TW538091B - Electroconductive resin composition - Google Patents

Abstract

A conductive polythiol-based epoxy resin composition which is improved in pot life and storage stability as compared with conventional polythiol-based epoxy resin compositions is disclosed. The conductive resin composition comprises as essential components (1) an epoxy resin having two or more epoxy groups per molecule, (2) a polythiol compound having two or more thiol groups per molecule, (3) a latent curing accelerator of the solid dispersion type, (4) a boric ester compound, and (5) conductive particles. It is suitable for use as a conductive material in a wide range of fields, including the field of electronics, where low-temperature rapid-setting properties are required.

Description

538091 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to a polythiol which has conductivity, low-temperature rapid curing, good storage stability, heat resistance, and moisture resistance. It is a one-liquid epoxy resin composition, which is widely used in the field of electronic materials as a circuit connection composition. In the prior art, an epoxy resin composition composed of polythiol as a hardener and a tertiary amine as a hardening accelerator can exhibit rapid hardening at low temperatures of 〇c ~-20 ° C. Especially in winter, it can be used as an important adhesive, sealant and casting. However, after the epoxy resin composition is generally mixed with the ingredients during the adaptation period, it can not achieve the shortcomings of mixing, defoaming, and coating operations within a very short time of seconds to hours. In addition, the operator must adjust its composition and composition appropriately. Therefore, the workability is poor, and the remaining unused composition cannot be stored. Therefore, it is not necessary to dispose of it after hardening, which is not ideal for resource conservation or environmental protection. Japanese Unexamined Patent Publication No. 0 6-2 1 1 9 6 9 and Japanese Unexamined Patent Application No. 06-2 1 19 7 0 contain a solid dispersion-type amine group-based latent hardening accelerator or an isocyanate group. A compound that reacts with a compound having at least one primary and / or secondary amine group in the molecule as an example of a polythiol epoxy resin composition composed of a hardening accelerator, which can improve the use time However, the storage stability of the complex is insufficient, and the low-temperature fast-curing property peculiar to the polythiol-based epoxy resin composition is also insufficient. Japanese Unexamined Patent Publication No. 10 — 2 9 8 5 2 6 proposes a circuit consisting of epoxy resin, polythiol, latent hardener, and conductive particles. This paper is sized to the Chinese National Standard (CNS) A4. (210 X 297 mm)

