KR20130029770A - Anisotropic conductive film, bonded body, and connection method - Google Patents

Abstract

An anisotropic conductive film containing conductive particles, a film-forming resin, a radically polymerizable compound, a curing agent for generating free radicals, and an amine salt obtained from a phosphoric acid (meth) acrylate and an amine silane coupling agent is provided.

Description

Anisotropic conductive film, bonded body and connection method {ANISOTROPIC CONDUCTIVE FILM, BONDED BODY, AND CONNECTION METHOD}

This invention is an anisotropic conductive film which can electrically and mechanically connect circuit members, such as an IC chip and a liquid crystal panel (LCD panel) in a liquid crystal display (LCD), and a bonding body and the connection method using the anisotropic conductive film It is about.

Conventionally, the tape-shaped connection material (for example, anisotropic conductive film (ACF; Anisotropic Conductive Film)) which apply | coated the thermosetting resin in which electroconductive particle disperse | distributed to the peeling film is used as a means to connect a circuit member.

This anisotropic conductive film adheres various terminals, for example, when connecting the terminal of a flexible printed circuit board (FPC) or an IC chip, and the ITO (Indium Tin Oxide) electrode formed on the glass substrate of an LCD panel. It is used when making electrical connection with shikim.

In the connection portion of the LCD panel, the wiring material and the insulating film are arranged alternately, but in the conventional ACF, there is a problem that the adhesiveness to the wiring material and the insulating film cannot be sufficiently satisfied.

Then, in patent document 1, the hardening | curing agent composition which mix | blended the amine salt compound which has the silicon containing group which the hydroxyl group or the hydrolyzable group couple | bonded with the silicon atom is proposed.

However, this proposal does not disclose or suggest the amine salt obtained from a phosphoric acid (meth) acrylate and an amine silane coupling agent, and also mentions that the adhesive strength and connection reliability with respect to ACF improve.

Moreover, although the amine salt which consists of phosphoric acid (meth) acrylate and tertiary amines is disclosed by patent document 2, it aims at reducing water content, and also shows the indication about what improves adhesiveness and uses for ACF. It is not.

Japanese Patent Laid-Open No. 11-279424 Japanese Laid-Open Patent Publication No. 7-118281

It is an object of the present invention to solve the above-mentioned conventional problems and to achieve the following objects. That is, an object of this invention is to provide the anisotropic conductive film which showed favorable adhesiveness to both a wiring material with high polarity and an insulating film with high hydrophobicity, and improved the storage stability, the joined body using the anisotropic conductive film, and the connection method.

As a result of diligent studies by the present inventors in order to solve the said subject, phosphoric acid (meth) acrylate is added in order to improve adhesive force (adhesive force), When used alone, the adhesiveness to an insulating film with high hydrophobicity is suppressed, It was easy to stick to another material (especially electroconductive particle) immediately, and as a result, there existed a fault that resistance value rose. On the other hand, when an amine silane coupling agent is added alone, the adhesiveness to an insulating film improves, but there existed a problem that adhesiveness to a wiring material falls.

Therefore, as a result of the present inventors' earnest examination, by containing an amine salt obtained from a phosphoric acid (meth) acrylate and an amine silane coupling agent, adhesiveness with respect to a highly polar wiring material and a high hydrophobic insulating film can be made compatible. Since the deactivation of the amine silane coupling agent can be prevented, the storage stability is improved, and since the binding of the phosphate (meth) acrylate to the surface of the conductive particles can be prevented, a low conduction resistance (connection resistance) can be obtained. I noticed.

This invention is based on the said knowledge by the present inventors, As means for solving the said subject, it is as follows. In other words,

<1> Anisotropic conductive film containing electroconductive particle, film formation resin, radically polymerizable compound, the hardening agent which generate | occur | produces a free radical, and the amine salt obtained from phosphoric acid (meth) acrylate and an amine silane coupling agent. to be.

It is an anisotropic conductive film as described in said <1> whose pH of <2> amine salt is 3-8.

A first circuit member in which an insulating film and a wiring member are alternately formed on a <3> surface;

A second circuit member having a wiring member or an electrode formed on a surface of the first circuit member that faces the wiring member;

It is equipped with the anisotropic conductive film in any one of said <1>-<2>,

The said 1st circuit member and the said 2nd circuit member are bonded together through the said anisotropic conductive film, It is a joined body characterized by the above-mentioned.

