KR20210131380A - Conductive composition and conductive adhesive - Google Patents

Abstract

(식 중, R₁은 탄소수 1 내지 6의 알킬렌기이고, R₂는 수소 원자 또는 메틸기이고, R₃ 및 R₄는 각각 독립적으로 수소 원자 또는 메틸기이고, R₅는 수소 원자 또는 탄소수 1 내지 6의 알킬기이고, n은 1 내지 6이다.)의 화합물을 포함하는 도전성 조성물을 제공한다.This invention has high fluidity|liquidity and makes it a subject to provide the electrically conductive composition and electrically conductive adhesive which have electroconductivity. The present invention comprises (A) conductive particles, (B) a thermosetting resin, (C) a curing agent, and (D) the following formula (1):

(Wherein, R ₁ is an alkylene group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ is a hydrogen atom or a carbon number 1 to 6 of an alkyl group, and n is 1 to 6.) Provided is a conductive composition comprising the compound of

Description

Conductive composition and conductive adhesive

The present invention relates to a conductive composition, a conductive adhesive containing the same, and a camera module including a cured product of the conductive adhesive.

In electronic devices and electrical devices, it is necessary to fix minute electronic components such as camera modules and light emitting diodes (LEDs). Adhesives are used to fix minute electronic components. In recent years, there has been an increasing demand for injecting an adhesive into a gap of a smaller size for fixing microscopic electronic components.

On the other hand, the electrically conductive paste used for bonding of wiring or an electronic component is known. For example, in Patent Document 1, a conductive paste having low electrical resistance and suitable as a wiring material is an electrically conductive paste containing conductive particles, a binder resin, and a solvent dissolving the binder resin, and containing carbon nanotubes, the solvent A conductive paste containing a polyether-based solvent having a specific structure is described. Moreover, patent document 1 describes that this conductive composition can be apply|coated on a base material by the dispensing method.

Japanese Patent Laid-Open No. 2010-165594

In electronic devices and electrical devices, it is necessary to fix minute electronic components such as camera modules and light emitting diodes (LEDs). For example, when attaching a camera module to an apparatus, the method called an active alignment construction method is employ|adopted as a thing storing it using a bracket.

In the active alignment method, first, the position of the camera module with respect to the bracket is adjusted, and the camera module is fixed with respect to the bracket with the adhesive for temporary fixing. Specifically, the temporary fixing adhesive is introduced, the position of the camera module is adjusted to determine the position, and the temporary fixing adhesive is UV cured to fix the camera module at a predetermined position with respect to the bracket.

Next, the conductive paste is introduced to a height of about half of the gap between the camera module and the bracket. Since the conductivity between the camera module and the bracket can be obtained by introducing the conductive paste, the camera module can be grounded with respect to the bracket.

Finally, the gap between the camera module and the bracket is filled by introducing an adhesive for bracket peel to the remaining part of the gap between the camera module and the bracket, and finally the camera module is fixed. Since the dimension of the clearance gap between a camera module and a bracket is small, high fluidity|liquidity is required for the adhesive agent for bracket peeling.

In order to bond a camera module, there has been an increasing demand in recent years for injecting an adhesive into a gap having a smaller dimension. Conventionally, an adhesive for injecting into a small-sized gap has been limited to an insulating adhesive. Since the conductive adhesive contains a large amount of conductive fillers (eg, metal particles) for imparting conductivity, it has low fluidity and has not been used as an adhesive for injection into small-sized gaps.

On the other hand, in order to lower the manufacturing cost of an electronic device and an electrical device, it is necessary to mount an electronic component more simply. When the fluidity|liquidity of a conductive adhesive is high, in the active alignment method mentioned above, there is a possibility that an electrically conductive paste and the adhesive agent for bracket peels can be replaced with one type of conductive adhesive. That is, by using a conductive adhesive with high fluidity, there is a possibility that two steps of a step of grounding the camera module to the bracket and a step of finally fixing the camera module can be performed in one step, and the manufacturing cost is high. decline can be expected.

Then, an object of this invention is to provide the electrically conductive composition and electrically conductive adhesive which have high fluidity|liquidity and also electroconductivity.

