reaction container after the dropping is finished, and continuously reacting for 180-240 minutes;
s8: reducing the temperature in the reaction vessel, stopping the machine and pouring out when the temperature in the reaction vessel is reduced to 40 ℃ to obtain the poly (methyl) acrylic acid copolymer.
In step S1, the components in the above ratio are selected to make butadiene have a suitable concentration in the solution, so as to ensure the conversion rate and reaction stability of the product production.
In step S2, the components in the above ratio are selected to allow the reaction monomers to be mixed more thoroughly, the reaction between the monomers is more moderate during the reaction process, and the conditions of local implosion and excessive heat release caused by different reactivity of the monomers during the reaction process are avoided.
In step S3, the tert-butyl peroxybenzoate in the above ratio is selected to prepare a mixture iii, which can further promote the reaction of each reaction monomer, improve the conversion rate, and avoid the influence of too high content of residual monomers in the obtained poly (meth) acrylic acid copolymer on the final product performance.
In step S4, the nitrogen is continuously introduced into the reaction vessel to ensure that the air in the reaction vessel is completely removed to reduce the inhibition of the reaction by oxygen.
In step S5, the temperature in the reaction vessel is raised to 100-120 ℃, and the reaction is continued for 10-15 minutes, so as to preheat the whole reaction vessel and ensure that the reaction can be stably carried out after solvent reflux and subsequent material addition.
In the step S6, the mixture II is uniformly dripped into the reaction container within 100-150 minutes, so that the reaction is more stable, if the dripping time is too short, the monomer concentration in the reaction container is too high, so that the reaction is too violent, the heat release of the reaction container is too large in a short time, so that the production safety hazard is caused, and the molecular weight of the poly (meth) acrylic acid copolymer is influenced, so that the product performance is influenced; if the dropping time is too long, the conditions of too low monomer reaction concentration and insufficient reaction are easy to occur, so that the reaction activity is reduced, and the further growth of the molecular chain of the poly (meth) acrylic acid copolymer is influenced.
In step S7, the mixture iii is further added dropwise into a reaction vessel to further react the incompletely reacted monomers in the previous step, thereby increasing the conversion rate, further increasing the molecular weight of the poly (meth) acrylic acid copolymer, and ensuring that the poly (meth) acrylic acid copolymer has better flexibility and cohesive strength.
In step S8, the reaction container is cooled to 40 ℃ and poured out, so that the poly (meth) acrylic acid copolymer is not volatilized too much due to too high temperature, and the poly (meth) acrylic acid copolymer has a suitable viscosity at the temperature, thereby facilitating pouring out and storing.
The poly (methyl) acrylic acid copolymer prepared by the steps not only has stronger toughness and better initial viscosity at low temperature, but also has higher cohesive strength, so the poly (methyl) acrylic acid copolymer is very suitable to be used as a raw material of a pressure-sensitive adhesive for a reflective film.
Preferably, in the method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film, the poly (meth) acrylic acid copolymer has reactive amino groups and carboxyl groups and has a weight average molecular weight of 80 to 130 ten thousand g/mol.
The weight average molecular weight of the poly (meth) acrylic acid copolymer is controlled to 80 to 130 kg/mol because the poly (meth) acrylic acid copolymer has a good viscosity within the above numerical range, and does not affect subsequent workability, and the weight average molecular weight within the range enables the poly (meth) acrylic acid copolymer to have more excellent flexibility and cohesive strength.
Preferably, in the method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film, the poly (meth) acrylic acid copolymer has an acid value of 6 to 50 mgKOH/mol.
The poly (meth) acrylic acid copolymer is controlled within an acid value range of 6-50 mgKOH/mol, so that the poly (meth) acrylic acid copolymer has proper polarity, good compatibility and high crosslinking reactivity of the poly (meth) acrylic acid copolymer with other resins or additives are guaranteed, and a molecular chain of the poly (meth) acrylic acid copolymer is in a dense cross-network structure within the acid value range, thereby being beneficial to improving the cohesive strength and the adhesive property of the resin.
