JPS6084303A - Electroconductor resin composition - Google Patents

Abstract

PURPOSE:The titled composition which, even when it is in the form of a relatively thick film, can cure within a relatively short time, comprising an energy ray- curable cation-plymerizable organic substance, an electroconductive powder, an anergy ray-sensitive cationic polymerzation catalyst, and a heat-sensitive cationic polymerization catalyst. CONSTITUTION:100pts.wt. energy ray-curable cation-polymerizable organic substance (e.g., hydrogenated bisphenol A diglycidyl ether) is mixed with 3- 600pts.wt. electroconductive powder (e.g., carbon black), 0.01-10pts.wt. energy raysensitive cationic polymerization catalyst selected from aromatic onium salts which upon irradiation with energy rays, release a Lewis acid having polymerization initiatability (e.g., triphenylphosphonium hexafluoroantimonate), and 0.03- 10pts.wt. heat-sensitive cationic polymerization catalyst selected from among organic onium salts which can be activated at 150 deg.C or below in the presence of the cation-polymerizable organic substance and induce its cationic polymerization (e.g., prenyltetramethylenesulfonium hexafluoroantimonate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an active energy ray-curable tetraelectric resin composition. For details, the essential ingredients are energy ray curable cationically polymerized Sumiariisomono Mitsugu, 4-ton powder, and energy ray sensitive cation: / N @ I>! This invention relates to an active energy hesocurable type 4/1:1 stinging resin composition containing an Ir medium and a heat-sensitive cationic polymerization catalyst.

In general, conductive resin compositions are prepared by blending metal powders such as silver and copper and charcoal A powder into thermosetting resins such as epoxy resins, alkyd resins, and phenolic resins as additives. The curing of thermosetting resins requires heating at high temperatures for long periods of time.
It takes 60 minutes to several hours at 0 to 200°C. Under these heat drying conditions, phenol and epoxy.

Not only is this inconvenient because it causes deterioration and thermal deformation of insulating substrates such as polyester, but it also has the drawbacks of extremely poor thermal energy efficiency and workability. Attempts have been made to obtain fast-curing conductive resin compositions by using ultraviolet curable resins as binders in resin compositions.However, these ultraviolet curable conductive resin compositions do not contain carbon powder, silver powder, etc. Because it contains an anti-glare agent, the transmittance of ultraviolet rays is significantly reduced and curing does not proceed sufficiently.

Particularly in the case of a certain thick coating film, only the surface layer is cured, while the interior of the coating film and the portions close to the substrate remain uncured. In addition, when used in applications that require a high degree of conductivity, it is necessary to use about 7Q to 9Qwt% of the metal fine powder based on the total composition, and the barrier effect of the metal fine powder is required. Therefore, the polymerization reaction due to ultraviolet absorption is significantly inhibited, and sufficient curing and drying cannot be carried out.

The present invention was completed as a result of extensive studies to eliminate the various drawbacks of such conventional energy ray curable conductive resin compositions.

The purpose of the present invention is to sufficiently cure a coating film containing a large amount of conductive powder and having a relatively large thickness by practical energy ray irradiation and/or heating at a relatively low temperature for a short time. An object of the present invention is to provide an energy storage curing type conductive resin composition.

The conductive resin composition of the present invention has as an essential component.

(value of the cationic polymerizable compound material that can be irradiated with energy rays), conductive powder, (0) an energy ray-sensitive cationic polymerization catalyst, and (dl) a heat-sensitive cationic polymerization medium. The conductive 14-lipid composition uses an energy ray-sensitive cationic polymerization catalyst and a heat-sensitive cationic polymerization catalyst as polymerization initiators in combination, so that a cationic polymerization reaction initiated by active energy rays and radiant heat rays from active energy rays or a comparison can be achieved. A cationic polymerization reaction that is initiated by heating at a relatively low temperature for a short time is carried out in parallel, allowing coatings with insufficient transparency to active energy rays such as ultraviolet rays to be sufficiently cured in a short period of time, even in good parts. It is.