Specific means for solving the above problems are as follows.

A first embodiment of the present invention is

(A) electroconductive particle, (B) thermosetting resin, (C) hardening|curing agent, and (D) following formula (1):

(Wherein, R ₁ is an alkylene group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ is a hydrogen atom or a carbon number 1 to 6 of an alkyl group, and n is 1 to 6.)

It is a conductive composition containing a compound of

A second embodiment of the present invention is a conductive adhesive comprising the conductive composition of the first embodiment.

3rd Embodiment of this invention is a camera module containing the hardened|cured material of the conductive adhesive of 2nd Embodiment.

According to the first embodiment of the present invention, a conductive composition having high fluidity and conductivity can be obtained. Further, according to the second embodiment of the present invention, a conductive adhesive having high fluidity and conductivity can be obtained. Further, according to the third embodiment of the present invention, it is possible to obtain a camera module fixed by using a conductive adhesive having high fluidity and conductivity.

1 is a schematic view of a jig for measuring the fluidity of a conductive composition as viewed from the side.
2 is a schematic view of a jig for measuring the fluidity of a conductive composition viewed from the top.
It is a schematic diagram which shows arrangement|positioning of the electrode for measuring the electrical resistance of a conductive composition, and a conductive composition.
It is a cross-sectional schematic diagram of an example of a jet dispensing apparatus (jet dispenser).

[Conductive composition]

The conductive composition which is 1st Embodiment of this invention is (A) electroconductive particle, (B) thermosetting resin, (C) hardening|curing agent, and (D) following formula (1):

(Wherein, R ₁ is an alkylene group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ is a hydrogen atom or a carbon number 1 to 6 of an alkyl group, and n is 1 to 6.)

and a compound represented by According to this embodiment, it is possible to obtain a conductive composition having high fluidity and conductivity.

(A) conductive particles

The conductive composition of this embodiment contains (A) electroconductive particle. (A) Although it does not restrict|limit especially as electroconductive particle, Electroconductive metal particle can be used. Examples of the metal of the metal particles may include silver (Ag), gold (Au), copper (Cu), nickel (Ni), palladium (Pd), platinum (Pt), tin (Sn), and alloys thereof. (A) Electroconductive particle may be used individually by 1 type of metal particle or alloy particle, and may use 2 or more types of metal particle or alloy particle together.

In this embodiment, it is preferable that (A) electroconductive particle is a silver particle or alloy particle containing silver, and it is more preferable that it is a silver particle. The electrical conductivity of silver is high compared to other metals. By using the silver particle as electroconductive particle, the electroconductive composition of higher electroconductivity can be obtained.

(A) The shape of electroconductive particle is not specifically limited, For example, it is possible to use spherical, granular, flake shape, or scale-like electroconductive particle. For example, by using spherical or granular electroconductive particle, the electroconductive composition of higher electroconductivity can be obtained.

(A) As for the average particle diameter of electroconductive particle, 0.1 micrometer - 50 micrometers are preferable, 0.1 micrometer - 10 micrometers are more preferable, More preferably, they are 0.1 micrometer - 7 micrometers, Most preferably, they are 0.1 micrometer - 5 micrometers. The average particle diameter here means the volume-based median diameter (d50) obtained by the laser diffraction scattering type particle size distribution measuring method.

(A) The manufacturing method of electroconductive particle is not specifically limited, For example, it can manufacture with the reduction method, the grinding|pulverization method, the electrolytic method, the atomizing method, the heat processing method, or a combination thereof. For example, it can manufacture with these manufacturing methods also about a silver particle. The flaky silver particles can be produced, for example, by crushing spherical or granular silver particles with a ball mill or the like.

(B) thermosetting resin

The conductive composition of this embodiment contains (B) thermosetting resin. (B) A thermosetting resin connects and fixes an adhesion|attachment object mutually, and also connects (A) electroconductive particle which is an inorganic material in an electrically conductive composition to each other.

(B) As the thermosetting resin, for example, epoxy resin, acrylic resin, urethane resin, vinyl ester resin, silicone resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, polyimide resin, etc. Can be used. These resins may be used independently and may mix and use 2 or more types.