A first circuit member in which an insulating film and a wiring member are alternately formed on a <4> surface;

In the connection method of the 2nd circuit member in which the wiring material or the electrode was formed in the surface which opposes the wiring material of the said 1st circuit member,

The anisotropic conductive film in any one of said <1>-<2> is clamped between the said 1st circuit member and a 2nd circuit member,

It is a connection method characterized by hardening the said anisotropic conductive film and connecting the said 1st circuit member and a said 2nd circuit member by pressurizing, heating from the said 1st circuit member and a 2nd circuit member.

ADVANTAGE OF THE INVENTION According to this invention, the said various problem in the past can be solved and the said objective can be achieved, and the anisotropic conductive film which showed favorable adhesiveness to both a wiring material with high polarity and a high hydrophobic insulating film, and improved storage stability, The joined body and the connection method using the anisotropic conductive film can be provided.

1 is a schematic view showing an example of the conjugate of the present invention.
It is a figure which shows the GC-MS analysis result of the polymerization compound of P-1M (phosphate acrylate) and KBE-903 (aminosilane coupling agent) in an Example.

(Anisotropic conductive film)

The anisotropic conductive film of this invention contains electroconductive particle, film formation resin, a radically polymerizable compound, the hardening agent which produces | generates a free radical, and the amine salt obtained from phosphoric acid (meth) acrylate and an amine silane coupling agent, In addition, it contains another component as needed.

<Amine salt obtained from phosphoric acid (meth) acrylate and an amine silane coupling agent>

The amine salt obtained from the said phosphoric acid (meth) acrylate and an amine silane coupling agent mixes phosphoric acid (meth) acrylate and an amine silane coupling agent, and superposed | polymerized by the acid base reaction, For example, It is an amine salt (polymerization compound) shown.

[Formula 1]

However, in said formula, n represents 1-2 and a represents 1-2.

Phosphoric Acid (meth) acrylate

There is no restriction | limiting in particular as said phosphoric acid (meth) acrylate, According to the objective, it can select suitably, For example, mono (2-methacryloyl oxyethyl) acid phosphate, di (2-methacryloyl oxy) Ethyl) acid phosphate, and the like.

All of these acidity is pH less than one.

As a specific example of the said phosphoric acid (meth) acrylate, the compound etc. which are represented by the following general formula are mentioned.

[Formula 2]

However, In the formula, R represents any of a hydrogen atom, CH ₂ Cl and CH _3. n represents 1-6, a represents 1-2.

(3)

However, in said formula, n shows 4-5 and a shows 1-2.

[Formula 4]

However, in said formula, n represents 1-2, a represents 1-2, and b represents 0-2.

Amine-based silane coupling agent

Examples of the amine silane coupling agent include an aminosilane coupling agent and a ureidosilane coupling agent.

As said aminosilane coupling agent, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-part Tylidene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane, etc. are mentioned.

As said ureidosilane coupling agent, 3-ureidopropyl triethoxysilane etc. are mentioned, for example.

As for the said amine silane coupling agent, all acidity is pH greater than 10.

Polymerization method

Since phosphoric acid (meth) acrylate is a strong acid (pH is less than 1) and the amine silane coupling agent is a strong base (pH is more than 10), polymerization proceeds easily by acid base reaction only by mixing the two. do. No addition of catalyst is necessary. Since the reaction involves exothermic heat, it is preferable to carry out the polymerization with a small dropwise addition. It is preferable to control reaction temperature at 20 degreeC-60 degreeC, and 40 degreeC-50 degreeC are more preferable. When the said reaction temperature is less than 20 degreeC, since a viscosity is high and dispersibility is lacking, a local reaction may occur easily and aggregate may generate | occur | produce. On the other hand, when the said reaction temperature exceeds 60 degreeC, reactivity becomes high and it becomes easy to produce an aggregate similarly.

It is preferable to perform the said reaction in the state diluted in solvent, such as toluene.

Although mass ratio (A: B) of the said phosphoric acid (meth) acrylate (A) and the said amine silane coupling agent (B) differs according to each molecular weight etc., it is preferable that it is 7: 3-3: 16, and 5 is It is more preferable that it is: 5-3: 16. When the ratio of the phosphate (meth) acrylate is too large, good adhesion to the insulating film may not be obtained, and when the ratio of the amine silane coupling agent is too large, good adhesion to the wiring member is not obtained. There is.

