CN118742618A - Environmentally friendly adhesive resin manufactured using a low-carbon emission process, adhesive composition comprising the same, and adhesive layer formed using the same - Google Patents

Abstract

The present invention relates to a method of manufacturing an environmentally friendly adhesive resin using a low carbon emission process, an adhesive resin manufactured thereby, an adhesive composition including the adhesive resin, and an adhesive layer formed using the same. In the present invention, a core-shell structured gum binder resin is produced using an amphiphilic polymer and a hydrophobic monomer. When the production method of the present invention is used, the amount of carbon emissions can be reduced as compared with the conventional process, and the viscosity of the binder resin can be smoothly reduced even with a small amount of solvent. In addition, when the present invention is used, energy consumed in drying the adhesive layer can be reduced, and an environmentally friendly adhesive layer excellent in adhesive force and heat resistance can be formed.

Description

Environmentally friendly adhesive resin manufactured using a low-carbon emission process, adhesive composition including the same, and adhesive layer formed using the same

Technical Field

The present invention relates to an environmentally friendly adhesive resin manufactured using a low-carbon emission process, an adhesive composition comprising the same, and an adhesive layer formed using the same. More specifically, it relates to a method for manufacturing an environmentally friendly adhesive resin using a low-carbon emission process, which can reduce greenhouse gas emissions by using a smaller amount of solvent than in the prior art, the adhesive resin manufactured thereby, an adhesive composition comprising the adhesive resin, and an adhesive layer formed using the same.

Background Art

In recent years, due to the seriousness of environmental pollution and climate change, the international community has been comprehensively discussing solutions to reduce carbon emissions. In response to this, the United Nations Intergovernmental Panel on Climate Change (IPCC) proposed a route to reduce carbon dioxide emissions by at least 45% compared to 2010 by 2030 at the 48th IPCC General Meeting in 2018. This carbon emission issue is also a big topic in chemical-based fields such as adhesives, so the focus on low-carbon manufacturing processes and products continues to increase.

Adhesives are generally composed of components such as resins manufactured by polymerizing monomers on solvents, solvents, and curing agents. In the manufacturing process of adhesives, a large amount of solvent is used for resin polymerization and viscosity adjustment, and the temperature for polymerization and adhesive layer formation needs to be adjusted. For this reason, when manufacturing adhesives, a considerable amount of energy is consumed in heating and drying, which has become a cause of carbon emissions. Therefore, it is necessary to develop a technology for reducing carbon emissions in the adhesive manufacturing process.

On the one hand, the existing environmentally friendly adhesive manufacturing technology is to exclude the use of highly harmful solvents (e.g., toluene) as described in the Republic of Korea Publication Patent Gazette No. 10-2012-0051596, or to develop in the direction of manufacturing a water-based adhesive dispersed in water as proposed in the Republic of Korea Granted Patent Gazette No. 10-1115681. However, the above technology is used to reduce the harmfulness of the adhesive itself without realizing the purpose of reducing carbon emissions in the manufacturing process such as heating and drying, and is therefore limited.

As described above, a technology for reducing the amount of carbon emitted in the adhesive manufacturing process has not yet been developed, and in order to respond to measures such as carbon emission regulations, it is urgently necessary to develop a low-carbonization process.

Summary of the invention

Technical issues

The object of the present invention is to provide a method for producing an environmentally friendly binder resin with excellent physical properties by using a low carbon emission process.

Another object of the present invention is to provide an environmentally friendly adhesive resin produced by the method.

Another object of the present invention is to provide an adhesive composition comprising the environmentally friendly adhesive resin.

Another object of the present invention is to provide an adhesive layer manufactured using the environmentally friendly adhesive resin.

Technical Solution

In order to achieve the above object, the present invention provides a method for producing an environmentally friendly adhesive resin, which comprises: (i) polymerizing a hydrophilic monomer and a hydrophobic monomer to produce an amphiphilic polymer; and (ii) adding a hydrophobic monomer to the amphiphilic polymer to react to produce a colloidal adhesive resin comprising a core and a shell, wherein the core comprises the hydrophobic monomer and the shell comprises the amphiphilic polymer.

It may be that in the step (i), the weight ratio of the hydrophilic monomer to the hydrophobic monomer is 1:1 to 1:15.

In the step (i), the hydrophilic monomer may include one or more monomers having one or more functional groups selected from the group consisting of a carboxyl group, a hydroxyl group, an amine and an ether in the molecule.