An energy-curable cationically polymerizable organic material (al is a cationically polymerizable compound that undergoes a polymerization or crosslinking reaction when irradiated with energy rays in the presence of an energy ray-sensitive cationic polymerization catalyst, which is a component of the uA composition of the present invention. For example, epoxy compounds.

181 or 271 of cyclic ether compounds, yellow ectone compounds, cyclic acetal compounds, cyclic thioether compounds, subiroorne ester compounds, vinyl compounds, etc.
It consists of a mixture of the above. Among such cationic polymerizable compounds, compounds having at least one or more epoxy groups in one molecule are preferred, such as conventionally known aromatic epoxy resins and alicyclic epoxy resins.

Examples include aliphatic epoxy resins. Here, preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols or their alkylene oxide adducts having at least one aromatic nucleus, such as bisphenol 8 or its alkylene oxide adducts and shrimp chlorubicin. Examples include glycidyl ether and epoxy novolank resin produced by reaction with dorine. Preferably, the alicyclic epoxy resin is a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or a cyclohexene/or cyclopentene ring-containing compound, mixed with a suitable oxidizing agent such as hydrogen peroxide or cyclopentene. Examples thereof include fuclohexe/oxide or cyclopentene oxide-containing compounds obtained by epoxidation with. Typical examples of alicyclic epoxy resins include hydrogenated bisphenol A sifuricidyl ether, 3,4-epoxycyclohexylmethyl-5,4-epoxycyclohexane carboxylate), and 2-(3,4-epoxycyclohexyl). -5,5-spiro-3,4-epoxy)cyclohexane-methadioquinane, bis(3,4-epoxycyclohexylmethyl)acyl, <-t.

Vinyl cyclohexe/dioxide, 4-vinylepoxycyclohexane, bis(5,4-epoxy-6-methylcyclohexylmethyl)adipe), 5,4-epoxy-6-methylcyclo#cipv-3,4-epoxy- 6-Methylcyclohexanecarboxylate, methine/bis(3,4-epoxycyclohexane), dicyclopentadiene dieboxide, ethylene glycol cyclo(3,4-epoxycyclohexylmethy/L/)neegle, ethylene bis(5, 4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, and the like.

Further preferred as the aliphatic epoxy resin are aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts thereof.

Polyglycidyl ester of aliphatic long chain polyprotic acid.

There are homopolymers and copolymers of glycidyl acrylate and glycidyl mequaacrylate, and representative examples include diglycidyl ether of 1,4-pucundiol, diglycidyl ether of 1,6-hexanediol,
One or more aliphatic polyhydric alcohols such as triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin. Examples include polyglycidyl ethers of polyether polyols obtained by adding alkylene oxide, and diglycidyl esters of aliphatic long-chain dibasic acids. In addition, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol,
Butyl phenol or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl N epoxy stearate, epoxidized linseed oil, epoxidized Examples include polybutadiene.

Examples of cationically polymerizable organic substances other than epoxy compounds include trimethylene oxide, 5,5-dimethylchetane, oxetane compounds such as 3,5-dichloromethylethane, tetrahydrofuran, 2,3-dimethyltetrahydro7rane, etc. Oxirane compounds such as trioxa/
, 1°6-cyoxirane, cyclic acetal compounds such as 1,5,6-trioxa/cyclooctane; β-propiolactone, ! - Cyclic lactonized @ products such as caprolactone; ethylene sulfide.

1. Thiirane compounds such as 2-propylene sulfide and thioehchlorohydrin; Chekun compounds such as 1,3-globin sulfide and 5,3-dimethylchetane: ethylene glycol divinyl ether, polyalkylene glycol divinyl ether, Vinyl ether compounds such as alkyl vinyl ether, 6,4-cihydropyra/-2-methyl (3,4-dihydrobyran-2-carboxylate); spiro-orthoester compounds obtained by reaction of epoxy compounds with lactones; vinylcyclohexane; Ethylene-attached unsaturated phase compounds such as imptyre/polybutadiene and derivatives of the above-mentioned compounds can be mentioned.