It is preferable that it is pH 3-8, and, as for the acidity degree of the said amine salt, 4-8 are more preferable. When the said pH is less than 3, the favorable adhesive force may not be obtained with respect to an insulating film, and when it exceeds 8, the favorable adhesive force with respect to a wiring material may not be obtained.

Here, the said pH can be measured using a pH meter etc., for example.

A polymerization inhibitor may be added to the amine salt to increase storage stability. In addition, storage is preferably refrigerated storage.

There is no restriction | limiting in particular as content in the said anisotropic conductive film of the amine salt obtained from the said phosphoric acid (meth) acrylate and the said amine silane coupling agent, Although it can select suitably according to the objective, For example, 0.1 mass%- It is preferable that it is 10 mass%, and it is more preferable that it is 1 mass%-5 mass%. When the said content is less than 0.1 mass%, adhesiveness with respect to both a highly polarizable wiring material and a high hydrophobic insulating film may fall, and when it exceeds 10 mass%, adhesiveness with both a highly polar wiring material and a high hydrophobic insulating film may be carried out. Although property is ensured, compatibility with a resin composition falls, and a residue may generate | occur | produce without melt | dissolving.

<Conductive Particle>

There is no restriction | limiting in particular as said electroconductive particle, According to the objective, it can select suitably, For example, a metal particle, a metal coating resin particle, etc. are mentioned.

Nickel, cobalt, silver, copper, gold, palladium etc. are mentioned as said metal particle. These may be used alone or in combination of two or more. Among these, nickel, silver and copper are particularly preferable. In order to prevent these surface oxidation, you may use the particle | grains which coated gold and palladium on the surface. Moreover, you may use what coated the insulating film with the metal protrusion or the organic substance on the surface.

As said metal coating resin particle, the particle | grains which coat | covered any metal among nickel, copper, gold, and palladium on the surface of a resin core are mentioned. Similarly, you may use the particle | grains which coated gold and palladium on the outermost surface. Moreover, you may use what coated the insulating film with the metal protrusion or the organic substance on the surface.

There is no restriction | limiting in particular as a coating method of the metal to the said resin core, According to the objective, it can select suitably, For example, an electroless plating method, a sputtering method, etc. are mentioned.

There is no restriction | limiting in particular as a material of the said resin core, According to the objective, it can select suitably, For example, a styrene-divinylbenzene copolymer, benzoguanamine resin, crosslinked polystyrene resin, an acrylic resin, a styrene-silica composite resin, etc. Can be mentioned.

There is no restriction | limiting in particular as content in the said anisotropic conductive film of the said electroconductive particle, According to the wiring pitch, connection area, etc. of a circuit member, it can adjust suitably.

<Film forming resin>

There is no restriction | limiting in particular as said film formation resin, According to the objective, it can select suitably, For example, a phenoxy resin, an epoxy resin, an unsaturated polyester resin, a saturated polyester resin, a urethane resin, butadiene resin, a polyimide resin, Polyamide resin, polyolefin resin, etc. are mentioned. The said film formation resin may be used individually by 1 type, and may use 2 or more types together. Among these, a phenoxy resin is especially preferable at the point of film forming property, workability, and connection reliability.

As said phenoxy resin, what was synthesize | combined suitably may be used as resin synthesize | combined from bisphenol A and epichlorohydrin, and a commercial item may be used.

<Radical polymerizable compound>

There is no restriction | limiting in particular as said radically polymerizable compound, According to the objective, it can select suitably, For example, an acryl compound, a liquid acrylate, etc. are illustrated, Specifically, methyl acrylate, ethyl acrylate, isopropyl acryl Elate, isobutyl acrylate, epoxy acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylol propane triacrylate, dimethylol tricyclodecane diacrylate, tetramethylene glycol tetraacrylate, 2-hydro Oxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclophene Tenyl acrylate, tricyclo decanyl acrylate, tris (acryloxyethyl) isocyanurate, urethane acrylate, epoxy acrylate, etc. are mentioned. have. Moreover, what made the said acrylate the methacrylate can also be used. These may be used alone or in combination of two or more.

<Hardener>

There is no restriction | limiting in particular as long as it can harden | cure binder resin as said hardening | curing agent, Although it can select suitably according to the objective, The hardening | curing agent which produces | generates free radical by heat or light is preferable.