The hydrophobic monomers in the steps (i) and (ii) may each independently include at least one monomer selected from the group consisting of vinyl ester monomers and alkyl (meth)acrylate monomers.

In the step (ii), 20 parts by weight or less of a hydrophilic monomer may be further added to 100 parts by weight of the hydrophobic monomer added to the amphiphilic polymer.

The total weight of the monomers used in the step (ii) may be 200 to 500 parts by weight relative to 100 parts by weight of the total weight of the monomers used in the step (i).

The reactions of step (i) and step (ii) may be carried out in a solvent.

In the step (i), 50 to 200 parts by weight of the solvent may be used based on 100 parts by weight of the total weight of the monomers.

In the step (ii), 10 to 150 parts by weight of the solvent may be used based on 100 parts by weight of the total weight of the monomers.

Preferably, the boiling point of the solvent used in the reaction in step (i) and step (ii) is 80° C. or lower.

The solvents used in the reactions of step (i) and step (ii) may be each independently a mixed solvent comprising ethyl acetate and one or more cosolvents.

The reactions of step (i) and step (ii) may be carried out using a polymerization initiator.

In addition, the present invention provides an environmentally friendly binder resin produced by the method.

In addition, the present invention provides an environmentally friendly adhesive composition comprising the environmentally friendly adhesive resin and a curing agent.

In the present invention, the curing agent may be contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the binder resin.

Alternatively, in the present invention, the adhesive composition may further include a coating solvent.

In the present invention, the coating solvent may be contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the binder resin.

In addition, the present invention provides an environmentally friendly adhesive layer formed using the environmentally friendly adhesive resin.

In the present invention, the adhesive layer may have a thickness of 5 to 500 μm.

Effects of the Invention

The adhesive resin manufacturing method of the present invention uses less solvent than the existing process, and when the resin is diluted with a solvent for coating the adhesive, the viscosity can be smoothly reduced with a small amount of solvent. In addition, the resin can be manufactured using a low boiling point solvent, thereby saving the time consumed when drying the adhesive layer, and the adhesive manufactured using the present invention shows excellent adhesion and heat resistance compared to the adhesive manufactured using the existing process. Therefore, when the present invention is used, an adhesive with excellent physical properties can be manufactured through an environmentally friendly process that greatly reduces carbon emissions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram schematically showing a process for producing an environmentally friendly binder resin according to one embodiment of the present invention.

DETAILED DESCRIPTION

The specific implementation forms of the present invention are further described in detail below. Unless otherwise defined, all technical and scientific terms used in this specification have the same meanings as those commonly understood by professionals skilled in the art to which the present invention belongs. Generally, the nomenclature used in this specification uses conventional nomenclature known in the art.

The invention relates to a method for manufacturing an environmentally friendly adhesive resin by using a low-carbon emission process.

The adhesive resin of the present invention has high concentration and excellent productivity, and when diluted with a solvent for coating, the viscosity can be smoothly reduced by using a small amount of solvent. Thus, the amount of solvent used can be reduced, and the content of solvent per unit area is low during coating, thereby saving energy used for solvent volatilization. In addition, when a low boiling point solvent is used, the drying temperature can be reduced, thereby further reducing energy consumption. In addition, when the adhesive resin of the present invention is used, an adhesive layer (tape, film, etc.) with excellent adhesion and heat resistance can be manufactured.

The present invention is characterized in that a core-shell structured colloid binder resin is produced by using an amphiphilic polymer and a hydrophobic monomer.

Specifically, the method for producing an environmentally friendly adhesive resin of the present invention includes: (i) polymerizing a hydrophilic monomer and a hydrophobic monomer to produce an amphiphilic polymer; and (ii) adding a hydrophobic monomer to the amphiphilic polymer to react to produce a colloidal adhesive resin comprising a core and a shell, wherein the core comprises a hydrophobic monomer and the shell comprises an amphiphilic polymer.

Fig. 1 is a diagram schematically illustrating a binder resin manufacturing method of the present invention. With reference to Fig. 1, when a relatively hydrophobic monomer is put into an amphiphilic polymer that is harvested by polymerizing a hydrophilic monomer and a hydrophobic monomer, the amphiphilic polymer substance and the hydrophobic monomer are in a mixed state. In this state, when reacting, the amphiphilic polymer and the hydrophobic monomer begin to form a core-shell structure, and micelles are formed by forming the amphiphilic polymer of the shell. While the molecular weight increases due to the further polymerization of the hydrophobic monomer, the hydrophobic monomer is located inside the micelle, thereby polymerizing. Thus, a colloid binder resin of a core-shell structure is manufactured.