Preferably, in the method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film, the poly (methyl) acrylic acid copolymer has a glass transition temperature of-55 to-40 ℃.
The poly (meth) acrylic acid copolymer is controlled within a glass transition temperature range of-55 to-40 ℃, so that the poly (meth) acrylic acid copolymer has excellent bonding property and flexibility, the poly (meth) acrylic acid copolymer is easily hardened due to an excessively high glass transition temperature, the bonding property is reduced, and the poly (meth) acrylic acid copolymer is easily subjected to glue anti-sticking and glue overflowing when used at a high temperature due to an excessively low glass transition temperature.
Preferably, in the method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film, the reactive liquid cyanogen butadiene rubber has a glass transition temperature of-65 to-35 ℃.
Within the above glass transition temperature range, the reactive liquid nitrile rubber has suitable impact resistance and flexibility.
Preferably, in the above method for manufacturing a high-elasticity pressure-sensitive adhesive for a light-reflecting film, the reactive liquid nitrile rubber has a terminal carboxyl group or an amino reactive group.
The reactive liquid butadiene-acrylonitrile rubber with the terminal carboxyl or amino reactive group can be directly reacted with an epoxy cross-linking agent or a poly (methyl) acrylic acid copolymer, so that the molecular structure of the butadiene-acrylonitrile rubber is integrated, the stability of the poly (methyl) acrylic acid copolymer is facilitated, and the molecular chains are cross-linked into a net structure with higher cohesive strength and toughness.
Preferably, in the method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film, the epoxy crosslinking agent is one or a mixture of two of the following chemical structures,
wherein R1 is alkyl or cycloalkyl or aromatic hydrocarbon, R2 is hydrogen or C2-C7 alkyl group.
The epoxy crosslinking agent with the structure has better reactivity and higher crosslinking compactness, thereby better ensuring the performance of the poly (methyl) acrylic acid copolymer.
Preferably, in the above method for manufacturing a high-elasticity pressure-sensitive adhesive for a reflective film, the expanded microspheres are dry microspheres which have been expanded.
The expanded dry microspheres do not need to be heated, the finally prepared high-elasticity pressure-sensitive adhesive for the reflective film does not need to be heated for use, the expanded dry microspheres contain air airbags inside, and when a product receives external impact, the air airbags can absorb a part of energy so as to better protect the product and reduce damage.
Preferably, in the method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film, the particle size of the expanded microspheres is 20-60 micrometers.
The particle size of the expanded microspheres is within the above range, and the external impact energy can be better absorbed.
Compared with the prior art, the invention has the outstanding beneficial effects that: firstly, the pressure-sensitive adhesive produced by the invention has excellent elasticity, and the high-flexibility poly (methyl) acrylic acid copolymer and the air sac in the expansion microsphere can absorb certain energy after being impacted by the outside, thereby reducing the damage of the product; secondly, the poly (methyl) acrylic acid copolymer has excellent initial adhesion and cohesion while having high elasticity, so that the product has better construction performance, and the pressure-sensitive adhesive can be attached to a base material only by applying a little external pressure when in use; finally, the pressure-sensitive adhesive finally prepared by the invention has excellent adhesive property, is not easy to fall off and warp after being attached on a base material, and has longer service life.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments, but they are not intended to limit the invention:
example 1
The preparation method of the high-elasticity pressure-sensitive adhesive for the reflective film comprises the following components in parts by weight:
100 parts of poly (meth) acrylic acid copolymer,
1.5 parts of reactive liquid cyanogen butadiene rubber,
0.1 part of epoxy cross-linking agent,
5 parts of expanded microspheres, namely 5 parts of expanded microspheres,
45 parts of an organic solvent, namely 45 parts of,
the organic solvent is one or a mixture of two of an ester solvent and a ketone solvent, and the preparation method comprises the following steps:
q1: at normal temperature, putting the organic solvent and the poly (methyl) acrylic acid copolymer in the weight ratio into a high-speed stirrer for pre-dispersion treatment, and stirring for 20 minutes at the stirring speed of 800r/min to obtain a dispersion A;
q2: adding the reactive liquid-state butadiene-acrylonitrile rubber and the expanded microspheres in the weight ratio into the dispersion liquid A, and continuously stirring for 30 minutes to obtain a dispersion liquid B;
q3: and adding the epoxy cross-linking agent in the weight ratio into the dispersion liquid B, and stirring for 15 minutes to obtain the high-elasticity pressure-sensitive adhesive for the reflective film.