-4T ^ 1 1 ^ 1 ^ 1 ^ 1 11 ^ 1 ϋ ϋ «ϋ ϋ I > ^ 1 ϋ ^ 1 ^ 1 ^ 1 n I ϋ n ϋ ϋ ϋ ϋ II ϋ Β ^ ·· ϋ ^ 1 ϋ ΙΒ .1 I (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 538091 A7 ______ B7 V. Description of the invention (2) Continuing the composition, but the Stability is insufficient. An object of the present invention is to provide a polythiol-based one-liquid epoxy composition having good storage stability and conductivity. In order to solve the above problems, the present inventors have found out that after (1) epoxy resin, (2) adding a polythiol compound having two or more thiol groups as a hardener in the molecule (3) A solid dispersion-type latent hardening accelerator as a hardening accelerator, (4) Borate compounds and (5) conductive particles can obtain conductivity, heat resistance, humidity resistance and storage stability One of the good liquid polythiol-based epoxy resin compositions further completes the present invention. That is, the present invention is based on (1) an epoxy resin containing two or more epoxy groups in a molecule, (2) a thiol compound having two or more thiol groups in a molecule, and (3) a solid dispersion-type latent hardening Accelerators, (4) borate compounds and (5) conductive particles as the epoxy resin composition with the necessary components. The epoxy resin used in the present invention is only required to have two or more epoxy groups per molecule. For example: Polyglycidyl ether obtained by reacting polyphenols such as bisphenol A, bisphenol F, bisphenol AD, isophenol, resorcinol, polyvalent alcohols such as glycerol, and polyethylene glycol with epichlorohydrin. ; Glycidyl ether ester is obtained after the interaction of hydroxycarboxylic acids similar to p-hydroxybenzoic acid, Θ-hydroxynaphthoic acid and epichlorohydrin; polycarboxylic acids similar to phthalic acid and terephthalic acid and epichlorohydrin Polyglycidyl ester obtained by mutual reaction; more phenolic resin for epoxidized phenol paint, phenolic resin for epoxidized cresol paint, epoxidized polyolefin, cycloaliphatic epoxy resin, other urethane-modified epoxy paper Standards are applicable to China National Standard (CNS) A4 (210 X 297 mm) -5- ---------- 馥! · 丨 Order --------- Line -------------- ^ ---- r ----- (Please read the phonetic on the back? Matters before filling in this Page) 538091 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) Resin and other examples are not limited to this. As the polythiol compound used in the present invention, from the standpoint of preservation stability, it is preferable to use the least amount of salt-containing impurities, such as trimethylolpropane tri (thioglycolate), pentaerythritol tetra ( Thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tri (/ 3-thiopropionate), pentaerythritol tetra (/ 3-thiopropionate), dipentaerythritol poly (/ 5-thiopropionate) and other polythiol compounds obtained after the esterification reaction with a hydrogenthio organic acid do not require the use of a salt-based substance in the manufacture. Examples of polythiol compounds. Also by 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanethiol, etc. alkyl polythiol compounds; polyethers containing terminal thiol groups; containing Polythioether with terminal thiol group; polythiol compound obtained after reaction of epoxy compound and hydrogen sulfide; polythiol compound with terminal thiol group obtained after reaction between polythioether compound and epoxy compound, and its manufacture In engineering, it is necessary to use a salt-based substance as a reaction catalyst_ After dealkaliization treatment, the alkali metal ion concentration is 50 ppm or less, and the polymer has 2 or more thiol groups in the molecule after the II production Use thiol compounds. By using an average of one molecule of epoxy with two or more epoxy groups, the purpose is to form a $ 3 dimension polymer with a polythiol compound having two or more thiol groups in the molecule. In theory, the reaction of the thiol group with the epoxy group is 1 pair i ^, but after the hardening test is actually performed, the thiol group is at least slightly hardened. The relative mixing ratio of cyclopeptide and thiol compound is based on the ratio of S Η equivalent 4 of thiol compound / epoxy equivalent ratio of epoxy resin to 0.5 ~ 1 · 5. ^ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)） ϋ-^ 1 ϋ ϋ I ϋ ϋ ϋ I —β ϋ One-port, I ϋ I i_i I ϋ ϋ IIII ϋ ϋ ϋ ϋ ϋ I ϋ ϋ ^ 1. ^ 1 _ (Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 538091 A7 B7 V. Description of the invention (4) Thiol group / epoxy When the group is less than 0.5, the hardening is insufficient. On the other hand, when the group is more than 1.5, the hardening reaction is caused by the residual hardener remaining unhardened. Therefore, if it is out of the above range, the function of the hardened material will not meet the purpose of the present invention, and it will be unsatisfactory. The solid dispersion-type latent hardening accelerator used in the present invention refers to a solid that is insoluble in epoxy resin at room temperature and is made into a functional compound that is an accelerator after being dissolved after heating. A solid imidazole compound at room temperature. Solid dispersion type amine-based addition type latent hardening accelerator, for example: reaction product of amine compound and epoxy compound (amine-epoxy addition system), reaction product of amine compound and isocyanate compound or amine compound and Examples of reaction products of urea compounds (urea-type addition system). The compounding amount of the solid dispersion type latent hardening accelerator varies depending on the type and the type of the epoxy resin to be compounded. Usually, when 100 parts by weight of the epoxy resin is used, 1 to 60 parts by weight is appropriate. The representative examples of the above-mentioned solid dispersion-type addition-based latent hardening accelerators are listed below, but they are not limited thereto. For example: "Amicuia PN-23", "Amicuia PN-H", "AmicuiaMY-24" as the amine-epoxy addition system, "Amicuia MY-24" trade name, Ajinomoto (share) system), "Hardona-X-3361S "(Trade name, A.C, R (share) system), Hardona-X-3670S" (trade name, A · C.R (share) system) "nobacuia HX-3742", "nobacuia HX-372 1" (Product name, Asahi Kasei (share) system) and other examples, such as urea type addition system "fujicuia FXE-1000", "fujicuia FXR-1 030" (trade name, Fuji Chemicals (stock) system) and other examples. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- m il! 丨 Order --------- Line 丨 ^- ------------- ^ ---- K ----- (Please read the note 2 on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 538091 A7 ------- B7 V. Explanation of the invention (5) In the present invention, the preservation stability of the polyol epoxy composition is improved, and the sequence of a boric acid ester compound which is an important function of liquefaction is unknown, and Capsules can be modified after reacting with the surface of a potential hardening accelerator. Representative examples of borate compounds are: trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, Tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, three Lauryl borate, trihexyl decyl borate, trioctyl decyl borate, tris (2-ethylhexyloxy) boron, bis (1, 4, 7, 1.0—tetraoxadecyl) (1 , 4,7,10,13 —pentaoxatetradecyl) (1,4,7-trioxundecyl) boron, tribenzyl borate, triphenyl borate, tris-o-monomethyl Examples of boronic acid esters, tri-m-toluene boronic acid esters, and triethanolamine boronic acid esters. As a method for adding such borate compounds, in addition to blending with various components such as epoxy resin, polythiol compound, and solid dispersion type latent hardening accelerator, it is also possible to mix the solid dispersion type latent hardening accelerator in advance. Place it after the agent. The mixing method can be carried out by contacting both in a solvent such as methyl ethyl ketone, toluene, or the like, in a solvent-free or liquid epoxy resin. The boronic acid ester compound is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin. If it is less than 0.1 parts by weight, the stability during the pot life is poor, and the effect is insufficient. Further, if it is more than 20 parts by weight, hardening is not satisfactory. Examples of the conductive particles used in the present invention include metal particles such as gold, silver, copper, nickel, solder, and carbon, which can be used alone or in combination. In consideration of electrical conductivity, humidity resistance, heat resistance, storage stability, the Chinese National Standard (CNS) A4 specification (210 χ 297 mm) is applied to this paper scale. -8- ------------ --------- Order --------- Line Win (Please read the notes on the back before filling this page)

