Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
  • C08G59/4253—Rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L13/00—Compositions of rubbers containing carboxyl groups
• • 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
  • C09J7/10—Adhesives in the form of films or foils without carriers
• • 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

Definitions

• the present invention relates to an epoxy resin composition, an adhesive film and an adhesive tape with excellent storage stability under room temperature which are used in athermal process of electrical and electronic materials.
• Heat-curing epoxy resins are widely used because of their excellent chemical resistance, very excellent thermal and dynamic properties, and high electrical insulation. Further, the epoxy resin exhibits excellent adhesion against many substrates, and is very suitable to be used as an adhesive material through a thermal process of electrical and electronic materials.
• the curing of the epoxy resin is performed according to various mechanisms.
• the curing using amine is performed in addition to the curing using phenol or anhydride.
• These materials are generally liquid and very well mixed with the epoxy resin. Accordingly, due to high reactivity and very low latency, such a type of epoxy resin composition is made of two components. This means that a resin (component A) and a curing agent (component B) are separated and stored and mixed at an accurate ratio immediately before use.
• the “latency” means that a mixture of the respective components is stable under a prescribed storage condition.
• Such a 2-component resin formulation is also referred to as a cold-curing resin formulation and the curing agent used for this is generally selected from the group consisting of amine or aminoamine.
• a 1-component heat-curing epoxy resin formulation is completely prepared in advance and immediately usable, and that is, the epoxy resin and the curing agent are mixed in a use field. Therefore, a mistake when mixing each component during use in the field is excluded. To this end, it is required to have a latent curing agent system that does not react (may be stored) with the epoxy resin at room temperature, but completely reacts with the epoxy resin immediately when heated by energy input.
• Patent Document 1 Korean Patent Publication No. 10-2014-0009246 Summary
• an object of the present invention is to provide an adhesive composition, an adhesive fdm, and an adhesive tape capable of exhibiting high performance by solving the problems in the related art.
• a solution to be solved by the present invention is to provide a curing polymer resin, particularly an epoxy resin composition that may be used in electrical and electronic materials.
• the present invention provides a epoxy resin composition
• a epoxy resin composition comprising: 100 parts by weight of a non-halogen epoxy resin; 5 to 20 parts by weight of a liquid type cyanamide-based heat-curing agent; 150 to 300 parts by weight of a thermoplastic rubber resin solution; and 0.01 to 0.5 parts by weight of a curing accelerator.
• the heat-curing agent may include a compound of Chemical Formula 1 below.
• the non-halogen epoxy resin may include at least one of cresol novolak type epoxy or a bisphenol A type epoxy.
• the thermoplastic rubber resin may be a carboxylic group-modified acrylic rubber and the carboxylic group-modified acrylic rubber may contain 0.05 to 4 wt% of the carboxyl group.
• the epoxy resin composition may be an electrical and electronic material with excellent storage stability under room temperature.
• the present invention may be an adhesive film comprising the epoxy resin composition and further, may be an adhesive tape comprising the adhesive film.
• the viscosity of the adhesive composition may be 50 to 2,000 cp.
• the adhesive composition is coated on a release film to form an adhesive layer, and the release film is laminated on the adhesive layer, wherein the heat resistance of the adhesive composition after curing may be 340°C to 380°C.
• the adhesive composition and the adhesive tape of the present invention is not tacky in early stage to have an excellent positioning property on an adhered surface, and is cured at a relatively low temperature of 150°C or less to have heat resistance of 300°C or higher while exhibiting excellent adhesion.
• the adhesive tape in the semi-cured state has excellent adhesion and heat resistance even under a long-term storage under room temerapure other than the storage at a low temperature of - 18°C
• th easiness of storage and usage may be greatly increased, and accordingly, costs caused by product storage/transport can be reduced.
• the adhesive composition of the present invention and the adhesive tape including the same can be variously applied in fields requiring storage stability under room temperature, such as adhering and manufacturing of electrical devices.
• Respective features of embodiments of the present invention can be partially or entirely connected or combined with each other, and can be technically interlocked or driven variously.
• an adhesive composition comprising a non-halogen epoxy resin, a heat-curing agent, a curing accelerator and a thermoplastic rubber resin.
• the non-halogen epoxy resin used herein is not particularly limited, and may contain silicon, urethane, polyimide, polyamide, etc., and may contain atoms except for halogen such as phosphorus, sulfur, nitrogen, in the structure.