It is preferable that the conductive composition of this embodiment contains at least one of an epoxy resin and an acrylic resin as (B) thermosetting resin. (B) When the thermosetting resin contains at least one of an epoxy resin and an acrylic resin, it is possible to more reliably fix the electronic component to be fixed.

It is preferable that the epoxy resin is liquid at room temperature (25°C±5°C). However, it is also possible to use a solid epoxy resin at room temperature by diluting it with a diluent or the like and making it liquid. Examples of the epoxy resin include bisphenol-type epoxy resins that are glycidyl ethers such as bisphenol A and bisphenol F: liquid glycidylamine such as diglycidylaniline, diglycidylorthotoluidine, and paraaminophenol-type epoxy resin type epoxy resin; (3',4'-epoxycyclohexane)methyl-3,4-epoxycyclohexylcarboxylate, 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4,1,0] alicyclic epoxy resins such as heptane; Hydrogenated epoxy resins such as 2,2-bis(4-hydroxycyclohexyl)propanediglycidyl ether, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyl A cyclohexane oligomer having an epoxy group such as disiloxane, a novolak-type epoxy resin, a naphthalene-type epoxy resin, or the like can be used. Any 1 type of epoxy resin mentioned above may be used for an epoxy resin, and may use 2 or more types together. From a viewpoint of storage stability, the bisphenol type epoxy resin which is glycidyl ether, such as bisphenol A and bisphenol F, is preferable.

It is preferable that the acrylic resin is liquid at room temperature (25°C±5°C). However, it is also possible to dilute the solid acrylic resin at room temperature with a diluent or the like and use it as a liquid. As a component used for a thermosetting acrylic resin, in consideration of ensuring heat resistance, a compound having two or more (meth)acryloyl groups is preferable, and a compound having two to six (meth)acryloyl groups is more preferable. and a compound having two (meth)acryloyl groups is more preferable. Further, in addition to the compound having two (meth)acryloyl groups, a compound having one (meth)acryloyl group may be used for adjusting the viscosity or physical properties of the cured product (adhesive strength, flexibility, etc.).

As the compound having one (meth)acryloyl group, for example, alkyl (meth)acrylate having 4 to 16 carbon atoms, β carboxyalkyl (meth)acrylate having 2 to 14 carbon atoms, alkylated phenyl having 2 to 14 carbon atoms ( Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned.

Examples of the compound having two (meth)acryloyl groups include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimerdiol di(meth)acrylate, dimethyloltricyclodecanedi (meth)acrylate etc. are mentioned.

In addition, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and polypropylene glycol di(meth)acrylate.

In addition, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, zinc di(meth)acrylate, cyclohexanediol di(meth)acrylate, cyclohexane Dimethanol di(meth)acrylate, cyclohexanediethanoldi(meth)acrylate, cyclohexanedialkyl alcohol di(meth)acrylate, dimethanol tricyclodecanedi(meth)acrylate, etc. are mentioned.

Moreover, the reaction product of 1 mol of bisphenol A, bisphenol F, or bisphenol AD, and 2 mol of glycidyl acrylate, the reaction product of 1 mol of bisphenol A, bisphenol F, or bisphenol AD, and 2 mol of glycidyl methacrylate, etc. are mentioned.

Any 1 type of acrylic resin mentioned above may be used for an acrylic resin, and may use 2 or more types together. From a fluid viewpoint, low molecular weight acrylic resins, such as ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate, are preferable.

Preferably the quantity of (B) thermosetting resin in an electroconductive composition is 30-80 mass parts with respect to 100 mass parts of (A) electroconductive particles, More preferably, it is 35-75 mass parts, More preferably, it is 40-70 mass is wealth When the amount of the (B) thermosetting resin in the conductive composition is within the above range, it is possible to ensure that the objects to be adhered are connected to each other and fixed. Moreover, (A) electroconductive particle which is an inorganic material in an electroconductive composition can be mutually connected and fixed, and predetermined electroconductivity by (A) electroconductive particle can be maintained.