In the step (i), the hydrophilic monomer may include one or more monomers having one or more functional groups such as carboxyl group, hydroxyl group, amine and ether in the molecule.

Specifically, as the hydrophilic monomer, acrylic acid (AA), methacrylic acid (MAA), β-carboxyethyl acrylate (β-CEA), itaconic acid, umaric acid, maleic acid, 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl acrylate (2-HPA), 2-hydroxypropyl methacrylate (2-HPMA), 4-hydroxybutyl acrylate (4-HBA), polyethylene glycol mono (meth) acrylate (polyethylene glycolmono (meth) acrylate), acryloyl morpholine (ACMO), 2-(dimethylamino)ethyl (meth) acrylate (2-(dimethylamino)ethyl methacrylate (DMAE(M)A), polyethylene glycol monomethyl ether (meth)acrylate (MPEG(M)A), 2-(2-ethoxyethoxy)ethyl (meth)acrylate (EOEOE(M)A) and the like.

In the step (i), the hydrophobic monomer may be a monomer having a water solubility (based on 20°C) of 5 g/100 mL or less, and may include one or more monomers such as vinyl ester monomers and alkyl (meth) acrylate monomers, and may preferably include one or more monomers such as vinyl ester monomers and alkyl (meth) acrylate monomers having a carbon number of 4 to 24.

For example, as the hydrophobic monomer, one or more monomers such as vinyl acetate (VA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), lauryl methacrylate (LMA), cyclohexyl methacrylate (CHMA), isooctyl acrylate (iso-octyl acrylate), stearyl acrylate, and vinyl 2-ethylhexanoate can be used.

In the step (i), the hydrophilic monomer and the hydrophobic monomer may be mixed in a weight ratio of 1:1 to 1:15, preferably 1:2.5 to 1:12. Within the above range, an amphiphilic polymer suitable for subsequent processes may be formed by polymerization of the hydrophilic monomer and the hydrophobic monomer.

In the step (i), the hydrophilic monomer and the hydrophobic monomer may react on a solvent and disperse into the solvent after the reaction. As the solvent, organic solvents such as esters, ketones, and alcohols may be used, preferably a low boiling point solvent having a boiling point of 80°C or less. As the low boiling point solvent, one or more solvents such as ethyl acetate (boiling point 77.1°C), ethanol (boiling point 78.4°C), acetone (boiling point 56.0°C), methanol (boiling point 64.7°C), and methylethyl ketone (boiling point 79.6°C) may be used.

In the present invention, when it is desired to recycle and reuse the solvent, ethyl acetate can be used alone as the solvent, or two mixed solvents can be used in which a cosolvent such as acetone or ethanol is mixed with the ethyl acetate. By using the cosolvent, the reaction temperature can be lowered and the amount of expensive ethyl acetate used can be reduced. As described above, when two mixed solvents are used, ethyl acetate and the cosolvent can be used in a weight ratio of 5:5 to 9:1, preferably 6:4 to 8:2.

The solvent may be used in an amount of 50 to 200 parts by weight, specifically 80 to 150 parts by weight, based on 100 parts by weight of the total monomers used in the step (i).

In the step (i), a polymerization initiator may be added for polymerization of the hydrophilic monomer and the hydrophobic monomer. The polymerization initiator generates free radicals, thereby inducing a cross-linking reaction.

The polymerization initiator is an additive that initiates polymerization of monomers by heat or light. A thermal polymerization initiator or a photopolymerization initiator may be used, and a thermal polymerization initiator may be preferably used.

For example, in the present invention, as a polymerization initiator, one or more initiators can be used, such as azo initiators such as 2,2-azobisisobutyronitrile, 2,2-azobis-2-methylbutyronitrile, and 2,2-azobis-2,4-dimethylvaleronitrile; peroxyester initiators such as dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis-4-tert-butylcyclohexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; and peroxydicarbonate compounds such as tert-butyl peroxydimethylhydroxyneodecanoate, pentyl peroxyneodecanoate, and tert-butyl peroxyneodecanoate.

The polymerization initiator may be used in an amount of 0.05 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total monomers used in step (i).