• examples of the epoxy resin applicable to the present invention may use a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, or an epoxy resin with hydrogen added thereto, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc., preferably, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak-type epoxy resin.
• cresol novolak-type epoxy resin with excellent reactivity with a heat-curing agent and high adhesive and high temperature heat resistance may be used, and may be used with bisphenol A-type epoxy to impart flexibility, initial tacky, and higher adhesion.
• the heat-curing agent used herein is required to combine their advantages without adoption of disadvantages of known amine curing agents and known dicyandiamid powder curing agents such as low latency or filtration of particles.
• the curing agent needs to have sufficiently high latency at a temperature of 15°C to 30°C, to entirely enable the crosslinking of the epoxy resin, to be dissolved or completely mixed in the epoxy resin, and to be suitable for an adhesive film coating film.
• the heat-curing agent used herein is preferably a liquid type cyanamide-based heat-curing agent.
• cyanamide or dicyandiamide may be used.
• the heat-curing agent may consist of cyanamide or dicyandiamide and a urea deviative.
• the urea deviative may be at least one selected from the group consisting of 1,1 -dimethyl urea, 3-(3-chloro-4-methylphenyl)-l,l-dimethyl urea, 3-(p-chlorophenyl)-l,l-dimethyl urea, 3 -phenyl- 1,1 -dim ethyl urea, 3 -(3 ,4-dichlorophenyl)- 1,1 -dimethyl urea, 1,1’- (methylene di-p-phenylene)-bis-(3 ,3 -dimethylurea), 3 -(3 -trifluoromethylphenyl)- 1,1- dimethyl urea, l,l’-(2-methyl-m-phenylene)-bis-(3,3-dimethylurea) and/or l,l’-(4-methyl- m-phenylene)-bis-(3, 3 -dimethyl urea).
• the cyanamide-based heat-curing agent of the present invention is preferably a liquid type heat-curing agent.
• the liquid type curing agent has sufficiently high latency at a temperature of of 15 °C to 30°C, needs to entirely enable the crosslinking of the epoxy resin, and may be dissolved or completely mixed in the epoxy resin.
• a tape manufactured by an epoxy composition prepared by adding the liquid heat-curing agent is much more excellent in adhesion at room temperature and adhesion under high temperature and high humid conditions than a tape manufactured by an epoxy composition prepared by adding a general solid type heat-curing agent.
• the present invention comprises dicyandiaimide represented by the following Chemical Formula 1 .
• liquid type dicyandiamide having a product name of DYHARD FLUID VP 184 by Alzchem Trostberg GmbH and 24 parts by weight of a solid may be used.
• the heat-curing agent may be mixed in an amount of 5 to 20 parts by weight based on 100 parts by weight of the epoxy resin. At this time, when the curing agent for the epoxy resin is less than 5 parts by weight, there is a problem that the non-halgen epoxy resin is not sufficiently cured, and when the curing agent for the epoxy resin is more than 20 parts by weight, it is not preferred in that there is a problem that the amount is excess to cure the non-halgen epoxy resin so that the adhesion is reduced, and when the non-halgen epoxy resin is not sufficiently cured, the heat resistance is not sufficient.
• the curing accelerator used herein may accelerate the reaction between the non- halogen epoxy resin and the curing agent for the epoxy resin by lowering a reaction temperature during reaction and quickens the reaction at the same temperature and time dumg curing as compared with an adhesive composition without applying the curing accelerator to increase the crosslinking density, so that a network structure of poly(meth)acrylate ester is densified to improve the heat resistance. Further, after the adhesive composition is cured, the adhesive composition may have a more minute network structure and larger stress when an adhesive layer is peeled, so that the peeling strength may be improved.
• an ethylisocyanate compound such as 2-methylimidazole, 2-ethyl-4 methylimidazole, 2- phenylimidazole, 2-phenyl-4-methylimidazole, and 2-phenyl-4-methyl-5- hydroxymethylimadazole, triphenylphosphine, and the like may be used alone or two or more thereof may be used in combination.
• 2- methylimidazole is faster in reaction rate than other curing accelerators, has no side group such as a phenyl or ethyl group to have no stereoscopic disorder in reaction, therey further accelerating the curing reaction.