(C) curing agent

The conductive composition of this embodiment contains (C) a hardening|curing agent. (C) The curing agent (B) has an action of lowering the activation energy of the curing reaction of the thermosetting resin, and (B) any compound known as a curing accelerator for the thermosetting resin can be used. (C) As a hardening|curing agent, an amine-type hardening|curing agent, a phenol-type hardening|curing agent, and an acid anhydride can be used, for example. These may be used independently and may use 2 or more types together. Moreover, it is preferable to use an amine hardening|curing agent from the point which has characteristics, such as a low viscosity and excellent moisture absorption resistance, and easy adjustment of a glass transition point (Tg).

As the amine curing agent, chain aliphatic amines, cyclic aliphatic amines, aromatic amines, aliphatic aromatic amines, and the like can be used. Specifically, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-amino) Cyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis(2-amino-2-methylpropyl)piperazine, diethyltoluenediamine, dimethyl Thiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, di Ethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, imidazole, benzimidazole, 2-ethyl-4-methylimidazole, 2-methyl Imidazole, tridimethylaminophenol, tridimethylaminomethylphenol, triethanolamine, benzylmethylamine, hexamethylenetetramine, triethylenediamine, quinoline, N-methylmorpholine, dimethylaniline, dimethylcyclohexylamine, 1,8 -Diazabicyclo(5,4,0)undecene-7(DBU), 1,4-diaza-bicyclo(2,2,2)octane, etc. can be used.

As a phenolic hardening|curing agent, the monomer which has a phenolic hydroxyl group, an oligomer, and the polymer in general are pointed out. Specifically, phenol novolak resins and their alkylated or allylated products, cresol novolak resins, phenol aralkyl (including phenylene and biphenylene skeletons) resins, naphthol aralkyl resins, triphenol methane resins, and dicyclo A pentadiene type phenol resin or the like can be used.

Examples of the acid anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, and methylcyclohexenetetracarboxyl. Acid dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerin bis(anhydrotrimellitate) monoacetate, dodecenyl anhydride succinic acid, aliphatic dibasic acid polyanhydride, chlorendic acid anhydride, methylbutenyltetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhymic anhydride, succinic anhydride substituted with an alkenyl group, glutaric anhydride and the like can be used.

(B) When the thermosetting resin has an ethylenically unsaturated group in its molecule and is a compound in which a polymerization reaction proceeds by radicals (eg, acrylic resin, vinyl ester resin), (C) a radical initiator may be used as the curing agent have. A radical initiator may just be a compound which generate|occur|produces a radical under fixed reaction conditions in order to advance a radical reaction. Although an organic peroxide, an azo compound, etc. are mentioned as a radical initiator, An organic peroxide is preferable.

The organic peroxide is, for example, at least one selected from ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and percarbonates; , specifically 1,1,3,3-tetramethylbutylperoxy2-ethylhexanate, t-butylperoxybenzoate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, 1 ,1,3,3-tetramethylbutylperoxyneodecanoate, t-butylperoxybenzoate, dicumylperoxide, tert-butylα-cumylperoxide, di-t-butylperoxide, di-t -Hexyl peroxide, di(2-t-butylperoxyisopropyl)benzene, 2,2-di(4,4-di-(butylperoxy)cyclohexyl)propane, p-mentane hydroperoxide, di Isopropylbenzenehydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumene hydroperoxide, 1,1-di(t-butylperoxy)cyclohexane, cyclohexanone peroxide , 1,1-di(t-hexylperoxy)cyclohexane, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. These can be used individually or in combination of 2 or more types. From the viewpoint of stability and reactivity, bis(4-tert-butylcyclohexyl)peroxydicarbonate, dicumylperoxide and tert-butylα-cumylperoxide are more preferable.

Examples of the azo compound include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'- Azobis(cyclohexane-1-carbonitrile), 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, 2,2'-azobis[2 -Methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N- cyclohexyl-2-methylpropionamide) and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. These can be used individually or in combination of 2 or more types.

A latent curing agent obtained by complexing or microencapsulating the above various curing agents can also be preferably used as the curing agent (C). As such a complexed or microencapsulated latent curing agent, for example, a surface of the amine-based curing agent coated with a polyurethane resin can be used.