In step (i), the monomers are reacted to form an amphiphilic polymer. For example, when a thermal polymerization initiator is used, the reaction mixture may be heated to initiate the polymerization reaction. Specifically, the reaction temperature may be raised to 50 to 100° C., preferably 70 to 90° C., and the polymerization may be completed by maintaining the reaction for 10 to 90 minutes, preferably 15 to 60 minutes.

According to the step (i), the hydrophilic monomer and the hydrophobic monomer are polymerized to obtain an amphiphilic polymer in which the hydrophilic part and the hydrophobic part coexist in one molecule.

Next, a hydrophobic monomer is added to the produced amphiphilic polymer to cause a reaction, thereby producing a colloid binder resin.

Examples of the types of hydrophobic monomers that can be used in step (ii) include the monomers described in the description of step (i). The hydrophobic monomer added in step (ii) may be the same as or different from the hydrophobic monomer used in the production of the amphiphilic polymer in step (i).

When the hydrophobic monomer is added, due to the difference in properties between the hydrophobic monomer and the amphiphilic polymer, the hydrophobic monomer is located inside the amphiphilic polymer while forming the core. Thus, a colloid-shaped adhesive resin including a core and a shell is manufactured, wherein the core includes the hydrophobic monomer and the shell includes the amphiphilic polymer. The adhesive resin is a non-aqueous dispersion (NAD) polymer phase, and through the formation of this NAD polymer phase, a high-concentration adhesive with relatively low viscosity can be manufactured, and the amount and content of solvent used can be reduced in the adhesive layer manufacturing process without reducing physical properties, thereby saving the energy consumed in the volatilization of solvent per unit area.

The weight of the hydrophobic monomer added in the step (ii) may be 180 to 500 parts by weight, specifically 230 to 450 parts by weight, based on 100 parts by weight of the monomer used in the production of the amphiphilic polymer in the step (i).

In the step (ii), a small amount of hydrophilic monomer may be added. Examples of the types of hydrophilic monomers that can be used in the step (ii) include the monomers described in the description of the step (i). The hydrophilic monomer added in the step (ii) may be the same as or different from the hydrophilic monomer used in the preparation of the amphiphilic polymer in the step (i).

The hydrophilic monomer may be added in an amount of 20 parts by weight or less relative to 100 parts by weight of the hydrophobic monomer added in step (ii), and may preferably be added in an amount of 0.1 to 10 parts by weight, and more preferably in an amount of 0.2 to 5 parts by weight. Within the above range, the viscosity can be more easily reduced by applying a solvent, and an adhesive resin having excellent adhesive strength of the tape can be manufactured. According to the above aspects, it is further preferred that the hydrophilic monomer be added in an amount of 0.5 to 3 parts by weight relative to 100 parts by weight of the hydrophobic monomer.

The total weight of the monomers used in the step (ii) may be 200 to 500 parts by weight, preferably 250 to 450 parts by weight, based on 100 parts by weight of the total weight of the monomers used in the step (i).

In the step (ii), a solvent and a polymerization initiator may be further added to cause a reaction. Examples of the types of solvents and polymerization initiators that can be used in the step (ii) include the monomers described in the description of the step (i), and the solvent and polymerization initiator used in the step (ii) may be the same as or different from those used in the step (i).

The solvent may be added in an amount of 10 to 150 parts by weight, specifically 20 to 100 parts by weight, relative to 100 parts by weight of the total monomers added in step (ii). The polymerization initiator may be added in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the total monomers added in step (ii).

After mixing the monomer mixture, in order to completely react the unreacted monomers, a solvent and a polymerization initiator may be further added, and the solvent and the polymerization initiator may be added in an amount ranging from 1 to 20 parts by weight and 0.05 to 3 parts by weight, respectively, relative to a total of 100 parts by weight of the monomers added in step (ii).

In order to adjust the non-volatile matter (NVM) of the manufactured binder resin, a process of further adding a solvent etc. can be further performed. The non-volatile matter (solid content) of the finally manufactured binder resin can be 50 to 70% by weight, specifically 60% by weight, and at this time, the viscosity can be 2000 to 10000 cPs, preferably 2000 to 8000 cPs.

The total weight of the solvent may be 30 to 100 parts by weight, preferably 50 to 80 parts by weight, relative to 100 parts by weight of the total monomers used in the process for producing the binder resin of the present invention (i.e., the overall process including step (i) and step (ii)). According to the present invention, a binder resin having excellent physical properties can be produced while using a small amount of solvent compared to the monomers used.

