JPH07228669A - Epoxy-acrylic resin composition - Google Patents

Abstract

PURPOSE: To provide an epoxy-acrylic resin compsn. which comprises an epoxy resin, an arom. amine, and a specific compd., can form a film by the exposure to ultraviolet rays, dispenses with a solvent and a heating step, and is excellent in reactivity and in which constituting ingredients are compatible with each other and are homogeneously mixed.

CONSTITUTION: This compsn. comprises (A) an epoxy resin, (B) an arom. amine of formula I [wherein R¹ is -CR³ ₂- (wherein R³ is CF₃, H, CH₃ or cyclohexyl), -SO₂-, or a divalent olefin group of formula II; and R² is H, Cl, CH₃, C₂H₅ or C₃H₇], (C) a compd. contg. at least one (meth)acryloyl group and having a solubility parameter of 9.2-12.4 [e.g. benzyl (meth)acrylate], and optionally (D) a compd. contg. at least one (meth)acryloyl group and at least one carboxyl group and (E) a compd. contg. at least one (meth)acryloyl group and at least one epoxy group.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy-acrylic resin composition, a film-like resin composition formed therefrom, and a cured product of such a film-like composition.

[0002]

2. Description of the Related Art Epoxy resin compositions are thermosetting, have high adhesive strength, are excellent in mechanical strength, heat resistance and the like, and are widely used as adhesives and materials for printed wiring boards. However, the epoxy resin composition is usually in a liquid state, and there are one-pack type, two-pack type, etc., but both have poor workability, and the thickness varies when applied, and when used as an adhesive, it is bonded. There was a problem that the power varied.

Therefore, a film-shaped epoxy composition is known as an improvement of the liquid epoxy resin composition. This product has good workability, and since the two liquids are mixed in advance, there are few variations in the characteristic values such as adhesive strength, and since it is not in solution, the curing agent and catalyst diffusion ratio is small,
It has the advantage of high potential or long shelf life. However, since the epoxy resin alone is generally insufficient in film-forming property, a film-forming resin such as polyvinyl butyral, polyamide, polyvinyl acetate, acrylic resin as described in, for example, US Pat. No. 3,449,280. It was usually essential to add polymeric materials such as.
Therefore, there are the following problems.

(A) A solvent is indispensable for dissolving the polymer material, and a heating step is required to volatilize the solvent later, and the epoxy resin may partially react in the heating step. There is. (B) To reduce the reactivity of the epoxy resin in order to control the reactivity in the heating step,
The epoxy resin and curing agent that can be used are limited. (C)
There is a problem that the content of the epoxy resin is relatively reduced and the adhesive strength, reactivity, etc. are lowered. (D) Epoxy resin is highly polar, and therefore has poor compatibility with the film-forming resin.
The types of film-forming resins that can be used are limited to those that are extremely expensive, and there is a risk of phase separation.

On the other hand, it is possible to prepare a film containing solid epoxy as the main component by volatilizing the solvent after heat melting or dissolving it in the solvent, but there are the following problems. (A) The epoxy resin may react in the heating step.
(B) Since the solid epoxy is the main component, the film forming property is insufficient and the handling is difficult. (C) The thickness of the film is limited. (D) Since the reactivity in the heating step is controlled, the reactivity of the epoxy resin is lowered, and the usable epoxy resin and curing agent are limited.

Therefore, in order to obtain a film-shaped epoxy resin composition which is heat-curable and is suitable for adhesives without using a solvent, US Pat. Nos. 5,086,088 and 4,55
No. 2,604, No. 4,092,443, No. 4,2
Radiation curable acrylic-epoxy resin compositions have been proposed in Nos. 52,593, 4,521,490 and 4,524,181.

However, these compositions are generally poor in compatibility between the epoxy resin and the acrylic resin and have problems such as lack of heat resistance and adhesive strength. In particular, when an aromatic amine is used as a curing agent, there is a tendency that the compatibility between the epoxy resin and the acrylic resin is poor. Therefore, the use of the aromatic amine is effective in the epoxy resin and the acrylic resin composition. Difficult and, as a result, has a high glass transition point after curing, specifically 150 ° C.
It was not possible to obtain a uniform resin composition having a glass transition point exceeding the above. Further, when an aromatic amine outside the scope of the present invention is used, there is a problem that the composition lacks potential.