Preferably, the poly (meth) acrylic acid copolymer comprises the following components in parts by weight:
4 parts of butadiene, namely butadiene, wherein,
20 parts of methyl acrylate, namely 20 parts of methyl acrylate,
50 parts of acrylic acid-2-ethyl ester,
8 parts of vinyl acetate, namely 8 parts of vinyl acetate,
0.8 part of itaconic acid, namely,
0.8 part of tert-butyl peroxybenzoate,
200 parts of ethyl acetate,
50 parts of toluene, namely toluene,
the manufacturing method comprises the following steps:
s1: mixing and stirring butadiene, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene at room temperature to prepare a mixture I;
s2: mixing and stirring methyl acrylate, acrylic acid-2-ethyl ester, vinyl acetate, itaconic acid and tert-butyl peroxybenzoate according to the weight ratio to prepare a mixture II;
s3: taking 70% of the total weight of the tert-butyl peroxybenzoate, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene, mixing and stirring to prepare a mixture III;
s4: putting the mixture I into a reaction vessel provided with a stirrer, a heater, a condenser and a nitrogen inlet pipe, opening the nitrogen inlet pipe and introducing nitrogen, and simultaneously opening the stirrer to stir the mixture I for 15 minutes;
s5: closing the nitrogen inlet pipe, stopping inputting nitrogen, opening the heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 10 minutes when the temperature in the reaction container is increased to 100-120 ℃;
s6: dropping the mixture II into the reaction container, uniformly dropping within 100 minutes, keeping the temperature in the reaction container after dropping, and continuously reacting for 120 minutes;
s7: dripping the mixture III into a reaction container, uniformly dripping within 40 minutes, keeping the temperature in the reaction container after dripping, and continuously reacting for 180 minutes;
s8: reducing the temperature in the reaction vessel, stopping the machine and pouring out when the temperature in the reaction vessel is reduced to 40 ℃ to obtain the poly (methyl) acrylic acid copolymer.
Preferably, the poly (meth) acrylic acid copolymer has reactive amino and carboxyl groups and has a weight average molecular weight of 80 ten thousand g/mol.
Preferably, the poly (meth) acrylic acid copolymer has an acid value of 6 mgKOH/mol.
Preferably, the poly (meth) acrylic acid copolymer has a glass transition temperature of-55 ℃.
Preferably, the reactive liquid nitrile rubber has a glass transition temperature of-65 ℃.
Preferably, the reactive liquid nitrile rubber has terminal carboxyl or amino reactive groups.
Preferably, the epoxy crosslinking agent is one or a mixture of two of the following chemical structures,
wherein R1 is alkyl or cycloalkyl or aromatic hydrocarbon, R2 is hydrogen or C2-C7 alkyl group.
Preferably, the expanded microspheres are dry microspheres that have been expanded.
Preferably, the expanded microspheres have a particle size of 20 microns.
Example 2
The preparation method of the high-elasticity pressure-sensitive adhesive for the reflective film comprises the following components in parts by weight:
100 parts of poly (meth) acrylic acid copolymer,
10 parts of reactive liquid cyanogen butadiene rubber,
0.8 part of epoxy cross-linking agent,
10 parts of expanded microspheres, namely 10 parts of expanded microspheres,
60 parts of an organic solvent, namely 60 parts of,
the organic solvent is one or a mixture of two of an ester solvent and a ketone solvent, and the preparation method comprises the following steps:
q1: at normal temperature, putting the organic solvent and the poly (methyl) acrylic acid copolymer in the weight ratio into a high-speed stirrer for pre-dispersion treatment, and stirring for 30 minutes at the stirring speed of 1500r/min to obtain a dispersion A;
q2: adding the reactive liquid-state butadiene-acrylonitrile rubber and the expanded microspheres in the weight ratio into the dispersion liquid A, and continuously stirring for 30 minutes to obtain a dispersion liquid B;
q3: and adding the epoxy cross-linking agent in the weight ratio into the dispersion liquid B, and stirring for 15 minutes to obtain the high-elasticity pressure-sensitive adhesive for the reflective film.