(C) As the amount of the curing agent, the equivalent ratio of the active groups of the (C) curing agent to the polymerization reactive groups of the (B) thermosetting resin is preferably 0.3 to 2.5, more preferably 0.6 to 1.5.

(D) a compound of formula (1)

The conductive composition of this embodiment is (D) following formula (1):

(Wherein, R ₁ is an alkylene group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ is a hydrogen atom or a carbon number 1 to 6 of an alkyl group, and n is 1 to 6.)

and a compound represented by (D) By including the compound of Formula (1), the electrically conductive composition which has high fluidity|liquidity can be obtained.

In formula (1), R ₁ is preferably an alkylene group having 2 to 4 carbon atoms, R ₂ is preferably a methyl group, R ₃ is preferably a methyl group, R ₄ is preferably a hydrogen atom, R ₅ is preferably an alkyl group having 2 to 5 carbon atoms, and n is preferably 2 to 4 carbon atoms.

A preferred compound of formula (1) is the formula (1A):

is a compound represented by

The present inventors discovered that the electrically conductive composition which has remarkably high fluidity|liquidity can be obtained especially by including the compound of (D) Formula (1) among various dispersing agents. (D) The following are considered as a reason which can obtain the electrically conductive composition which has high fluidity|liquidity by including the compound of Formula (1). (D) By including the compound of Formula (1), the compound of Formula (1) is adsorbed on the surface of (A) electroconductive particle, and electroconductive particle can be further disperse|distributed by steric hindrance repulsion and electrostatic repulsion, and also re-agglomerate is thought to be preventing Moreover, when the wetting of the surface of electroconductive particle advances, a viscosity becomes low and it is thought that a thixotropy index (TI value) becomes low. In particular, when the hydrophobic group containing the imidazole moiety in the compound of Formula (1) adsorb|sucks to the surface of (A) electroconductive particle, it is thought that fluidity|liquidity can be improved remarkably.

In this embodiment, Preferably the quantity of the compound represented by (D) Formula (1) in an electroconductive composition is 0.1-5.0 mass parts with respect to 100 mass parts of (A) electroconductive particles, More preferably, 0.2 to 3.0 parts by mass. (D) By carrying out quantity of the compound represented by Formula (1) in this range, fluidity|liquidity improves more and the resin composition with a low resistance value can be provided.

(E) triglycerides of unsaturated fatty acids

The conductive composition of the present embodiment may further contain (E) a triglyceride of an unsaturated fatty acid. Thereby, the conductivity of the resin composition can be further improved.

(E) The unsaturated fatty acid triglyceride refers to an acylglycerol in which three unsaturated fatty acids are ester-bonded to one molecule of glycerol. The unsaturated fatty acid is a fatty acid having one or more unsaturated carbon bonds, and includes monounsaturated fatty acids, diunsaturated fatty acids, triunsaturated fatty acids and the like, but monounsaturated fatty acids are preferred. Examples of monounsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, sapinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenic acid, erucic acid, nervonic acid, ricinolic acid, and the like. However, oleic acid and ricinolic acid are preferred. Examples of the diunsaturated fatty acid include linoleic acid, eicosadienoic acid, and docosadienoic acid, and linoleic acid is preferred. As a triunsaturated fatty acid, linolenic acid, pinolenic acid, eleostearic acid, eicosatrienoic acid etc. are mentioned, for example.

(E) The triglyceride of unsaturated fatty acids may have three identical unsaturated fatty acids bonded to each other in one molecule, and one unsaturated fatty acid may be bonded to each other in one molecule, and two identical unsaturated fatty acids and different unsaturated fatty acids may be bonded in one molecule. One fatty acid may couple|bond with it. As a triglyceride of the (E) unsaturated fatty acid which has three same unsaturated fatty acids in 1 molecule, the triglyceride by which 3 ricinolic acid couple|bonded is mentioned, for example. Examples of triglycerides of (E) unsaturated fatty acids to which other unsaturated fatty acids are bonded one by one in one molecule include triglycerides to which ricinolic acid, oleic acid, and linoleic acid are each bonded. As triglycerides of (E) unsaturated fatty acids in which two identical unsaturated fatty acids and one different unsaturated fatty acid are bonded in one molecule, for example, triglycerides in which two oleic acid and one ricinolic acid are bonded, and ricin and triglycerides in which two oleic acids and one oleic acid are bonded.