-ϋ i ^ i n · 1 ϋ I 538091 A7 B7 V. Description of the invention (6) Nickel powder is the most ideal one. In addition, the particles may be coated on the surface with a periodical filling material or plastic as a core. The average particle diameter of the conductive particles measured by the micro-guiding method is from 0 · 1 to 2 0 // m in terms of workability, dispersibility and conductivity. The addition amount of the conductive particles is 100 parts by weight (1) to (4) when the resin composition is a combination of 100 to 1 OO 0 parts by weight, preferably 2 0 0 ~ 500 parts by weight are preferred because of workability and conductivity. If it is less than 100 parts by weight, the conductivity will be insufficient. On the other hand, if it is more than 100 parts by weight, the workability will be poor. It is possible to add fillers, diluents, and solvents to the epoxy resin composition of the present invention if necessary. , Pigments, flexible adhesives, coupling agents, oxidation inhibitors, thixotropic adhesives, dispersants and other additives. [Best Embodiment of the Invention] Hereinafter, the present invention will be described in more detail with reference to examples. The evaluation method is as follows. Storage stability (applicable period): Measure the number of days until the fluidity of the conductive resin composition stored in a 25 t thermostatic bath disappears. Volume antagonistic rate: After coating a conductive resin composition on a PET (polyethylene terephthalate) film, the thickness is about 50 mm // width 3 mm, length 150 mm, and then hardened at 80 ° C for 30 minutes Measured at 2 5 ° C. This paper is sized for Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page.) Printed by the Intellectual Property Bureau Employee Consumer Cooperatives- y-