It is preferable to use an organic peroxide as a curing agent for generating free radicals by the heat or light, and from the viewpoint of reactivity and storage stability, an organic half-life temperature of 90 ° C. to 180 ° C. for 10 minutes and a 10-hour half life temperature of 40 ° C. or more Peroxides are preferred.

In order to connect for 10 seconds or less, it is preferable that the half-life temperature is 180 degrees C or less for 1 minute, and when the half-life temperature is 40 degrees C or less for 10 hours, storage at 5 degrees C or less of refrigeration may become difficult.

As a hardener which generates free radicals by light, it is a material which absorbs in an ultraviolet wavelength, for example, an alkylphenone, benzoin, a benzophenone, a dicarbonyl compound, thioxanthone, an acylphosphine oxide, or these Derivatives; and the like. These may be used alone or in combination of two or more.

- Other ingredients -

There is no restriction | limiting in particular as said other components, According to the objective, it can select suitably, For example, a filler, a softener, an accelerator, an antioxidant, a coloring agent (pigment, dye), an organic solvent, an ion catcher, etc. are mentioned. . There is no restriction | limiting in particular in the addition amount of the said other component, According to the objective, it can select suitably.

The anisotropic conductive film, for example, conductive particles, film-forming resins, radically polymerizable compounds, curing agents for generating free radicals, and amine salts obtained from phosphoric acid (meth) acrylates and amine-based silane coupling agents, further required The coating liquid containing other components (organic solvent, etc.) can be prepared, and this coating liquid can be formed by apply | coating on a base material, drying, and removing an organic solvent.

There is no restriction | limiting in particular in the thickness of the said anisotropic conductive film, According to the objective, it can select suitably, For example, it is preferable that it is 1 micrometer-50 micrometers, and it is more preferable that it is 10 micrometers-40 micrometers.

The said anisotropic conductive film is arrange | positioned on a peeling film by apply | coating on a peeling film and drying.

There is no restriction | limiting in particular about the shape, a structure, a size, thickness, a material (material), etc. as said peeling film, Although it can select suitably according to the objective, The thing with favorable peelability and high heat resistance is preferable, for example, The peeling PET (polyethylene terephthalate) sheet etc. which apply | coated the peeling agent, such as silicone, are mentioned preferably. In addition, a PTFE (polytetrafluoroethylene) sheet may be used.

(Bonded body)

The joined body of the present invention includes the first circuit member, the second circuit member, and the anisotropic conductive film of the present invention, and further includes other members appropriately selected as necessary.

The said 1st circuit member and the said 2nd circuit member are joined through the said anisotropic conductive film.

<1st circuit member>

As said 1st circuit member, if the insulating film and wiring material are alternately formed in the surface, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, it has an insulating film on a board | substrate, and wiring material has a predetermined space | interval on the insulating film. And an insulating film is exposed between the wiring members. In addition, it is not limited to the above, Even if the wiring material is not formed on the insulating film, it is sufficient if the insulating film and the wiring material are alternately formed on the surface of the first circuit member.

There is no restriction | limiting in particular as said board | substrate, Although it can select suitably according to the objective, For example, a glass substrate is preferable.

As said insulating film, SiNx, another organic type insulating film etc. are mentioned, for example.

As a wiring material of a said 1st circuit member, For example, metals, such as aluminum, chromium, titanium, copper, molybdenum; Metal oxides (transparent electrode materials), such as ITO and IZO, etc. are mentioned, You may laminate | stack 1 type, or 2 or more types of metals and metal oxides (transparent electrode materials).

<Second circuit member>

The said 2nd circuit member is a wiring material or an electrode formed in the surface which faces the wiring material of the said 1st circuit member, For example, the flexible board which has a wiring material, an IC chip, etc. are mentioned.

As a wiring material or an electrode of a said 2nd circuit member, Cu, NiSn plating, NiAu plating, etc. are mentioned, for example.

Here, as shown in FIG. 1, the 1st circuit member 10 has the glass substrate 11, the insulating layer 12 on the board | substrate, and the wiring material 13 on the insulating layer at predetermined intervals, Formed.

The second circuit member 20 is formed with the substrate 21 and the wiring member or the electrode 22 spaced apart from each other by a predetermined interval.

The bonding body 100 has the 1st circuit member 10, the 2nd circuit member 20, and the said anisotropic conductive film 1 of this invention.

When the wiring member or the electrode 22 of the second circuit member 20, the conductive particles 2 in the anisotropic conductive film 1, and the wiring member 13 in the first circuit member 10 are conducted, The first circuit member 10 and the second circuit member 20 are electrically connected.