The triglycerides of these unsaturated fatty acids can be used individually or in combination of 2 or more types.

(E) A more preferable example of the triglyceride of an unsaturated fatty acid is a triglyceride of ricinolic acid, the following formula (2):

is a compound represented by

Castor oil is a kind of vegetable oil, triglyceride of unsaturated fatty acids (87% ricinolic acid, 7% oleic acid, 3% linoleic acid) and a small amount of saturated fatty acid (3% palmitic acid, stearic acid, etc.) includes (E) As triglyceride of unsaturated fatty acid, castor oil can also be used.

As quantity of the triglyceride of (E) unsaturated fatty acid in an electroconductive composition, it is preferable that it is 0.3-5 mass parts with respect to 100 mass parts of (A) electroconductive particles, and it is more preferable that it is 0.4-4 mass parts. By setting it as the quantity in this range, electroconductivity can be improved more.

(F) other ingredients

The conductive composition of this embodiment may contain the thing suitably selected from (F) other additives, for example, a dispersing agent, a rheology modifier, a pigment, etc.

[Method for Producing Conductive Composition]

The conductive composition of this embodiment can be manufactured by mixing each said component using, for example, a grinder, a pot mill, a 3-axis roll mill, a rotary mixer, a 2-axis mixer, etc.

[Use of conductive composition]

The use of an electroconductive composition is demonstrated. The conductive composition of this embodiment can be used as a conductive adhesive and/or a sealing material by apply|coating to a predetermined place. Therefore, the conductive adhesive containing the conductive composition of the said 1st Embodiment is one Embodiment of this invention. The application method is arbitrary, and it can apply|coat using well-known methods, such as dispensing, jet dispensing, stencil printing, screen printing, pin transfer, and stamping, for example.

After apply|coating the conductive composition or conductive adhesive of this invention to a predetermined position, it can harden|cure by heat-processing the apply|coated conductive composition or conductive adhesive. The heat treatment can be cured by raising the temperature from 60°C to 100°C in 20 to 40 minutes, and then maintaining the temperature after heating for 50 to 70 minutes. Specifically, it can be cured by raising the temperature to 80°C in 30 minutes, and then maintaining the temperature at 80°C for 60 minutes.

The conductive composition or conductive adhesive of the present invention can be used as a conductive adhesive for camera modules. The conductive composition or conductive adhesive of the present invention has both high fluidity and predetermined electrical conductivity. Therefore, the electrically conductive composition or electrically conductive adhesive of this invention can satisfy the fluidity|liquidity and electroconductivity request|requirement required at the time of fixing a camera module.

For adhesion of the camera module to the bracket, there is an increasing demand in recent years for injecting an adhesive into a gap having a smaller dimension. Specifically, the gap between the bracket and the camera module is several hundred μm (for example, 300 μm to 600 μm), and it is necessary to inject the adhesive over a length of several mm. After the camera module is fixed to the bracket with the temporary fixing adhesive, the conductive adhesive of the present embodiment is jet-dispensed, so that the conductive adhesive can be supplied (injected) into a small gap between the camera module and the bracket. Since the conductive adhesive of this embodiment has conductivity, it has two functions: an electrically conductive paste (grounding paste) and a bracket peeling adhesive (sealing adhesive). Accordingly, the conductive adhesive of the present embodiment can be used as one adhesive instead of using two types of the conductive paste and the adhesive for bracket filling. Thereafter, the supplied conductive composition or conductive adhesive is cured by heat treatment, and the camera module is finally fixed to the bracket. Therefore, the camera module containing the hardened|cured material of the conductive adhesive of this invention is also one Embodiment of this invention.

As described above, by using the conductive adhesive of the present embodiment having high fluidity and conductivity, two steps of a step of grounding the camera module to the bracket and a step of finally fixing the camera module are one step. There is a possibility that it can be carried out, and a reduction in manufacturing cost can be expected.