• the curing accelerator may be contained in 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the non-halogen epoxy resin, and when the content is 0.01 parts by weight, a dense network structure cannot be formed, and thus, there is a problem that the heat resistance of the adhesive composition is deteriorated. Further, when the content is more than 0.5 parts by weight, an excessively dense network structure is formed, and as a result, it is not preferred in that there are problems that the peeling strength is lowered, the storage stability under room temperature of the adhesive tape is decreased due to high reactivity.
• thermoplastic rubber resin used herein a urethane resin, a polyester resin, a methacrylic acid resin, an acrylic acid ester resin, a carboxylic group-modified acrylic rubber, etc. are included, and it is preferred to use a carboxyl group-containing acrylonitrile butadiene rubber.
• the carboxyl group-containing acrylic rubber has elasticity as a rubber-based resin and imparts an effect of satisfying flexibility and high peeling strength to the adhesive by forming a curing reaction with epoxy
• the carboxyl group-containing acrylonitrile butadiene rubber uses preferably CTBN, and for example, includes PNR-1H (JSR Co.) and Nippol 1072 (ZEON Co.).
• thermoplastic resin is in a solid state and usable after being dissolved in a polar solvent such as methyl ethyl ketone for addition to the adhesive composition of the present invention, and exists in a liquid state in which the thermoplastic rubber resin is dissolved in the solvent.
• the solid may be used about 15% to 35% of the solution, and a generally commercially available solid may be used in 26.5%. It is preferred that the content of the thermoplastic resin is cotained in 150 parts by weight to 300 parts by weight with respect to 100 part by weight of an epoxy basic resin based on the solid content.
• the peeling perperty from the base film is too low, and when the content is more than 300 parts by weight, it is not preferable because the high peeling sttengh is shown, but the surface of the adhesive is too tacky, and the heat resistance after heat-curing through a thermal compression process is lowered.
• an adhesive film formed from the adhesive composition.
• the adhesive film has low tacky and low adhesion before a thermal compression process, but has high adhesion and thermal stability through the thermal compression process.
• the adhesive film according to an embodiment is an adhesive film including a reaction product of a base epoxy resin, a heat-curing agent, a thermoplastic rubber resin, and a curing reaction accelerator.
• the adhesive film is curable through the thermal compression process, curable at a lower temperature due to the curing reaction accelerator, and has excellent flexibility as compared with other heat-curing resin compositions due to the a thermoplastic rubber resin.
• an adhesive tape including a base film; and an adhesive film disposed on one surface of the base film.
• the adhesive film included in the adhesive tape according to the embodiment has the same composition and properties as the adhesive film of an embodiment as described above.
• the adhesive tape may be provided as a single-sided adhesive tape having only the one adhesive film as an adhesive layer, or as an inorganic material type adhesive tape without the base film.
• the adhesive layer added in the inorganic material adhesive tape may include the adhesive composition of an embodiment as described above.
• Materials suitable for the base film may include, for example, paper including both flat or smooth paper and textured paper such as crepe paper, natural or synthetic polymer films, natural and/or synthetic fibers and nonwoven fabrics prepared from combinations thereof, fiber reinforced polymer films, fiber or yam reinforced polymer films or nonwoven fabrics, and a multi-layer laminated structure.
• a type of release film used for the adhesive tape is not particularly limited, but may be, for example, at least one selected from the group consisting of a polyester (PET) film, a polyethylene (PE) film, a polypropylene (PP) film, and paper. Further, the release film may include a silicone coating layer on a surface in contact with the adhesive film. The thickness of the release film may be 5 pm and 100 pm, but may be thinner or thicker as necessary.
• an epoxy resin as a non-halogen epoxy resin, a carboxyl group-containign acrylonitrile butadiene rubber solution dissolved with 26.5 wt% of a solid weight in a polar solvent, liquid type dicyandiamide as an epoxy curing agent, and a solid type curing accelerator were added in a polar solvent such as methyl ethyle ketone and stirred until the solid type curing accelerator was fully dissolved to obtain an adhesive composition.
• the components and contents of respective materials in the final composition were as follows (in Tables below, the numerical values in parentheses were parts by weight of a solid for each component converted based on 100 parts by weight of the solid of the epoxy resin, and the solid of each adhesive composition obtained by stirring with the solvent was fixed to 35 parts by weight).