(Connection method)

The connection method of the present invention includes a first circuit member in which an insulating film and a wiring member are alternately formed on a surface thereof,

In the connection method of the 2nd circuit member in which the wiring material or the electrode was formed in the surface which opposes the wiring material of the said 1st circuit member,

The anisotropic conductive film of the present invention is sandwiched between the first circuit member and the second circuit member,

The anisotropic conductive film is cured by pressing while heating from the first circuit member and the second circuit member to connect the first circuit member and the second circuit member.

As a wiring material of a said 1st circuit member, For example, metals, such as aluminum, chromium, titanium, copper, molybdenum; Metal oxides (transparent electrode materials), such as ITO and IZO, etc. are mentioned, You may laminate | stack 1 type, or 2 or more types of metals and metal oxides (transparent electrode materials).

As said insulating film, SiNx, another organic type insulating film etc. are mentioned, for example.

As a wiring material or an electrode of a said 2nd circuit member, Cu, NiSn plating, NiAu plating, etc. are mentioned, for example.

Crimping condition

The said heating is determined according to a total amount of heat, and when it completes joining in connection time 10 second or less, it is preferable that heating temperature is performed at 120 degreeC-220 degreeC.

Although the said crimping | compression-bonding differs according to the kind of circuit member, it cannot be prescribed | regulated in one word, for example, in the case of a TAB tape, the pressure is 2 Mpa-6 Mpa, and in the case of an IC chip, the pressure of 20 Mpa-120 Mpa, COF In the case, it is preferable to carry out for 3 to 10 second each by the pressure of 2 Mpa-6 Mpa.

Example

Hereinafter, although the Example of this invention is described, this invention is not limited to the following Example at all.

(Production Example 1)

According to the compounding quantity (mass part) of the combination shown in following Table 1, the amine silane coupling agent was dripped and stirred, cooling phosphate acrylate in an ice bath (since synthesis | combination involves heat generation). The amine salts A1-A8 obtained from the phosphate acrylate and an amine silane coupling agent were synthesize | combined.

About each obtained amine salt, acidity was measured using the pH meter (brand name: HM-30P, the Toa DKK Corporation make). The results are shown in Table 1.

[Table 1]

* Phosphate acrylate (P-1M): mono- (2-methacryloyloxyethyl) acid phosphate, manufactured by Kyoeisha Chemical Co., Ltd., pH <1

* Phosphate acrylate (P-2M): di- (2-methacryloyloxyethyl) acid phosphate, manufactured by Kyoeisha Chemical Co., Ltd., pH <1

* Amine silane coupling agent (KBE-903): N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., pH = 10.5

* Amine silane coupling agent (KBM-573): N-phenyl-3-aminopropyl trimethoxysilane, the Shin-Etsu Chemical Co., Ltd. product, pH = 10.5

* Amine silane coupling agent (AY43-031): 3-ureidopropyltriethoxysilane, manufactured by Toray Dow Corning, Inc., pH = 10.1

<Analysis result of amine salt obtained from P-1M (phosphate acrylate) and KBE-903 (amine silane coupling agent)>

GC-MS analysis

Device name: Part number 6890N / 5975 manufactured by AGILENT TECHNOLOGIES

Measurement condition: A sample was prepared by dissolving 10 mg of the sample in 90 mL of THF solvent. 1 ml of the sample solution was injected into GC-MS and the measurement was performed. After holding at 280 degreeC of vaporization conditions and 40 degreeC / 5 minute inside columns, it heated up to 320 degreeC at the temperature of 10 degreeC / min, and hold | maintained for 7 minutes, and the measurement was complete | finished.

The measurement was performed about the following four types. The results are shown in FIG.

Phosphate acrylate (P-1M)

Amine silane coupling agent (KBE-903)

Amine salt A2 (P-1M: KBE-903 = 7: 3 (mass ratio))

Amine salt A3 (P-1M: KBE-903 = 5: 5 (mass ratio))

Since the peak derived from KBE-903 was not confirmed in amine salt A2, it turned out that all P-1M remains without being amine-chloride.

Since peak derived from KBE-903 was confirmed by amine salt A3, it is thought that all P-1M was amine-chloride and KBE-903 which was not consumed in the process of amine chloride was detected 9.8% of the total area.