It is preferable that the electrical resistivity (rho) of the conductive adhesive of this embodiment is 1.0x10 ^-4 to 5.0x10 ^{-1 Ω·cm.} It is sufficient that the conductive adhesive of this embodiment has the electroconductivity for taking a grounding, and it is not necessary to request|require high electroconductivity.

As described above, in order to take the grounding of the camera module to the bracket, and finally to fix the camera module, the conductive composition or the conductive adhesive of the present invention can be used.

Since the conductive adhesive of the present embodiment can be supplied to a gap having a small dimension, it can be preferably used for fixing minute elements such as a camera module and an image sensor module to a predetermined place in an apparatus. In addition, since the conductive adhesive of this embodiment can be used for sealing and bonding a narrow gap, the formation of circuits and electrodes of electronic components such as chip resistors and light emitting diodes (LEDs), bonding of electronic components to a substrate, etc. It is possible to use

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Preparation of conductive composition]

The following components were mixed in the ratio shown in Table 1, and the conductive composition of an Example and a comparative example was prepared. Specifically, each component was mixed with a planetary mixer, further dispersed with a 3-axis roll mill, and prepared by forming a paste. In addition, all the ratios of each component shown in Table 1 are shown by mass part.

(A) conductive particles

(Silver particle 1) Flake-like particle, average particle diameter 6㎛ (manufactured by METALOR, product name: EA-0001)

(Silver particle 2) Spherical particle, average particle diameter 5 µm (manufactured by METALOR)

(B) thermosetting resin

(Thermosetting resin 1) Bisphenol F-type epoxy resin/bisphenol A-type epoxy resin mixture (aromatic epoxy resin) (DIC Corporation make, EXA835LV, epoxy equivalent 165)

(Thermosetting resin 2) Aminophenol type liquid epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., product name: jER630D)

(C) curing agent

(curing agent 1) amine curing agent (manufactured by Fuji Kasei Kogyo Co., Ltd., product name: Fuji Cure-FXR-1020)

(Curing agent 2) Amine-based curing agent (manufactured by Fuji Kasei Kogyo Co., Ltd., product name: Fuji Cure-FXR-1121)

(D) a compound of formula (1)

Dispersant DISPERBYK-2163 (manufactured by Big-Chemie Japan Co., Ltd.) (Contains 45% of the compound of formula (1A) as an active ingredient. The amount in Table 1 is the amount of the compound of formula (1A).)

(E) triglycerides of unsaturated fatty acids

Triglyceride of castor oil (manufactured by Ito Seiyu Co., Ltd.) (unsaturated fatty acid (ricinolic acid 87%, oleic acid 7%, linoleic acid 3%) and a small amount of saturated fatty acid (palmitic acid, stearic acid, etc. 3%) Including ceride. The amount in Table 1 is the amount of triglyceride of an unsaturated fatty acid.)

[Method for measuring viscosity]

The viscosities of the conductive compositions of Examples and Comparative Examples were measured at a temperature of 25°C using a Brookfield (Type B) viscometer immediately after preparing the conductive composition. The measurement of the viscosity was performed at the rotation speed of 10 rpm with respect to each conductive adhesive of an Example and a comparative example. Table 1 below shows the measurement results.

[Method of measuring liquidity]

"Fluidity (sec/mm)" in Table 1 is an index showing the fluidity of the conductive composition when jet-dispensed into a gap of 600 µm. Specifically, the flow rate of the conductive composition was measured using the jig shown in FIG. 1 (a schematic view seen from the side) and FIG. 2 (a schematic view seen from the upper surface). That is, as shown in Figs. 1 and 2, the glass plate 12 is disposed on the stainless plate 14 with a spacer 16 interposed therebetween so that the gap d becomes 600 µm, in the vicinity of the opening of the gap (Fig. 1). The conductive compositions 20 of Examples and Comparative Examples were disposed by jet dispensing to the portion of the arrow. Flowability by measuring the time t (sec) when the flow of the conductive composition 20 into the gap becomes a predetermined distance L (mm) = 20 mm, and calculating the flow time t/L (sec/mm) per 1 mm was done with The fluidity|liquidity measurement was performed at 40 degreeC. Table 1 below shows the measurement results.