Further, in order to adjust the viscosity and the curing speed, a bifunctional or higher acrylic ester may be used, but in such a case, the compatibility between the epoxy resin and the acrylic ester resin becomes further poor. , Gelled,
Syneresis (a phenomenon in which the gel contracts in volume and eliminates liquid components) occurs, and it has been difficult to use for pressure-curable non-fluid adhesives such as structural adhesives for aircraft.

Further, in recent years, with the miniaturization and refinement of electronic parts, these circuits have also been densified, and in order to electrically connect the precision circuits, a predetermined amount of conductive particles is contained in the insulating adhesive. The conductive adhesive contained is often used. In particular, an anisotropic conductive adhesive film known as a Z-axis film (hereinafter referred to as "ZAF") has been proposed and used.

Such a ZAF film has conductivity only in the thickness direction of the film by adhesion, and maintains insulation in the plane direction, so that it is possible to electrically connect circuits in the vertical direction. It will be possible. However, JP-A-6
The anisotropic conductive adhesive films disclosed in JP-A No. 2-181379, JP-A No. 1-113480 and JP-A No. 1-309206 have poor heat resistance and adhesive strength, resulting in poor electrical connection stability. was there. Further, since such a film has a low glass transition point, it requires a special cooling step in order to shift to a glass state after pressurization and heating to obtain a reliable electrical connection. That is, if the glass transition point is high, the glass state can be instantaneously transferred, and such a step can be omitted. Further, since pressure and heat are applied in a short time, an organic solvent is used in the conventional adhesive, so that there is a problem of foaming due to volatile components contained in the adhesive. Therefore, there are problems such as deterioration of heat resistance and easy penetration of water, resulting in deterioration of electric insulation.

[0011]

DISCLOSURE OF THE INVENTION In view of the above problems, the present invention provides (a) a film which can be formed by irradiation with ultraviolet rays as a film before thermosetting, and (b) requires a solvent and a heating step for forming the film. When it is formed into a film, the compatibility of the (c) constituents is good, (d) the whole is uniform, (e) the reactivity and the potential are excellent, and (f) the workability is good. , (G) can be heat-cured, and (h) has no problem of syneresis, and as a film after heat-curing,
(I) Tg is high, specifically, at 150 ° C. or higher,
It is intended to provide an epoxy-acrylic resin composition (j) having high toughness and (k) low hygroscopicity, a film-shaped resin composition using the same, and a cured product thereof.

Another object of the present invention is to provide an anisotropic conductive adhesive film containing a predetermined amount of conductive particles and having excellent electrical connectivity.

[0013]

The first aspect of the present invention is as follows.
(A) Epoxy resin (hereinafter referred to as "compound (a)"), (b) General formula (1):

[0014]

[Chemical 3]

(Wherein R ¹ is --CR ³ _2- (wherein R ³ independently represents CF ₃ , H, CH ₃ or cyclohexyl), --SO _2-, or a divalent group represented by the following formula: A fluorene group;

[0016]

[Chemical 4]

R ² is independently H, Cl, CH ₃ , C ₂
H ₅ or C ₃ H ₇ . ) Has an aromatic amine (hereinafter referred to as "compound (b)") and (c) one or more acryloyl groups and / or methacryloyl groups in the molecule, and its solubility parameter is 9.2 to 12. .4
An epoxy-acrylic resin composition containing the compound (hereinafter referred to as "compound (c)").

A second aspect of the present invention is an anisotropic conductive composition which is the epoxy-acrylic resin composition according to the first aspect and further contains conductive particles (g). A third aspect of the present invention is a film-shaped resin composition obtained by polymerizing the composition according to the first or second aspect by ultraviolet irradiation. A fourth aspect of the present invention is a film adhesive or an anisotropic conductive adhesive film comprising the film resin composition of the third aspect.

A fifth aspect of the present invention is an epoxy-acrylic resin cured product obtained by heating and curing the film composition of the third aspect. Other aspects of the invention will be readily apparent from the description below. First, the compounds constituting the epoxy-acrylic resin composition of the present invention will be described.

The epoxy resin of the compound (a) is a compound having a highly reactive epoxy group in the molecule,
Many are known that have different chemical structures. Examples thereof include various epoxy resins such as bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, cresol novolac type epoxy, fluorene epoxy, glycidyl amine, and aliphatic epoxy, and one or more of them are used. be able to.