Thus, by mixing KBE-903 having a mass ratio (P-1M: KBE-903) of P-1M and KBE-903 of at least 7: 3 (pH 3.3), preferably at least 5: Can be substantially eliminated, and it can be seen that the P-1M can be prevented from being adversely affected.

NMR analysis

Device Name: Mercury 300 manufactured by VARIAN

Measurement conditions: A sample was prepared by dissolving 5 mg of the sample in 0.75 ml of CDCl ₃ (heavy chloroform). The integration count was 16 times and the waiting time was performed for 5 seconds.

NMR analysis was performed about three types of P-1M, KBE-903, and an amine salt (P-1M: KBE-903 = 5: 5 (mass ratio)).

Based on peak values derived from A (-CH ₃ ) and B (= CH ₂ ) of P-1M, it was confirmed that the peak derived from -OH was significantly reduced in the amine salt. In addition, A (-CH ₃₎ and _{B (= CH 2) B (} = CH 2) in that it was not a change in the ratio of it was found that the reaction did not.

Similarly, based on the peak value derived from -CH ₂ from KBE-903, it was confirmed that almost no change was observed in the peak derived from NH ₂ from the amine salt.

Therefore, it is presumed that the obtained amine salt has the following structural formula. In addition, since there are two hydroxyl groups in phosphate acrylate, although both hydroxyl groups may be amine-chloride at all, the following structural formula shows the case where only one hydroxyl group is amine-chloride.

[Chemical Formula 5]

(Example 1)

60 parts by mass of phenoxy resin (trade name: YP50, manufactured by Toto Chemical Co., Ltd.), 35 parts by mass of radically polymerizable resin (product name: EB-600, manufactured by Daicel Cytech Co., Ltd.), phosphate acrylate and amine system shown in Table 1 In an adhesive composed of 3 parts by mass of an amine salt A1 obtained from a silane coupling agent and 2 parts by mass of a reaction initiator (trade name: Perhexa C, manufactured by Nippon Oil Holding Co., Ltd.), a conductive core having an average particle diameter of 4 μm in which NiAu plating was applied to the resin core Particles (trade name: AUL704, manufactured by Sekisui Chemical Co., Ltd.) were dispersed to have a particle density of 10,000 particles / cc, to prepare an anisotropic conductive film S1 having a thickness of 15 µm.

(Example 2)

Example 1 WHEREIN: Except having substituted the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent by the amine salt A2 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S2 was produced.

(Example 3)

Example 1 WHEREIN: Except having substituted the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent by the amine salt A3 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S3 was produced.

(Example 4)

Example 1 WHEREIN: Except having substituted the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent by the amine salt A4 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S4 was produced.

(Example 5)

In Example 1, except having replaced the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent with the amine salt A5 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S5 was produced.

(Example 6)

In Example 1, except having replaced the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent with the amine salt A6 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S6 was produced.

(Example 7)

Example 1 WHEREIN: Except having substituted the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent by the amine salt A7 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S7 was produced.

(Example 8)

Example 1 WHEREIN: Except having substituted the amine salt A1 obtained from the phosphate acrylate and an amine silane coupling agent by the amine salt A8 obtained from the phosphate acrylate and amine silane coupling agent shown in Table 1, In the same manner as in 1, anisotropic conductive film S8 was produced.

(Comparative Example 1)

When it does not contain phosphate acrylate and amine silane coupling agent

60 parts by mass of a phenoxy resin (trade name: YP50, manufactured by Toto Chemical Co., Ltd.), 35 parts by mass of a radically polymerizable resin (trade name: EB-600, manufactured by Daicel Cytech Co., Ltd.), and a reaction initiator (trade name: Perhexa C, Nippon Oil Holding Co., Ltd.) Electroconductive particle (article name: AUL704, Sekisui Chemical Industry Co., Ltd. product) was disperse | distributed so that it might become particle density of 10,000 pieces / sec, and the anisotropic conductive film R1 of thickness 15micrometer was manufactured.

(Comparative Example 2)

When it contains only phosphate acrylate

In Comparative Example 1, an anisotropic conductive film R2 was produced in the same manner as in Comparative Example 1 except that 1 part by mass of phosphate acrylate (trade name: P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) was blended.

(Comparative Example 3)

When containing only amine silane coupling agent

In Comparative Example 1, anisotropic conductive film R3 was produced in the same manner as in Comparative Example 1 except that 1 part by mass of an amine silane coupling agent (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended.