Specifically, according to the general manufacturing process of the binder resin, when the amount of solvent is reduced in the manufacturing process in order to adjust the non-volatile matter to 45% by weight or more, there are disadvantages that the binder resin cannot be obtained due to gelation of the monomer in the middle of the reaction, or when the non-volatile matter is 60% by weight, the viscosity exceeds 1000 cPs, and a very large amount of coating solvent is required in the subsequent process. On the contrary, when the process of the present invention is used, the non-volatile matter can be adjusted to 50% by weight or more under the condition of a viscosity of 2000 to 10000 cPs, preferably a viscosity of 3000 to 8000 cPs, and the viscosity can be adjusted to a suitable coating viscosity in the coating process with a small amount of solvent.

Therefore, when the present invention is used, the amount of organic solvent used can be saved. In particular, when a low boiling point solvent is used, the reaction can proceed smoothly, thereby significantly reducing the amount of greenhouse gas emitted in the adhesive manufacturing process.

The reaction of step (ii) is terminated by the method, thereby manufacturing a colloid-shaped adhesive resin including a core and a shell, wherein the core includes a hydrophobic monomer and the shell includes an amphiphilic polymer. When the present invention is used, a high-concentration adhesive resin can be manufactured using a low-carbon emission process, so the productivity of the resin is excellent. In addition, the adhesive resin of the present invention is high-concentration, and even so, in the subsequent process, the viscosity can be easily reduced using a small amount of solvent, so the amount of solvent required in the coating and the energy consumed in the volatilization of the solvent after the coating are low, and when the adhesive resin of the present invention is used, an environmentally friendly adhesive with excellent adhesion and heat resistance can be manufactured.

In addition, the present invention provides an environmentally friendly adhesive composition including the environmentally friendly adhesive resin.

The adhesive composition of the present invention includes the adhesive resin produced according to the present invention and a curing agent.

In the present invention, as the curing agent, a multifunctional curing agent used in the adhesive composition can be used, for example, one or more curing agents selected from the group consisting of isocyanate compounds, epoxy compounds, aziridine compounds and metal chelate compounds.

Specifically, as the curing agent, diphenylmethane-4,4'-diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,3-diisocyanatomethylcyclohexane, tetramethylxylene isocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylene diisocyanate adduct of trimethylolpropane, toluene diisocyanate adduct of trimethylolpropane, hexamethylene diisocyanate adduct of trimethylolpropane, toluene diisocyanate isocyanurate (TDI isocyanurate), hexamethylene diisocyanate isocyanurate (HDI isocyanurate) can be used. isocyanurate), isophorone diisocyanate isocyanurate (IPDIisocyanurate), etc.; ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine, N,N,N',N'-tetraglycidyl xylenediamine, glycerol diglycidyl ether, etc.; aziridine compounds such as N,N'-toluene-2,4-bis(1-aziridineamide), N,N'-diphenylmethane-4,4'-bis(1-aziridineamide), triethylenemelamine, bisisophthaloyl 1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, etc.; one or more compounds such as metal chelate compounds in which polyvalent metals such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and/or vanadium are coordinated to acetylacetone or ethylacetoacetic acid.

The curing agent may be used in an amount of 0.01 to 5 parts by weight, specifically 0.05 to 1 part by weight, based on 100 parts by weight of the binder resin. Within the above range, the adhesive force and other physical properties can be appropriately adjusted.

The adhesive composition of the present invention may further include a solvent for viscosity adjustment for coating. In order to distinguish the solvent used in the adhesive composition from the solvent of the adhesive resin when describing the present invention, the solvent of the composition is referred to as a "coating solvent".

In the present invention, as the coating solvent included in the adhesive composition, organic solvents such as esters, ketones, and alcohols can be used. In particular, when a low boiling point solvent with a boiling point of 80°C or less is used as the coating solvent, the adhesive can be dried even at a low temperature in the subsequent process, so it is preferred. As the low boiling point solvent, one or more solvents such as ethyl acetate, ethanol, acetone, and methanol can be used.

The coating solvent may be used in an amount of 5 to 40 parts by weight, preferably 8 to 30 parts by weight, and more preferably 10 to 25 parts by weight, based on 100 parts by weight of the binder resin.