These cationic polymerizable compounds can be used alone or in combination of two or more kinds depending on the desired performance.

The derivative powder (b) used in the present invention is silver.

Conductive metal powders such as platinum, gold, copper, nickel, aluminum, palladium, iron, tin, lead, zinc, molybdenum, etc., and powders of their alloys.

Inexpensive conductive metal powders such as iron, copper, nickel, zinc, tin, lead, and aluminum coated with precious metals such as gold and silver, carbon black, a7ethylene plaque, graphite, graphite, ferrite, and grafted carbon, etc. Carbon fine powder/, c, etc. can be mentioned. Other materials include fine carbon powder, glass powder, glass fiber, etc. whose surfaces are coated with highly conductive metals such as gold and silver.

These conductive powders can be used alone or in combination depending on the required conductivity and purpose, and the type, shape, and size of the conductive fine powder can be adjusted as appropriate depending on the purpose of use of the composition. You can choose.

The energy ray-sensitive cationic polymerization catalyst (0) used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization upon irradiation with energy rays, and particularly preferred is a Lewis acid having the ability to initiate polymerization upon irradiation. It belongs to a group of double salts, which are onium salts that release . /
J) Typical such compounds have the general formula [R11R2b
R5oR4,Z]+1[MXn-1-ml-1nC In the formula, the cation is onium.

2 is S, Se, Te, P, As, Sb, Bi
, O, halogen (e.g. I, Br, Cl)
, HmiN, and R1°R2, R3, and R' are organic groups which may be the same or different. a, b, c, d
are integers from 0 to 3, and a + b + a
+d has no effect on the valence of 2. M is a metal or metalloid which is the central atom of the halide complex.
), and B, P, As.

Sb, Fe', Sn, Bi, AI! , Oa,
In, Ti, Zn, Sc, V.

Or, Mn, Co4. X is halogen °C.

m is the net charge of the halide complex ion r+,
n Halide is the number of halogen atoms in the complex ion. ].

Specific examples of the anion Mxn+m in the above general formula are tetrafluoroborate (BF4-), hexafluorophosphate (py, -), hexafluoroantimone) (SbF6-), hexafluorophosphate) ( A51F""), hexachloroantimonate Cf3b016"), and the like.

Furthermore, an anion of the general formula MXn(OR)'' can also be used. Other ions include perchlorate ion (atO,-),) fluoromethyl sulfite
lR't on (OF, SO, -), fluorosulfonic acid ion (FSCI'),) luenesulfonic acid anion No. 7
% trinitrobe/zensulfone anion and the like.

Among such onium salts, it is particularly effective to use aromatic onium salts as cationic polymerization catalysts.
Among them, JP-A-50-151996, JP-A-50-1
Aromatic halonium salts described in JP-A-58680, etc., JP-A-50-151997, JP-A-52-50899,
JP-A-56-55420, JP-A-55-125105
VIA group aromatic onium salts described in JP-A No. 1987, etc.
VA group aromatic onium salts described in JP-A No. 0-158698, etc., JP-A-56-8428, JP-A-56-1494
No. 02 1% Oxysulfoxonium salts described in JP-A No. 57-192429, etc., aromatic diazonium salts described in Japanese Patent Publication No. 49-17040, etc., U.S. Patent @ 415
Thiopyrylium salts described in No. 9655 Mei #JHF and the like are preferred.

Such a cationic polymerization catalyst can also be used in combination with a photosensitizer such as benzophenone, pency/isopropyl ether, and thioxanthone.

Another main component of the composition of the present invention is a heat-sensitive cationic polymerization catalyst (dJ), which is an onium salt that can be activated in the presence of a cationic polymerizable organic substance at temperatures below 11150°C to cause cationic polymerization. In addition, in order to effectively achieve the purpose of the present invention, other conditions (21260m
(3) It is preferable that the activation energy for thermal decomposition is 11 to 20 Kcal/mole or more.