(Comparative Example 4)

When only the ureidosilane coupling agent is contained

In Comparative Example 1, anisotropic conductive film R4 was produced in the same manner as in Comparative Example 1 except that 1 part by mass of a ureidosilane coupling agent (trade name: AY43-031, manufactured by Toray Dow Corning Co., Ltd.) was blended.

(Comparative Example 5)

In the case of phosphate acrylate + isocyanate silane coupling agent (using isocyanate silane coupling agent of JP 2003-282637 A)

In Comparative Example 1, 1 part by mass of phosphate acrylate (trade name: P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) and 1 part by mass of isocyanate-based silane coupling agent (trade name: Y5187, manufactured by Shin-Etsu Chemical Co., Ltd.) Except for the same thing as in Comparative Example 1, an anisotropic conductive film R5 was produced.

(Comparative Example 6)

When each is compounded in the system, without forming an amine salt from a phosphate acrylate and a ureidosilane coupling agent beforehand-

In Comparative Example 1, 1 part by mass of phosphate acrylate (trade name: P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) and 1 part by mass of ureidosilane coupling agent (trade name: AY43-031, manufactured by Tore Dow Corning Corporation) Except as mix | blended with, it carried out similarly to the comparative example 1, and manufactured the anisotropic conductive film R6.

(Comparative Example 7)

When each is combined with the system, without forming an amine salt from a phosphate acrylate and an amine silane coupling agent beforehand-

In Comparative Example 1, 1 part by mass of a phosphate acrylate (product name: P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) and an amine silane coupling agent (product name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) alone Except mix | blended, it carried out similarly to the comparative example 1, and manufactured the anisotropic conductive film R7.

(Comparative Example 8)

When amine compounds other than phosphate acrylate + amine silane coupling agent are used

A monoethanolamine salt (molecular structure: NH ₃ CH ₂ OH) was added dropwise while stirring phosphate acrylate (trade name: P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) to generate an amine salt B1. PH of the obtained amine salt B1 was measured using the pH meter (brand name: HM-30P, Toa DKK Corporation make), and pH was 7.2.

In Comparative Example 1, an anisotropic conductive film R8 was produced in the same manner as in Comparative Example 1 except that 3 parts by mass of the amine salt B1 prepared above was used.

<Evaluation of Storage Stability>

Next, using each anisotropic conductive film of Examples 1-8 and Comparative Examples 1-8 immediately after manufacture, and each anisotropic conductive film after exposure for 48 hours in 30% of 60% RH environment, it was carried out as follows. Each package was manufactured and conduction resistance and adhesive strength were measured as follows. And storage stability was evaluated by the contrast after 48 hours of exposure in the 60% RH environment at the beginning and 30 degreeC.

<Production of Mounting Body>

As the evaluation substrate, COF (50 µm P, Cu 8 µm t-Sn plating, 38 µm t-Sperflex substrate) and IZO coated glass (total surface IZO coat, glass thickness 0.7 mm) were bonded.

Each anisotropic conductive film of Examples 1-8 and Comparative Examples 1-8 was slit to 1.5 mm width, and was affixed on IZO coating glass. After temporarily fixing COF on it, using 100-micrometer-thick Teflon (trademark) as a cushioning material with a width of 1.5 mm of a heat tool, it bonded together for 10 second by bonding conditions 190 degreeC and 3 Mpa, and manufactures each package. It was.

Moreover, each mounting body was produced similarly except having changed IZO coating glass into SiNx coating glass (full surface SiNx coat, glass thickness 0.7mm).

<Measurement of Conducting Resistance of the Mounting Body>

About each mounting body manufactured using the said IZO coating glass, the conduction resistance after initial stage (after connection) and 85 degreeC, 85% RH, and 500 hours was measured. The conduction resistance was measured using a digital multimeter (part number: digital multimeter 7555, manufactured by Yokogawa Electric Co., Ltd.) to measure the conduction resistance when a current of 1 mA was flown by the 4-probe method. Table 2 shows the result of each package which was connected immediately after manufacture of each anisotropic conductive film, and the result of each package which was connected after exposing each anisotropic conductive film at 30 degreeC 60% RH for 48 hours is shown in Table 3. .