By adding the coating solvent, the viscosity of the adhesive composition can be adjusted to 500 to 3000 cPs, preferably 1000 to 2000 cPs, thereby exhibiting coating properties suitable for forming an adhesive layer.

In the case of a general binder resin, a considerable amount of coating solvent needs to be added to obtain a viscosity suitable for coating. On the contrary, the binder resin of the present invention has a high viscosity characteristic and smoothly reduces the viscosity when a coating solvent is added. Therefore, according to the present invention, the coating property of the binder is excellent even when a small amount of coating solvent is mixed, and the amount of energy consumed in the volatilization of the coating solvent is small.

In addition, the adhesive composition of the present invention may further include one or more adhesive agents, crosslinking catalysts, silane coupling agents and other additives used to adjust the physical properties of the adhesive. The additives may be used in an amount that does not affect the effects of the invention, for example, 0.0001 to 50 parts by weight relative to 100 parts by weight of the non-volatile matter of the adhesive resin.

The present invention also provides an environmentally friendly adhesive layer formed using the adhesive resin. The adhesive layer is a layer formed by applying and drying the adhesive composition and can be used in various forms such as adhesive tapes and adhesive films.

The adhesive layer is formed by applying the adhesive composition of the present invention to a substrate. The thickness of the adhesive layer can be adjusted according to the intended use, for example, in the range of 5 to 500 μm, preferably in the range of 10 to 200 μm.

The substrate forming the adhesive layer can be selected according to the use form such as tape substrate, release film, adherend, etc. In addition, as the substrate, a material on which the adhesive composition can be applied, such as a substrate of polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, polyurethane, etc., can be used. Among them, when polyethylene terephthalate is used as a rigid material, it can play a buffering role by absorbing impact, so it is preferred.

The adhesive composition may be applied by various coating methods used in the adhesive coating field, such as comma coating, blade coating, rod coating, gravure coating, slot die coating, spin coating, etc. In particular, when a roll-to-roll process is used, comma coating, gravure coating, slot die coating, etc. may be performed, so that even if a low-carbon emission process is applied, production efficiency can be improved.

After applying the adhesive composition, it can be dried at a temperature of 60 to 150° C., preferably 80 to 120° C., and more preferably 85 to 110° C. to produce an adhesive layer. The drying process can be performed for 30 to 240 seconds, preferably 60 to 120 seconds, and specifically 90 to 150 seconds.

After the drying process, a aging process at 30 to 60° C. may be performed, and the aging time may be adjusted to about 12 to 60 hours.

When the present invention is used, when forming an adhesive layer, coating can be easily performed even with a low boiling point solvent, so the drying temperature can be set to 120° C. or less, preferably 110° C. or less, for example 100° C., and the manufactured adhesive layer exhibits excellent adhesive force and heat resistance. In addition, since the amount of solvent used in the adhesive manufacturing process is small and the time consumed in volatilization is short, the production efficiency is excellent, and the adhesive can be manufactured by an environmentally friendly process with low carbon emissions.

Example

The present invention will be described in further detail below by way of examples. However, these examples are provided to illustrate some experimental methods and structures for the purpose of illustrating the present invention, and the scope of the present invention is not limited to these examples.

Production Example 1: Production of Binder Resin

Example: Production of acrylic adhesive resin using non-aqueous dispersion

In order to produce the binder resin, a reaction flask having a stirrer, a reflux cooler, a thermometer and a dropping funnel was prepared.

After the monomer mixture A was added to the reaction device, 9.6 g of ethanol and 18.4 g of ethyl acetate were added to the mixture, and 0.1 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator. After the addition, the temperature was raised to 80° C. to initiate the reaction, and the reaction was maintained for 30 minutes to form an amphiphilic polymer.

Next, the monomer mixture B was added to the monomer dropping funnel, and 10.4 g of ethanol, 17.6 g of ethyl acetate and 0.4 g of polymerization initiator AIBN were mixed and added to the initiator dropping funnel, and the dropping was performed simultaneously for 90 minutes. After the dropping was completed, the reaction was maintained for 60 minutes, and 10 g of ethyl acetate and 0.3 g of polymerization initiator AIBN were poured into the initiator dropping funnel, and the mixture was dripped for 30 minutes to completely react the unreacted monomers. After the reaction, the mixture was cooled, and the non-volatile matter (NVM) was adjusted to 60% level with ethyl acetate, and the reaction was terminated.