Preferred heat-sensitive onium LHs that satisfy the above conditions are those having a special radical group selected from aliphatic sulfonium salts.

It can be represented by the following general formula (Il).

Here, R1 and R2 are the same or different ia or unsubstituted aliphatic or aliphatic groups R,, R2! (Also, unsaturated phase bonds, alkoxy groups, nitro groups, halogen groups, hydroxyl groups.

carboxyl group, ester group, ether group, cyano group,
It can contain functional groups such as carbonyl groups, sulfone stripes, and thionyl groups. Y is an aliphatic group having a lattice-attracting a-travel group at the 6-position or β-position with respect to the ionic atom,
It is preferable to use the following general formula or (e).

■ R4 (ITJ (E)) Here, R3-R6 are groups selected from hydrogen atoms and substituted or unsubstituted aliphatic groups, and R6 and R4 or R5 and R6 may be the same or different.Y/ is It is an electron-withdrawing functional group.

Here, the term "electron-withdrawing functional group" refers to a group that exerts an attractive effect on electrons of adjacent carbon atoms, and examples of such groups include nitro groups and cyano groups.

Alkenyl group, alkynyl group, carboxyl group.

Includes carbonyl group, hydroxyl group, ester group, sulfone 75, halo)y'n group, etc. Among these, particularly preferred are allyl groups or tertiary aliphatic groups in which Y is substituted with at least one aliphatic group.

Further, the anion A is a halogen-containing complex ion selected from metal halides, for example BF4''.

pF6-, sbp,-, 5bat6-, AIIF,
-, 5by5CoH) - is preferred. Further, other anions include atom.

Examples include a゛v3so, -, yso; and the like.

Such sulfonium salts are relatively easily synthesized.1 For example, a sulfonium salt with a norogen anion is synthesized by reacting the corresponding sulfide with a highly active alkyl halide, and then HMQIn, N! LMQm,k
MQm, NH4MQ, (where M is B, P.

8b, As, Fe, A/, Cu, Ti, c
d, Zn, Sn, Q is a halogen atom, m is an integer from 1 to 6), or by directly adding triethyloxynium tetra to sulfide. It can also be synthesized in good yield by reacting a Mehrwein reagent such as fluoroborate. In addition, when a tertiary aliphatic group is reacted with a sulfide, the reaction can be carried out under acidic conditions using the corresponding alcohol as a starting material to obtain a good sulfonium salt.

The composition ratio of the composition of the present invention can be varied widely depending on the required performance. For example, conductive powder (bJ is 3 to 600 parts by weight, preferably 5 to
400M part, energy ray sensitive cationic polymerization catalyst (0) is 0.01 to 10 parts, preferably 0.05 to 10 parts
5 parts by weight, heat-sensitive cationic polymerization catalyst (dl is 0.03
It can be contained in a range of 10 M parts, preferably 0.05 to 7 M parts.

The composition of the present invention may be used as long as it does not impair the effects of the present invention.

6 types of modifying resins such as acrylic resins and polyester resins other than the cationically polymerizable organic substances described above; colorants such as pigments and dyes; overnight foaming agents; leveling agents; Appropriate amounts of various Mllll additives such as carbon dioxide, antioxidants, fillers such as phosphorescent grass powder, etc. can be mixed and used.

The composition of the present invention can be applied to various insulating substrates, molded containers, etc.
After impregnating and injecting, it can be cured by irradiation with energy rays and/or heating.

The active energy rays used when cross-curing the composition of the present invention include ultraviolet rays, electron beams, xfti radiation, and high frequency waves, among which
Ultraviolet rays having a wavelength of 0 A are economically preferable, and the light sources that can be used include high- and low-pressure mercury lamps, quinanone lamps, sodium lamps, germicidal lamps, alkali metal lamps, dilution lamps, laser beams, and the like. Furthermore, for molded products such as thick coatings and sheets, the object of the present invention can be advantageously achieved by a method using high-energy electron beam irradiation.