<Measurement of Adhesive Strength of the Mounting Body>

About each package manufactured using the said IZO coating glass and the said SiNx coating glass, the adhesive strength after 500 hours at the initial stage (after connection) and 85 degreeC and 85% RH was measured. The adhesive strength measured the adhesive strength at the time of pulling up COF by 50 mm / sec. Measurement speed using the tensile tester (product number: RTC1201, AND). Table 2 shows the result of each package which was connected immediately after manufacture of each anisotropic conductive film, and the result of each package which was connected after exposing each anisotropic conductive film at 30 degreeC 60% RH for 48 hours is shown in Table 3. .

<< Result of the mounted body which was connected immediately after manufacturing an anisotropic conductive film >>

TABLE 2-1

Table 2-2

<< Result of the package which connected after exposing the anisotropic conductive film to 60% RH for 48 hours at 30 degreeC >>

Table 3-1

Table 3-2

From the results of Table 2 and Table 3, Comparative Example 1 expresses the properties immediately after the anisotropic conductive film is produced, but the storage stability is poor. Therefore, the anisotropic conductive film was exposed to 60% RH at 30 ° C. for 48 hours compared to immediately after the production. It turned out that the adhesive strength after this falls.

Moreover, when the compounding quantity of phosphate acrylate was large, it turned out that conduction resistance becomes high and the adhesive force with respect to IZO improves, but the adhesive force with respect to SiNx tends to fall.

Moreover, when the compounding quantity of an amine silane coupling agent is large, it turned out that conduction resistance falls and the adhesive force to SiNx improves, but the adhesive force to IZO tends to fall.

In the anisotropic conductive film containing the amine salt produced | generated from the phosphate acrylate and the amine silane coupling agent, favorable conduction | reliability reliability and adhesive strength were shown (Examples 1-8). Especially in Examples 2-4 and Examples 6-8 which pH of an amine salt is the range of 3-8, favorable conduction resistance value and adhesive strength were shown after 60% RH and 48-hour exposure test at 30 degreeC.

On the other hand, good conduction reliability and adhesiveness were not obtained only by containing the raw material (phosphate acrylate, an amine silane coupling agent) which does not contain an amine salt and produces | generates an amine salt (Comparative Examples 1-4). Moreover, also when silane coupling agents other than an amine silane coupling agent were used, the result was the same (Comparative Examples 4 and 5). Moreover, even if the raw material of an amine salt was mix | blended, even when an amine salt was not formed previously, the favorable result was not obtained (Comparative Examples 6 and 7). Even in the amine salt, good results were not obtained in the amine salts formed other than the phosphate acrylate and the amine silane coupling agent (Comparative Example 8).

Industrial availability

The anisotropic conductive film of the present invention is, for example, a connection between a terminal of a flexible printed circuit board (FPC) or an IC chip and an ITO (Indium Tin Oxide) electrode formed on a glass substrate of an LCD panel, a connection of a COF and a PWB, and a TCP and a PWB. It is used suitably for the connection of circuit members, such as the connection of a, a connection of a COF and a glass substrate, a connection of a COF and a COF, a connection of an IC board | substrate and a glass substrate, and a connection of an IC board | substrate and a PWB.

1: anisotropic conductive film
2: electroconductive particle
10: first circuit member
11: glass substrate
12: Insulating film
13: wiring material
20: second circuit member
21: substrate
22: wiring material or electrode
100: conjugate

Claims (4)

An anisotropic conductive film containing conductive particles, a film-forming resin, a radically polymerizable compound, a curing agent for generating free radicals, and an amine salt obtained from a phosphoric acid (meth) acrylate and an amine silane coupling agent. The method of claim 1,
The anisotropic conductive film whose pH of an amine salt is 3-8. A first circuit member having an insulating film and a wiring member alternately formed on a surface thereof;
A second circuit member having a wiring member or an electrode formed on a surface of the first circuit member that faces the wiring member;
The anisotropic conductive film of Claim 1 or 2 is provided,
The said 1st circuit member and the said 2nd circuit member are joined through the said anisotropic conductive film, The bonding body characterized by the above-mentioned. A first circuit member having an insulating film and a wiring member alternately formed on a surface thereof;
In the connection method of the 2nd circuit member in which the wiring material or the electrode was formed in the surface which opposes the wiring material of the said 1st circuit member,
The anisotropic conductive film of Claim 1 or 2 is clamped between the said 1st circuit member and the said 2nd circuit member,
The said anisotropic conductive film is hardened | cured by pressurizing while heating from the said 1st circuit member and the said 2nd circuit member, and the said 1st circuit member and the said 2nd circuit member are connected, It is characterized by the above-mentioned.

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