Preferably, the poly (meth) acrylic acid copolymer comprises the following components in parts by weight:
8 parts of butadiene, namely 8 parts of butadiene,
30 parts of methyl acrylate, namely 30 parts of methyl acrylate,
65 parts of acrylic acid-2-ethyl ester,
14 parts of vinyl acetate, 14 parts of ethylene acetate,
1.5 parts of itaconic acid, namely,
2.5 parts of tert-butyl peroxybenzoate,
320 parts of ethyl acetate, namely 320 parts of ethyl acetate,
80 parts of toluene, namely toluene,
the manufacturing method comprises the following steps:
s1: mixing and stirring butadiene, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene at room temperature to prepare a mixture I;
s2: mixing and stirring methyl acrylate, acrylic acid-2-ethyl ester, vinyl acetate, itaconic acid and tert-butyl peroxybenzoate according to the weight ratio to prepare a mixture II;
s3: taking 70% of the total weight of the tert-butyl peroxybenzoate, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene, mixing and stirring to prepare a mixture III;
s4: putting the mixture I into a reaction vessel provided with a stirrer, a heater, a condenser and a nitrogen inlet pipe, opening the nitrogen inlet pipe and introducing nitrogen, and simultaneously opening the stirrer to stir the mixture I for 30 minutes;
s5: closing the nitrogen inlet pipe, stopping inputting nitrogen, opening the heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 15 minutes when the temperature in the reaction container is increased to 120 ℃;
s6: dropping the mixture II into the reaction container, uniformly dropping within 150 minutes, keeping the temperature in the reaction container after dropping, and continuously reacting for 180 minutes;
s7: dropping the mixture III into a reaction container, uniformly dropping within 90 minutes, keeping the temperature in the reaction container after dropping, and continuously reacting for 240 minutes;
s8: reducing the temperature in the reaction vessel, stopping the machine and pouring out when the temperature in the reaction vessel is reduced to 40 ℃ to obtain the poly (methyl) acrylic acid copolymer.
Preferably, the poly (meth) acrylic acid copolymer has reactive amino and carboxyl groups and has a weight average molecular weight of 130 ten thousand g/mol.
Preferably, the poly (meth) acrylic acid copolymer has an acid value of 50 mgKOH/mol.
Preferably, the poly (meth) acrylic acid copolymer has a glass transition temperature of-40 ℃.
Preferably, the reactive liquid nitrile rubber has a glass transition temperature of-35 ℃.
Preferably, the reactive liquid nitrile rubber has terminal carboxyl or amino reactive groups.
Preferably, the epoxy crosslinking agent is one or a mixture of two of the following chemical structures,
wherein R1 is alkyl or cycloalkyl or aromatic hydrocarbon, R2 is hydrogen or C2-C7 alkyl group.
Preferably, the expanded microspheres are dry microspheres that have been expanded.
Preferably, the expanded microspheres have a particle size of 60 microns.
Example 3
The preparation method of the high-elasticity pressure-sensitive adhesive for the reflective film comprises the following components in parts by weight:
100 parts of poly (meth) acrylic acid copolymer,
5.8 parts of reactive liquid cyanogen butadiene rubber,
0.45 part of epoxy cross-linking agent,
7.5 parts of expanded microspheres, namely,
52.5 parts of an organic solvent, namely,
the organic solvent is one or a mixture of two of an ester solvent and a ketone solvent, and the preparation method comprises the following steps:
q1: at normal temperature, putting the organic solvent and the poly (methyl) acrylic acid copolymer in the weight ratio into a high-speed stirrer for pre-dispersion treatment, and stirring for 25 minutes at a stirring speed of 1150r/min to obtain a dispersion A;
q2: adding the reactive liquid-state butadiene-acrylonitrile rubber and the expanded microspheres in the weight ratio into the dispersion liquid A, and continuously stirring for 30 minutes to obtain a dispersion liquid B;
q3: and adding the epoxy cross-linking agent in the weight ratio into the dispersion liquid B, and stirring for 15 minutes to obtain the high-elasticity pressure-sensitive adhesive for the reflective film.