The compound (b) is a curing agent for the epoxy resin compound (a). In order for the cured product of the compounds (a) and (b) to be a cross-linked polymer, the compound (b) must be Three or more active hydrogens are required in one molecule. Further, the compound (b) needs to withstand a film forming step by curing with ultraviolet rays or the like at room temperature after mixing with the compounds (a) and (c) to realize a long pot life. . It is generally known that aromatic amines are weaker in basicity than aliphatic amines and that their reactivity with epoxy resins at room temperature is much slower than aliphatic amines due to steric hindrance due to aromatic rings (( H. Lee and K. Ne
ville "Handbook of Epoxy Resins" Chapter8 McGRAW-HI
(See LLBook Company 1982). In particular, the general formula (1)
The aromatic amine having a structure represented by: has a particularly long pot life and is essential to the present invention. Specifically, diaminodiphenylsulfone and its derivative, diaminodiphenylmethane and its derivative, diaminodiphenylfluorene and its derivative and the like, for example, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3 , 3'-Dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 4,4'-
Diaminodiphenyl sulfone, 3,3'-dichloro-
4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenyl sulfone, 9,9'-bis (4-aminophenyl) fluorene, 9,9 ' -Bis (3-chloro-4-aminophenyl) fluorene, 9,9'-bis (3-methyl-4-aminophenyl) fluorene, 9,9'-bis (3-ethyl-4-aminophenyl) fluorene, etc. And one or more of these can be used.

Regarding the amount of the compound (b) added, it is known that the glass transition temperature of the cured product becomes the highest (the best heat resistance) when the compound (a) is blended in an amount of an equivalent amount. . It is also possible to use the compound (b) in an amount greater than or less than the equimolar equivalent amount relative to the compound (a) for the purpose of adjusting the crosslink density, but if it exceeds 2 times the equimolar equivalent amount or less than 0.5 times the equivalent amount. If used, the glass transition temperature is extremely lowered, which is not preferable.

The compound (c) is required to have at least one acryloyl group and / or methacryloyl group in the molecule in order to be easily polymerized by irradiation with ultraviolet rays, and at the same time, the compounds (a) and ( Not only is it compatible with and can be mixed with b), but it is also necessary to maintain a uniform state after solidification by polymerization by irradiation with ultraviolet rays. Otherwise, the film solidified by such polymerization becomes non-uniform due to phase separation, and it becomes difficult to obtain high heat resistance and reliability of adhesive strength after thermosetting.

In order for the compound (c) having an acryloyl group and / or a methacryloyl group in the molecule to be compatible with the compounds (a) and (b), the method of Fedors (RFFedors, Polym. Eng. .Sci., 14, 147 (1974)) solubility parameter (S) of compound (c)
It is necessary that P) be 9.2 to 12.4. Specific examples of the compound (c) include benzyl acrylate, benzyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, 2-hydroxy-3-phenoxyp 2-. Hydroxy-3-phenoxypropyl acrylate, Ropyl methacrylate, 2-hydroxy-3-dicyclopentaoxypropyl 2-hydroxy-3-dicyclopentaoxypropyl methacrylate, acrylate, 2-
Hydroxy-3-dicyclopenteoxypropyl acrylate, 2-hydroxy-3-dicyclopenteoxypropyl methacrylate, 2-hydroxy-3-phenylphenoxy acrylate, 2-hydroxy-3-phenylphenoxymethacrylate, phenoxyacrylate, phenoxy Methacrylate, phenoxyethyl acrylate, phenoxyethyl (meth) acrylate, phenyl acrylate, phenyl methacrylate, phthalate acrylate, phthalate methacrylate, phthalate diacrylate, phthalate dimethacrylate, dicyclopentanyl diacrylate, dicyclo Pentanyl dimethacrylate, bisphenol A epoxy diacrylate, bisphenol A epoxy dimethacrylate, diacrylo Shi ethyl isocyanurate,
Examples thereof include dimethacryloxyethyl isocyanurate, trisacryloxyethyl isocyanurate, trismethacryloxyethyl isocyanurate, and modified products of these compounds, and one or more of these can be used.