As the reaction proceeds, it is observed that the amphiphilic polymer and the relatively hydrophobic monomer are converted into core-shell keratin particles, and the transparent solution gradually turns milky white.

The monomer components used in the experiment and the physical properties of the synthesized adhesive are shown in the following Table 1. The viscosity was measured at 25°C according to ASTM D2196.

【Table 1】

Comparative Example: Production of acrylic adhesive resin by general solution polymerization

The same reaction apparatus as in the manufacturing example was prepared, and 30 g (30 wt%) of the monomer mixture C was added to the reaction apparatus, and then 15 g of ethanol and 30 g of ethyl acetate were added to the mixture, and 0.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator. After the addition, the temperature was raised to 80° C. to initiate the reaction, and the reaction was maintained for 30 minutes.

Next, 70 g (70 wt%) of monomer mixture C, 21.5 g of ethyl acetate and 0.3 g of polymerization initiator AIBN were dripped for 90 minutes. After the dripping was completed, the reaction was maintained for 60 minutes, and after 33 g of ethyl acetate and 0.5 g of polymerization initiator AIBN were dripped for 60 minutes, the reaction was maintained for 30 minutes, and then after the reaction was terminated, the non-volatile matter (NVM) was adjusted with ethyl acetate. It is intended to adjust the non-volatile matter to a level of 50 to 60% by reducing the amount of solvent. However, when the amount of solvent is reduced, the final product cannot be obtained due to the gelation of the monomers in the middle of the reaction, so a polymerizable amount of solvent is added to produce a resin.

The monomer components used in the experiment and the physical properties of the synthesized adhesive are shown in the following Table 2. The viscosity was measured at 25°C according to ASTM D2196.

【Table 2】

Experimental Example 1: Measurement of viscosity changes with various solvent addition amounts

When the coating is comma-shaped, the viscosity is measured with the amount of solvent dilution in order to adjust to 1000 to 2000 cPs, which is the appropriate coating viscosity. For 100 g of the binder resin harvested in the examples and comparative examples, the viscosity change is measured while adding ethyl acetate. When it is confirmed that the viscosity drops to about 1000 cPs, the solvent is no longer added and the experiment is terminated. The viscosity change measurement results are shown in Tables 3 and 4.

【Table 3】

【Table 4】

Referring to the experimental results, it is found that the adhesive of the present invention has a high solid content and can adjust the viscosity to less than 2000 cPs using 15 to 20 g of solvent. That is, it can be confirmed that since a small amount of solvent is used in the adhesive of the present invention compared to general adhesives, carbon emissions are small, and less energy is consumed in the volatilization of the solvent when forming the adhesive layer.

On the contrary, when the adhesive of the comparative example was manufactured using a general process, the solid content itself was low and the solvent contained in the adhesive was large. Even so, at least 25 g of solvent was required when diluting the adhesive to adjust the viscosity of the adhesive. Therefore, it can be confirmed that the adhesive resin of the comparative example not only used a large amount of solvent in the manufacturing process, but also consumed more energy for volatilizing the solvent per unit area when manufacturing the adhesive layer.

From the experimental results, it was confirmed that when the binder resin of the present invention produced by a low-carbon emission process is used, the amount of organic solvent required for coating can be reduced.

Manufacturing Example 2: Manufacturing of Adhesive Tape

In order to perform comma coating, 0.5 g of a curing agent (aekyung chemical AK-75) and ethyl acetate were added to 100 g of the adhesive resin of Manufacturing Example 1 to prepare an adhesive composition. When ethyl acetate was added for adjusting the coating viscosity, 20 g was added to the adhesive resin of the example, and 30 g was added to the adhesive resin of the comparative example.

To produce the adhesive tape, a 25 μm thick adhesive layer was formed using a comma coater, a 25 μm thick PET film was used as a release film, and a 50 μm thick PET film was used as a base film.

After coating the adhesive layer, a drying process was performed at 100° C. for 120 seconds and then aged at 43° C. for 48 hours, thereby manufacturing an adhesive tape.

Experimental Example 2: Comparison of Physical Properties of Adhesive Tapes

With respect to the adhesive tape of Production Example 2, adhesive strength and heat resistance were measured.

Adhesion was measured using a UTM device in accordance with KS T 1028. A 25 mm wide tape was pressed onto a SUS304 adherend using a 2.0 kg rubber roller, and then left at room temperature for 30 minutes, and the 180° peel value was measured at a speed of 300 mm/min.