• the order and conditions for mixing a base polymer, a curing resin, a crosslinking agent, and an initiator in the preparation of the adhesive composition are not particularly limited, and the process may be suitably modified if necessary.
• the viscosity may be adjusted by using a solvent in each mixing step.
• the preparation method of the adhesive composition is not particularly limited, and the process conditions may be appropriately modified if necessary.
• o-cresol novolac type epoxy Kukdo Chemical Co., Ltd., product name_KDCP130EK80, 80 parts by weight of solid
• Bisphenol A type epoxy Kukdo Chemical Co., Ltd, product name_YD128, 100 parts by weight of solid
• Liquid type DICY liquid type dicyandiamide: AlzChem Trostberg GmbH, product name DYHARD FLUID VP 184, 24 parts by weight of solid
• 2-methylimidazole CHEMHUD CO., LTD., product name_2MI, 100 parts by weight of solid - CTBN Solution (Carboxylic Terminated Butadiene Acrylonitrile rubber solution in MEK): CHEMHUD CO., LTD., product name_UH-1072, 26.5wt% of solid Test Examples
• An adhesive composition was coated on a 120 pm -thick release base fdm at a rate of about 2 m/min.
• the coated fdm was dried in a total 6 m of oven having three drying zones (at temperatures of 50°C, 80°C, and 120°C, respectively) having lengths of 2 m.
• a tape having a 10 pm -thick adhesive layer formed on the release base fdm was obtained, and a 25 pm-thick release PET film was laminated on the surface of the adhesive layer to prevent unnecessary contamination before the test.
• a release fdm on an adhesive fdm was removed, and the adhesive fdm was laminated between a stainless steel (SUS304) specimen and a polyimide fdm and then thermally fused and pressed for 30 minutes under conditions of 60 kgf/mm 3 at 140°C to prepare a bonding specimen.
• SUS304 stainless steel
• the adhesion (unit: Kgf/in) was measured.
• the adhesion was measured after the adhesive tape was stored at 22°C and 50% RH for 20 minutes, and the adhesion was measured after the adhesive tape was stored at 85°C and 85% RH for 5 days, respectively.
• a sample was cut to a width of 1 inch and used, and the adhesion test was repeated three times to obtain an average value.
• the glass transition temperature of the adhesive tape may be measured using a difference scanning calorimetry (DSC).
• DSC difference scanning calorimetry
• a release film on an adhesive film was removed, and the adhesive film was laminated between a stainless steel (SUS304) specimen and a polyimide film and then thermally pressed for 30 minutes under conditions of 60 kgf/mm 3 at 140°C to prepare a bonding specimen.
• a sample was made in a size of 5 cm x 5 cm on a hot plate at a high temperature and in contact with a hot plate surface of the stainless steel surface for 60 sec for each temperature, and whether bubbles occurred between the stainless steel and the polyimide film was confirmed, and then temperatures at which the bubbles did not occur were represented.
• An adhestive tape was stored at 22°C and 50% RH, and then a release film on an adhesive film was removed at an interval of 5 days, and the adhesive film was laminated between a stainless steel (SUS304) specimen and a polyimide film and then thermally fused and pressed for 30 minutes under conditions of 60 kgf/mm 3 at 140°C to prepare a bonding specimen.
• SUS304 stainless steel
• the adhesion (unit: Kgf/in) was mesaured to prepare the adhesive tape, and then as compared to a result measured within 1 day, a storage day at which the adhesion out of an error range of ⁇ 10% was measured was represented as a date capable of storage under room temperature.
• tapes prepared with different compositions were poor in terms of at least one property of the adhesion, the heat resistance, and the storage stability under room temperature.
• Comparative Examples 1 and 3 it was confirmed that a curing agent having high storage stability under room temperature of raw materials of the adhesive composition was used, but the adhesion and the heat resistance were low due to a relative low thermal compression process condition.
• Comparative Examples 4 to 7 it can be confirmed that the storage stability under room temperature was lowered or the heat resistance was not sufficient according to the content of the liquid type heatcuring agent.

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• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)

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Citations (4)

• 2020
  • 2020-12-30 KR KR1020200187505A patent/KR20220095721A/ko unknown
• 2021
  • 2021-12-16 WO PCT/IB2021/061880 patent/WO2022144676A1/en active Application Filing

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