[Method of measuring electrical resistance]

The "resistance value (Ω)" of Table 1 is a measured value of electrical resistance when the conductive composition of an Example and a comparative example is hardened. The measurement of electrical resistance was performed using the electrode 24 as shown in FIG. That is, as shown in FIG. 3, on the hardened|cured glass plate 12, the pair of strip|belt-shaped electrodes 24 was arrange|positioned so that the space|interval D of the electrode 24 might become 40 mm. On the glass plate 12 and the pair of electrodes 24, the conductive compositions of Examples and Comparative Examples were placed and cured by a stencil printing method so that the width W was 10 mm. The arranged conductive composition was cured by raising the temperature to 80°C in 30 minutes, and then maintaining the temperature at 80°C for 60 minutes. The film thickness of the conductive composition when hardened|cured was 20 micrometers. By measuring the electrical resistance value between the cured pair of electrodes 24 with an ohmmeter R, the electrical resistance values of Examples and Comparative Examples were obtained. In addition, for the measurement of the film thickness, the Tokyo Seimitsu Co., Ltd. surface roughness shape measuring instrument (model number: Surfcom 1500SD-2) was used. In addition, the digital multimeter (model number: 2001) manufactured by TFF Keisley Instruments was used for the measurement of the electrical resistance value. Table 1 below shows the measurement results.

The conductive compositions of Examples 1 to 9 containing the compound of Formula (1) had low viscosity and high fluidity so that the result shown in Table 1 might show. On the other hand, the conductive composition of Comparative Example 1 which does not contain the compound of Formula (1) has high viscosity and low fluidity, does not flow 3 mm from the opening in the fluidity measurement test, and does not reach a predetermined distance L of the test piece. didn't

Moreover, the electric resistance value of the electroconductive composition of Examples 1-9 containing the compound of Formula (1) was also the range of 4.2-720 (ohm), and it was a suitable value in the use of taking grounding. (E) Examples 7 to 9 further containing the triglyceride of an unsaturated fatty acid have a low resistance value compared with Example 1 which does not contain the (E) component, and it can be said that electroconductivity improved.

From the above, it was found that the conductive compositions of Examples 1 to 9 containing the compound of Formula (1) showed high fluidity and had moderate electrical conductivity. Therefore, it can be said that the conductive composition of this invention can be used suitably as a conductive adhesive for fixing of a camera module, for example.

As for the indication of Japanese Patent Application No. 2019-034127 (application date: February 27, 2019), the whole is taken in into this specification by reference.

All publications, patent applications, and technical standards described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

12: glass plate
14: stainless steel plate
16: spacer
20: conductive composition
22: glass plate
24: electrode
R: ohmmeter
50: jet dispenser
52: needle
54: seal (sealing member)
56: nozzle
S: stroke

Claims (10)

(A) electroconductive particle, (B) thermosetting resin, (C) hardening|curing agent, and (D) following formula (1):

(Wherein, R ₁ is an alkylene group having 1 to 6 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group, and R ₅ is a hydrogen atom or a carbon number 1 to 6 of an alkyl group, and n is 1 to 6.)
A conductive composition comprising a compound of The conductive composition of Claim 1 whose (A) electroconductive particle is a silver particle. The conductive composition according to claim 1 or 2, wherein (B) the thermosetting resin is at least one of an epoxy resin and an acrylic resin. The conductive composition according to any one of claims 1 to 3, wherein (C) the curing agent is an amine curing agent. The electroconductivity of any one of Claims 1-4 whose quantity of the compound represented by (D) Formula (1) in an electroconductive composition is 0.1-5.0 mass parts with respect to 100 mass parts of (A) electroconductive particles. composition. The conductive composition according to any one of claims 1 to 5, further comprising (E) a triglyceride of an unsaturated fatty acid. The electroconductive composition of Claim 6 whose quantity of the triglyceride of (E) unsaturated fatty acid in an electroconductive composition is 0.3-5 mass parts with respect to 100 mass parts of (A) electroconductive particles. The conductive adhesive containing the conductive composition in any one of Claims 1-7. The conductive adhesive according to claim 8, which is for a camera module. The camera module containing the hardened|cured material of the conductive adhesive of Claim 8 or 9.

Images