For heat resistance, a sample of 25 x 150 mm was made, and after pressing SUS at 25 x 25 mm under a weight of 2.0 kg, it was left at room temperature for 30 minutes. Then, a weight of 500 g was applied, and the temperature was raised by 10°C every 10 minutes at 50°C, and the temperature was recorded when it was detached.

The room-temperature adhesion and heat resistance of the adhesive tapes measured by the experiment are shown in Table 5 below.

【Table 5】

The experimental results show that the adhesive resin produced by the method of the present invention tends to have a similar or higher adhesive strength of the tape than the adhesive resin produced by the general solution polymerization method using the same monomer, and also has excellent heat resistance.

From this result, it can be confirmed that when the low carbon emission process of the present invention is applied to the adhesive tape manufacturing process to utilize an adhesive composition with a high non-volatile content, a small amount of solvent is used compared to existing products, thereby being able to produce an adhesive with reduced carbon emissions while having better physical properties such as adhesion and heat resistance.

The above describes a part of the implementation forms of the present invention. However, the present invention is not limited to the above-mentioned implementation forms and can be modified and deformed within the scope of the gist of the present invention. Such modifications and deformations also fall within the technical concept of the present invention.

Claims (19)

1. A method of making an environmentally friendly binder resin comprising:

(i) A step of polymerizing a hydrophilic monomer and a hydrophobic monomer to produce an amphiphilic polymer; and

(Ii) A step of manufacturing a colloidal binder resin including a core and a shell by adding a hydrophobic monomer to the amphiphilic polymer to react, wherein the core includes the hydrophobic monomer and the shell includes the amphiphilic polymer.

2. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

In the step (i) of the above,

The weight ratio of hydrophilic monomer to hydrophobic monomer is 1:1 to 1:15.

3. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

In the step (i) of the above,

The hydrophilic monomer includes 1 or more hydrophilic monomers having 1 or more functional groups selected from the group consisting of carboxyl groups, hydroxyl groups, amines, and ethers in the molecule.

4. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

The hydrophobic monomers of the steps (i) and (ii) each independently include 1 or more hydrophobic monomers selected from the group consisting of vinyl ester monomers and alkyl (meth) acrylate monomers.

5. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

In the step (ii) of the process,

Further, 20 parts by weight or less of a hydrophilic monomer is added to 100 parts by weight of a hydrophobic monomer added to an amphiphilic polymer.

6. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

The total weight of the monomers used in the step (ii) is 200 to 500 parts by weight relative to 100 parts by weight of the total weight of the monomers used in the step (i).

7. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

The reaction of step (i) and step (ii) is carried out in a solvent.

8. The method for producing an environmentally friendly adhesive resin as claimed in claim 7, wherein,

In the step (i) of the above,

50 To 200 parts by weight of a solvent are used relative to 100 parts by weight of the total monomer weight.

9. The method for producing an environmentally friendly adhesive resin as claimed in claim 7, wherein,

In the step (ii) of the process,

10 To 150 parts by weight of a solvent are used relative to 100 parts by weight of the total monomer weight.

10. The method for producing an environmentally friendly adhesive resin as claimed in claim 7, wherein,

The boiling point of the solvent is below 80 ℃.

11. The method for producing an environmentally friendly adhesive resin as claimed in claim 7, wherein,

The solvents of the step (i) and the step (ii) are each independently a mixed solvent comprising ethyl acetate and 1 or more co-solvents.

12. The method for producing an environmentally friendly adhesive resin as claimed in claim 1, wherein,

The reaction of the step (i) and the step (ii) is performed using a polymerization initiator.

13. An environmentally friendly binder resin made by the method of any one of claims 1 to 12.

14. An environmentally friendly adhesive composition comprising the environmentally friendly adhesive resin of claim 13 and a curing agent.

15. The environmentally friendly adhesive composition according to claim 14, wherein,

The curing agent is contained in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the binder resin.

16. The environmentally friendly adhesive composition according to claim 14, wherein,

The adhesive composition further includes a coating solvent.

17. The environmentally friendly adhesive composition according to claim 16, wherein,

The coating solvent is contained in an amount of 5 to 40 parts by weight relative to 100 parts by weight of the binder resin.

18. An environmentally friendly adhesive layer formed using the environmentally friendly adhesive resin of claim 13.

19. The environmentally friendly adhesive layer as claimed in claim 18, wherein,

The thickness of the adhesive layer is 5 to 500 μm.