Preferably, the poly (meth) acrylic acid copolymer comprises the following components in parts by weight:
6 parts of butadiene, namely butadiene, wherein,
25 parts of methyl acrylate,
57.5 parts of acrylic acid-2-ethyl ester,
11 parts of vinyl acetate, namely 11 parts of vinyl acetate,
1.15 parts of itaconic acid, namely,
1.65 parts of tert-butyl peroxybenzoate,
260 parts of ethyl acetate, namely 260 parts of ethyl acetate,
65 parts of toluene,
the manufacturing method comprises the following steps:
s1: mixing and stirring butadiene, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene at room temperature to prepare a mixture I;
s2: mixing and stirring methyl acrylate, acrylic acid-2-ethyl ester, vinyl acetate, itaconic acid and tert-butyl peroxybenzoate according to the weight ratio to prepare a mixture II;
s3: taking 70% of the total weight of the tert-butyl peroxybenzoate, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene, mixing and stirring to prepare a mixture III;
s4: putting the mixture I into a reaction vessel provided with a stirrer, a heater, a condenser and a nitrogen inlet pipe, opening the nitrogen inlet pipe and introducing nitrogen, and simultaneously opening the stirrer to stir the mixture I for 23 minutes;
s5: closing the nitrogen inlet pipe, stopping inputting nitrogen, opening the heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 13 minutes when the temperature in the reaction container is increased to 100-120 ℃;
s6: dropping the mixture II into the reaction container, uniformly dropping within 125 minutes, and keeping the temperature in the reaction container and continuously reacting for 150 minutes;
s7: dropping the mixture III into a reaction container, uniformly dropping within 65 minutes, keeping the temperature in the reaction container after dropping, and continuously reacting for 210 minutes;
s8: reducing the temperature in the reaction vessel, stopping the machine and pouring out when the temperature in the reaction vessel is reduced to 40 ℃ to obtain the poly (methyl) acrylic acid copolymer.
Preferably, the poly (meth) acrylic acid copolymer has reactive amino and carboxyl groups and has a weight average molecular weight of 105 ten thousand g/mol.
Preferably, the poly (meth) acrylic acid copolymer has an acid value of 28 mgKOH/mol.
Preferably, the poly (meth) acrylic acid copolymer has a glass transition temperature of-42.5 ℃.
Preferably, the reactive liquid nitrile rubber has a glass transition temperature of-50 ℃.
Preferably, the reactive liquid nitrile rubber has terminal carboxyl or amino reactive groups.
Preferably, the epoxy crosslinking agent is one or a mixture of two of the following chemical structures,
wherein R1 is alkyl or cycloalkyl or aromatic hydrocarbon, R2 is hydrogen or C2-C7 alkyl group.
Preferably, the expanded microspheres are dry microspheres that have been expanded.
Preferably, the expanded microspheres have a particle size of 40 microns.
Example 4
Taking the high-elasticity pressure-sensitive adhesive for the reflective film obtained in each example, taking the existing pressure-sensitive adhesive as a comparative example 1, taking the existing liquid butadiene cyanide rubber as a comparative example 2, and carrying out tests on three properties of initial adhesion, holding power and impact resistance, wherein the test method comprises the following steps:
firstly, initial adhesion testing: a test sample is dried by a coating device through an oven to obtain a dry test coating with the thickness of 30 microns, a J.DOW method is adopted, rolling balls with the diameters of 2/32 inches-32/32 inches are used on a smooth surface with the inclination angle of 30 degrees, sliding downwards from the starting point of the sliding assisting distance is carried out, and the maximum stopping ball number of the steel ball on the rubber surface is measured.