When curing the composition of the present invention, for example, when irradiating with an air-cooled high-pressure mercury lamp, the radiant heat rays of the mercury can be utilized, so additional heating is often not necessary.
In active energy irradiation device 4, which does not generate much heat rays, heating is performed before, at the same time, or after active energy ray irradiation.
By using F, a complete curing reaction can be carried out more effectively. In addition, the composition of the present invention can be hardened by irradiating it with energy rays, but in some cases it is also possible to cure it by heating alone, and it can be cured for a few seconds at a temperature range of 50 to 150°C. It can be hardened in about a few minutes.

While conventional thermosetting four-electrode resin compositions require heating at high temperatures for long periods of time, the composition of the present invention takes advantage of the fast curing property due to energy ray curing, while also being able to cure with energy rays. The deep layer of the coating film, which is difficult to penetrate, is designed to undergo a thermal reaction at a relatively low temperature and in a short period of time, resulting in rapid curing as a whole, which significantly improves workability, and at the same time improves adhesion to the substrate and It is possible to improve heat deformation, deterioration, etc. of various objects and base materials such as hypochondriasis and hypochondrium characteristics.

Specific uses of the present invention include conductive paints, specialty inks, 4-electrode adhesives, electromagnetic wave coatings, conductive film sheets, magnetic shielding paints, conductive molds, etc. Examples include molding materials and impregnated materials. In particular, epoxy resin has excellent hypothermia properties, so it can be used for electric circuit boards, chips, capacitors, resistors, 4-electronic elements, switches, motors, etc.
Applicable to the field of child parts.

Hereinafter, typical examples of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples. Hit "parts" means parts by weight.

Example 1 75 parts of 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 25 parts of trimethylolpropane triglycidyl ether, and 0.5 part of a silicone surfactant were mixed together to form a homogeneous resin. Triphenylsulfonium hexafluoroantimone (as energy ray sensitive cation ffi financial m) for 100 parts of this resin) 0-71! IVS and 0.7 parts of prenyltetramethylene sulfonicum hexafluoroantimonate as a heat-sensitive cationic polymerization catalyst were thoroughly mixed to obtain a uniform energy ray-curable resin composition. 60 parts of flat silver powder was added to 40 parts of this composition and dispersed sufficiently uniformly to obtain a viscous paste-like conductive resin composition. This was printed on an insulating substrate to a thickness of 20 μm by screen printing, and was cured by irradiation for 40 seconds at an irradiation distance of 13 cm using a 80 W/0/1 mercury lamp irradiation device. The cured coating film was sufficiently cured in the deep layer, and had a sheet resistance of 100 mΩ, a chain wheel hardness of 5H, and a cross-cut tape peel test of 100/100.

Example 2 30 parts of 34-epoxycyclohexylmethyl-6,4-epoxycyclohexanecarboxylate, bis(3,
Mix 60 parts of 4-epoxycyclohexylmethyl) adipate, 10 parts of cresyl glycidyl ether, and 1 part of a silicone surfactant to make a homogeneous resin.
1 part of bis-(4-(diphenylsulfonio)phere) sulfide bisdihexafluoroantimonate as cationic radiation-sensitive cation M for 100 parts of fat; '''0.5 part of tramethylene sulfonium hexafluoroir/thinanate was thoroughly mixed to obtain a homogeneous composition. To 40 parts of this composition, 4 parts of flat silver powder was added.
5 parts and 15 parts of spherical #shape were added and dispersed sufficiently uniformly to form a viscous paste-like conductive resin composition, which was printed onto a polyimide film substrate to a thickness of 2 by screen printing.
0μ and cured by irradiating for 30 seconds under an 80 W/rm mercury lamp (6-ray device).The resulting cured coating had a sheet resistance of 150 mΩ and a pencil hardness of 2H.