-0 ϋ n I 一》 0,. ^ 1 · _1 I · ϋ ϋ -ϋ II. ^ 1 n ϋ ϋ «ϋ II n. ^ 1 ϋ ϋ ϋ I ϋ. ^ 1 ϋ. ^ 1 ϋ I ϋ I 538091 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (7) Determine the volume antagonistic rate. Humidity resistance test: Put the hardened material prepared by the above method in a 60 ° C, 90% constant temperature and humidity tank, and then evaluate the change in volume antagonistic rate over time. Heat resistance test: After the hardened material prepared by the above method is placed in a constant temperature air tank at 100 ° C, the change in volume antagonistic rate over time is evaluated. Example 1 To 100 parts by weight of bisphenol A type epoxy resin "EP-8 2 8" (trade name, made by Petrochemical Shell epoxi (stock)) was added 6 parts by weight of tributyl boric acid, followed by stirring and mixing. . Add 10 parts by weight of "Amicma PN-23" (trade name, Ajinomoto (manufactured by Ajinomoto)), which is a solid dispersion-type latent hardening accelerator, and mix thoroughly. After adding 7 5 parts by weight of pentaerythritol tetrathiopropionate "E Η 3 1 7" (trade name, Adecahandona manufactured by Asahi Denka Kogyo Co., Ltd.) as a polythiol compound, a universal mixer was used for sufficient vacuum. After mixing, a resin composition is prepared. For this 100 parts by weight of the resin composition, 400 parts by weight of nickel powder (average particle size: 3 · 5 // m) as conductive particles were mixed and used as a conductive resin composition for evaluation. Thing. Example 2 1 0 0 parts by weight of bisphenol A epoxy resin "EP-8 2 8" (trade name, petrochemical shell epoxi (shares)) added 6 parts by weight of this paper standard applicable Chinese national standards (CNS ) A4 size (210 X 297 mm), " " I— ϋ «ϋ ί ϋ ι ^ 1 II 0 ^ 1 ϋ ^ 1 ^ 1 ι ϋ ϋ One: ον ι ^ 1 ^ 1 ^ 1 I ϋ II ammmm IH -ϋ II ϋ «I ϋ I n I ϋ II -ϋ III ϋ ϋ ϋ I (Please read the note on the back? Matters before filling out this page) 538091 A7 _ B7 V. Description of the invention (8) Triethyl After boric acid is mixed. Furthermore, 10 parts by weight of "fujicuia FXE 1000" (trade name, manufactured by Fuji Chemical Industry Co., Ltd.) as a solid dispersion-type latent hardening accelerator was added. Furthermore, 75 parts by weight of trimethylolpropane tris (/ 3-thiopropionate) "TM TP" (trade name, manufactured by Yodo Chemical Co., Ltd.), which is a polythiol compound, was added and the mixture was fully performed with a universal mixer. After the vacuum mixing, a resin composition was prepared. To this 100 parts by weight of the resin composition, 400 parts by weight of nickel powder (average particle size: 3 · 5 // m) as conductive particles was added and mixed to prepare a conductive resin composition for evaluation. Example 3 To 100 parts by weight of bisphenol AF-type epoxy resin "ZX-1059" (trade name, manufactured by Tohto Kasei Co., Ltd.) was added 6 parts by weight of triethylboronic acid and mixed thoroughly. Add 15 parts by weight of "Anucuia PN-23" (trade name, manufactured by Ajinomoto (Shares)) as a solid dispersion-type latent hardening accelerator and mix thoroughly. In addition, 80 parts by weight of trimethylolpropane tri (Θ-thiopropionate "T M T P" (trade name, manufactured by Yodo Chemical Co., Ltd.) as a polythiol compound was added as a polythiol compound, and the vacuum was sufficiently performed with a universal mixer. After mixing, a resin composition is prepared. 400 parts by weight of nickel powder (average particle size: 3 · 5 // m) as conductive particles is added to 100 parts by weight of the resin composition, and the mixture is prepared. Conductive resin composition for evaluation. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -I ϋ · 一 δν-^ 1 1 · ϋ I i_i ϋ ϋ l —.1 1 ϋ ϋ ϋ H ϋ ϋ ^ 1 n ϋ · ϋ. 538091 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (9) Example 4 To 100 parts by weight of bisphenol A type epoxy resin "EP-8 2 8" (trade name, manufactured by Petrochemical Shell epoxi) was added 6 parts by weight of tributyl borate to charge Parts are mixed. Then add 15 parts by weight for solid dispersion-type latent hardening promotion "Amicuia PN-23" (trade name: Ajinomoto (shares)) is fully mixed. Add 80 parts by weight of trihydroxypropane tri (/ 3 -thiopropionic acid) as a polythiol compound. Esters) "TM TP" (trade name, manufactured by Yodo Chemical Co., Ltd.) After fully vacuum mixing with a universal mixer, a resin composition is prepared. 100 parts by weight of this resin composition is added as conductive particles. Nickel powder (average particle size: 3 · 5 // m), silver powder (average particle size: 7 · 0 // m), copper powder (average particle size: 1 5 // m), and carbon black (average particle size: 1 // m) were separately added and mixed in an amount of 400 parts by weight to prepare a conductive resin composition for evaluation. Comparative Example 1 Conduction for evaluation was conducted in the same manner as in Example 1 except that borate was not mixed. Resin composition. Comparative Example 2 A conductive resin composition for modulation and evaluation was prepared in the same manner as in Example 1 except that the polythiol was not mixed. The results are shown in Table 1. This paper is sized to the Chinese National Standard (CNS) A4 size m〇X 297 mm) (Please read the notes on the back before filling this page)