Wherein the measuring environment is 23 ℃/65% RH; the sliding assisting distance is 100 mm; the glide distance was 100 mm.
Evaluation criteria: the larger the ball number of the steel ball finally stopped on the rubber surface in the test is, the better the initial adhesion is.
Secondly, testing the retention force: the test piece was attached to an adherend, rolled 10 times by a 2kg rubber roller, and then a 1kg weight was hung in the oven in the vertical direction, and the moving distance of the adhesive surface was measured after 1 hour, and the shorter the moving distance, the higher the cohesive strength of the sample.
Wherein the test piece is a test sample with the width of 20mm cut from a sample with gum; the adherend (substrate) was an SUS #304 steel plate polished with No. 280 water-resistant abrasive paper; the attaching area is 20mm multiplied by 20 mm; the measurement temperature was 40 ℃.
Evaluation criteria: the shorter the distance the glue side moves during the test, the better the holding force.
Thirdly, testing impact resistance: attaching the semi-finished product of the reflective film to various test pressure-sensitive adhesives, then attaching the semi-finished product to an aluminum plate substrate with the thickness of 1.0mm, placing the aluminum plate substrate in an environment with the temperature of minus 20 +/-3 ℃ for 1 hour, taking out the aluminum plate substrate and carrying out an impact test within 5 min. During impact test, the reflective film surface of the sample is placed upwards, a solid steel ball with the diameter of 25mm freely falls on the reflective film surface for 1 time at a position 2m above the sample, and the falling point is as far as possible at the center of the sample. After testing, the reflective film samples were inspected for appearance and the test results recorded.
Evaluation criteria: 1, no depression and no cracking on the film surface; 2, the film surface is sunken, but no cracking phenomenon exists; 3, the film surface is sunken and slightly cracked; 4, the film surface is obviously concave and cracks seriously.
The high-elasticity pressure-sensitive adhesive for the reflective film obtained in each example of the invention and the comparative example performance parameters are shown in table 1:
wherein comparative example 1 is ETERAC 70862 oily pressure-sensitive adhesive manufactured by Changxing special materials Co., Ltd, and comparative example 2 is Hypro 2000X168LC VTB liquid nitrile butadiene rubber manufactured by CVC Co., Ltd.
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the present invention.
Claims (7)
1. A manufacturing method of high-elasticity pressure-sensitive adhesive for reflective film is characterized in that: comprises the following components in parts by weight:
100 parts of poly (meth) acrylic acid copolymer,
1.5 to 10 parts of reactive liquid nitrile butadiene rubber,
0.1 to 0.8 part of epoxy crosslinking agent,
5-10 parts of expanded microspheres,
45-60 parts of an organic solvent,
the organic solvent is one or a mixture of two of an ester solvent and a ketone solvent, the expanded microspheres are expanded dry microspheres, the particle size of the expanded microspheres is 20-60 micrometers, and the preparation method comprises the following steps:
q1: at normal temperature, putting the organic solvent and the poly (methyl) acrylic acid copolymer in the weight ratio into a high-speed stirrer for pre-dispersion treatment, and stirring for 20-30 minutes at the stirring speed of 800-1500 r/min to obtain a dispersion A;
q2: adding the reactive liquid-state butadiene-acrylonitrile rubber and the expanded microspheres in the weight ratio into the dispersion liquid A, and continuously stirring for 30 minutes to obtain a dispersion liquid B;
q3: adding the epoxy cross-linking agent in the weight ratio into the dispersion liquid B, and stirring for 15 minutes to obtain the high-elasticity pressure-sensitive adhesive for the reflective film;
wherein, the poly (methyl) acrylic acid copolymer comprises the following components in parts by weight:
4-8 parts of butadiene, namely butadiene,
20-30 parts of methyl acrylate,
50-65 parts of acrylic acid-2-ethyl ester,
8-14 parts of vinyl acetate, and the like,
0.8 to 1.5 parts of itaconic acid,
0.8 to 2.5 parts of tert-butyl peroxybenzoate,
200 to 320 parts of ethyl acetate,
50-80 parts of toluene,
the manufacturing method comprises the following steps:
s1: mixing and stirring butadiene, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene at room temperature to prepare a mixture I;
s2: mixing and stirring methyl acrylate, acrylic acid-2-ethyl ester, vinyl acetate, itaconic acid and tert-butyl peroxybenzoate according to the weight ratio to prepare a mixture II;
s3: taking 70% of the total weight of the tert-butyl peroxybenzoate, 50% of the total weight of the ethyl acetate and 50% of the total weight of the toluene, mixing and stirring to prepare a mixture III;
s4: putting the mixture I into a reaction container provided with a stirrer, a heater, a condenser and a nitrogen inlet pipe, opening the nitrogen inlet pipe and introducing nitrogen, and simultaneously opening the stirrer to stir the mixture I for 15-30 minutes;
s5: closing the nitrogen inlet pipe, stopping inputting nitrogen, opening the heater to increase the temperature in the reaction container, and keeping the reaction temperature in the reaction container and continuously reacting for 10-15 minutes when the temperature in the reaction container is increased to 100-120 ℃;
s6: dropping the mixture II into a reaction container, uniformly dropping the mixture II within 100-150 minutes, keeping the temperature in the reaction container after the dropping is finished, and continuously reacting for 120-180 minutes;
s7: dropping the mixture III into the reaction container, uniformly dropping the mixture in 40-90 minutes, keeping the temperature in the reaction container after the dropping is finished, and continuously reacting for 180-240 minutes;
s8: reducing the temperature in the reaction vessel, stopping the machine and pouring out when the temperature in the reaction vessel is reduced to 40 ℃ to obtain the poly (methyl) acrylic acid copolymer.
2. The method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film according to claim 1, wherein the method comprises the following steps: the poly (meth) acrylic acid copolymer has reactive amino groups and carboxyl groups, and has a weight average molecular weight of 80 to 130 ten thousand g/mol.
3. The method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film according to claim 1, wherein the method comprises the following steps: the poly (meth) acrylic acid copolymer has an acid value of 6 to 50 mgKOH/mol.
4. The method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film according to claim 1, wherein the method comprises the following steps: the poly (meth) acrylic acid copolymer has a glass transition temperature of-55 to-40 ℃.
5. The method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film according to claim 1, wherein the method comprises the following steps: the reactive liquid nitrile butadiene rubber has a glass transition temperature of-65 to-35 ℃.
6. The method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film according to claim 1, wherein the method comprises the following steps: the reactive liquid nitrile rubbers have terminal carboxyl or amino reactive groups.
7. The method for manufacturing the high-elasticity pressure-sensitive adhesive for the reflective film according to claim 1, wherein the method comprises the following steps: the epoxy cross-linking agent is one or a mixture of two of the following chemical structures,
wherein R1 is alkyl or cycloalkyl or aromatic hydrocarbon, R2 is hydrogen or C2-C7 alkyl group.
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| CN106147661A (en) * | 2015-05-12 | 2016-11-23 | 德莎欧洲公司 | Pressure-sensitive adhesive |
| CN106893534A (en) * | 2017-03-02 | 2017-06-27 | 浙江龙游道明光学有限公司 | For road sign reflective membrane hot soarfing from pressure sensitive adhesive and preparation method thereof |
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| CN102559101B (en) * | 2011-12-07 | 2014-01-01 | 新丰杰力电工材料有限公司 | Thermal-spalling acrylic ester pressure-sensitive adhesive, adhesive tape and preparation method thereof |
| JP2013147541A (en) * | 2012-01-17 | 2013-08-01 | Nitto Denko Corp | Polymer for adhesive, adhesive composition and heat-peelable adhesive sheet |
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| CN106147661A (en) * | 2015-05-12 | 2016-11-23 | 德莎欧洲公司 | Pressure-sensitive adhesive |
| CN106893534A (en) * | 2017-03-02 | 2017-06-27 | 浙江龙游道明光学有限公司 | For road sign reflective membrane hot soarfing from pressure sensitive adhesive and preparation method thereof |
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