Cross force deep peel test was 1007100.

Even in a 180° bending test with the coated surface facing either the outside or the inside, the paint film was found to have sufficient flexibility and flexability without any scratches.

Example 6 The cured coating film was cured under the curing conditions of Example 1 by irradiating with a C* silver lamp for 5 seconds and then heating at 150°C for 2 minutes, and the cured coating film was cured using a mercury lamp alone. showed similar filamentous 11th appearance.

Example 4 50 parts of 54-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 50 parts of vinylcyclohexene dioxide, and 1 part of a silicone surfactant are thoroughly mixed to form a uniform resin. This resin 10
For each 0 parts, add 1 part of energy ray-sensitive cationic polymerization catalyst and cytetriphenylsulfonium hexafluoroandemone, and 0.5 part of prenyltetrimethylenesulfonium hexafluoroantimonate as heat-sensitive cationic polymerization catalyst (mix to homogeneous An energy ray-curable resin composition was obtained. 45 parts of this composition was mixed with 55 parts of graphite as a conductive powder using a roll mill so as to be sufficiently uniform to obtain a conductive resin composition. This was applied to an insulating substrate. 2 on top
When screen printed to have a resistance of 0μ and irradiated with ultraviolet rays for 60 seconds under a 120W/@ high pressure mercury lamp, the sort resistance was 35.
A cured coating film of 0Ω was obtained. It also had excellent chemical resistance.

Example 5 In Example 4, as a curing condition, instead of ultraviolet irradiation using a high-pressure mercury lamp, an electron beam at an accelerated pressure of 150 KeV was irradiated to a dose of 15 Mrad using an electron beam irradiation device. A conductive coating film similar to y was obtained.

Comparative Example 1 A conductive resin composition prepared in Example 1 except that only the heat-sensitive cationic polymerization catalyst prenylteto-2-methylenesulfonium hexafluoroantimonate was removed was subjected to JIM. This energy ray-curable conductive resin composition was printed on an insulating substrate and irradiated with ultraviolet rays under the same curing conditions as in Example 1, but only the surface portion of the coating was cured, while the deeper portions of the coating were sufficiently cured. I didn't. Furthermore, although ultraviolet ray irradiation was performed for 60 seconds, the inside of the coating film was not cured.

Comparative Example 2 A conductive resin composition was prepared in the same manner as in Example 4 except that only the heat-sensitive cationic polymerization catalyst prenyltetramethylene sulfonium hexafluoroantimonate was removed. This was printed on an insulating substrate in the same manner as in Example 4 and irradiated with ultraviolet rays, but the true layer portion of the coating was not sufficiently cured.

Comparative example 3 10 parts of phenolic resin, 20 parts of epoxy resin.

A thermosetting conductive composition was obtained from 15 parts of butanol, 15 parts of Kijirole, 220 parts of acetylens 2F, and 20 parts of graphite. This composition was printed on an insulating substrate to a thickness of 20μ by screen printing, and
After heat curing at 0° C. for 5 hours, a conductive coating film with a sheet resistance of 300Ω was formed.

Applicant's agent Kaoru Furutani

Claims (1)

[Scope of Claims] 1. As essential components, (a) an energy diverticulative cationically polymerizable organic substance, (b) a conductive powder, (0) an energy ray-sensitive cationic polymerization catalyst, and a heat-sensitive cationic polymerization catalyst. 2. The conductive resin composition according to claim 1, wherein the energy ray-curable cationic polymerizable organic substance of the Al component is an epoxy group-containing compound. 5. The conductivity according to claim 1 or 2, wherein the energy ray-sensitive cationic polymerization catalyst of component (c) is an aromatic onium salt capable of releasing a Lewis acid upon receiving energy rays. Resin composition. 4. The heat-sensitive cationic polymerization catalyst of component (a) is capable of releasing a Lewis acid by heat (any one of claims 1 to 5 which is a sulfonium salt The conductive iV1 lipid composition described in .