538091 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-------- Order · --------. (Please read the notes on the back before filling out this page) 5. Description of the invention (10) Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Volume Antagonism 10'3 10'3 10'3 10'3 Non-determinable humidity resistance 600 1〇-3 10'3 Ι03 Heat resistance 600 1〇-2 10 02 10_2 1 2 · 2 after 10'3 hours After 25 hours at 25 ° C, apply 1 month to 1 month to 1 month to 2 hours and 1 month. The above examples 1 to 3 have an initial volume antagonism of 10 to 3. Heat resistance test and humidity resistance test It remains at 10-2 after 600 hours. Also, those who are stable after being stored at 25 ° C for more than one month. On the other hand, Comparative Example 1 in which no borate was added was a case where the comparative example was completely hardened 2 hours after preparation. In addition, Comparative Example 2 in which no polythiol was added had an initial volume antagonism too low to be measured. Table 2 shows the results obtained when the conductive particles were changed according to Example 4. 538091 A7 B7 V. Description of the invention (11) Table 2 Volume of Ni powder, Ag powder, Cu powder, carbon black, antagonistic 10.3 101 10.3, 2 ~ 3 After 600 hours of humidity resistance, 10 · 2 10'1 must not be applied at 25 ° C The period of 1 month or more, 10 days, 7 days, 14 days, as the nickel powder as the conductive particles, the initial volume antagonism is 10 ^ 3, and the moisture resistance test will remain 10-2 after 600 hours. However, the initial volume of the silver powder was large, and the copper powder had a significant decrease after its moisture resistance test. Carbon black was also significantly reduced in volume antagonism after 600 hours and could not be measured. [Industrial Applicability] The present invention can provide a conductive resin composition having a long pot life and improved storage stability. The volume antagonism rate of this resin composition after heating and hardening is 10 to 3, and the heat resistance test and humidity resistance test are still maintained after 600 hours. Therefore, the resin composition is the same as the prior art polythiol epoxy resin composition. After comparison, the present invention not only improves workability, but also saves resources and is extremely useful. At the same time, it is more suitable for low-temperature quick-hardening electrical fields and even conductive materials in all fields. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative ϋ 一 1 1 tT I. ^ 1 · ϋ ϋ -1 I line ------------ I — ----.----- -Ί4-

Claims (1)

53809 ^ Α8 Β8 C8 D8 6. Scope of patent application1. A conductive resin composition characterized by (1) an epoxy resin with two or more epoxy groups in the molecule, and (2) two or more in the molecule. A thiol-based polythiol compound, (3) a solid dispersion-type latent hardening accelerator, (4) a borate compound, and (5) conductive particles are required components. 2. The conductive resin composition according to item 1 of the scope of patent application, wherein the mixing ratio of (1) epoxy resin and (2) polythiol compound is greater than S S equivalent number of polythiol compound / epoxy resin Epoxy equivalent ratio is 0.5 to 1.5, and (1) 100 parts by weight of epoxy resin is added (3) solid dispersion type latent hardening accelerator is 1 to 60 parts by weight, (4) The borate compound is a composition composed of 0.1 to 20 parts by weight and 4 components of (1) to (4) and 100 to 100 parts by weight of conductive particles. The accomplished. 3. The conductive resin composition according to any one of the items 1 to 2 of the scope of patent application, wherein the conductive particles are nickel powder. (Please read the precautions on the back before filling out this page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) Α4 specification (210 X 297 mm)