Regarding the amount of the compound (c) added, 5 parts by weight or more should be added to 100 parts by weight of the total amount of the compounds (a) and (b) in order to give a sufficient cohesive force to the ultraviolet-cured film. On the other hand, on the other hand, 100 parts by weight of the total amount of the compounds (a) and (b) is 100 parts by weight so that the adhesive strength when the film is heat-cured is sufficiently high.
It should be less than or equal to parts by weight. If necessary, a compound having two or more acryloyl groups and / or methacryloyl groups may be added to the compound (c) to introduce a crosslinked structure into the acrylic and / or methacrylic phase. .

The composition of the first aspect of the present invention may contain a compound (d) having at least one acryloyl group and / or methacryloyl group and one or more carboxyl group in the molecule, or otherwise. Alternatively, the compound (e) having at least one acryloyl group and / or methacryloyl group and one or more epoxy group in the molecule may be contained.

As the compound (d), acrylic acid,
Methacrylic acid, acryloyloxyethyl phthalic acid,
Examples thereof include methacryloyloxyethyl phthalic acid, acryloyloxyethyl succinic acid, and methacryloyloxyethyl succinic acid. Examples of the compound (e) include glycidyl acrylate and glycidyl methacrylate, and monoacrylates and monomethacrylates of various polyfunctional epoxy compounds.

In the epoxy-acrylic resin composition of the present invention, the compound (d) and / or (e) is added in an appropriate amount to introduce cross-linking between the epoxy phase and the acrylic and / or methacrylic phase. And the epoxy phase,
It is possible to reduce the size of the non-uniform structure due to phase separation with the acrylic phase when heat set, resulting in improved adhesion. These compounds (d) and (e)
Of at least one of the compounds (a) and (b)
It is preferable that the amount is 0.3 to 50 parts by weight based on 100 parts by weight in total. This is because if it is out of this range, a sufficient adhesive force of the film adhesive may not be obtained.

The epoxy-acrylic resin composition of the present invention may contain a solid catalyst (f) for increasing the reactivity of the compound (b). Examples of such solid catalyst (f) include 3-boron fluoride amine complex, sulfur compound, salicylic acid, salicylic acid metal salt, tertiary amine compound, and cobalt acetylacetonate, copper acetylacetonate, manganese acetylacetonate. And other metal chelate compounds. Here, the content of the solid catalyst (f) is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the compounds (a) and (b). This is because if the catalyst content is less than 0.1 parts by weight, the catalytic effect is poor, and conversely if it exceeds 30 parts by weight, the potential of the composition decreases. Therefore, in order to further improve the good balance between the catalytic effect and the latent potential, the content of the solid catalyst (f) is optimally in the range of 0.5 to 10 parts by weight.

Further, the epoxy-acrylic resin composition of the present invention preferably further contains conductive particles in order to further expand its use and obtain usable noteworthy characteristics. The conductive particles can be arbitrarily selected from known materials, but may be metal particles alone, agglomerated metal particles, molten metal particles, or particles obtained by coating a polymer core material with a metal. In particular, particles in which a polymer core material is coated with a metal are preferable in terms of excellent electrical connection stability and easy dispersion and mixing.

Here, the content of the conductive particles is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the compounds (a), (b) and (c). This is because if the content of the conductive particles is less than 0.1 parts by weight, it becomes difficult to secure the conductivity, while if it exceeds 30 parts by weight, the horizontal insulating property becomes poor and a short circuit between circuits may occur. . Therefore, in consideration of such balance, it is optimal to use the conductive particles in the range of 3 to 20 parts by weight.

Next, a method of forming a film from the epoxy-acrylic resin composition of the present invention will be described. As a method of forming a film, for example, a method of adding a predetermined amount of a photoradical initiator as a radical generator to such a resin composition and irradiating with ultraviolet rays is suitable.
Ultraviolet curing is an effective means for forming a film because it is simple and can be cured quickly. As the photo radical initiator used in the present invention, 2-hydroxy-2-methyl-
1-phenylpropan-1-one, benzoin, acetophenone and the like can be mentioned. Such a photo radical initiator is
0.01-10 based on 100 parts by weight of the compound (c).
It is preferable to add it in the range of parts by weight, and optimally it is 0.
It is in the range of 05 to 5 parts by weight.

In forming the resin composition of the present invention into a film, any method may be used, for example, the resin composition is sandwiched between two flat peelable films, and a knife is provided on a suitable substrate or film. Coating using a coating means such as a coater or a roll coater, and others can be used. The method of polymerization by the ultraviolet irradiation, in particular,
There is a method of adding a photo radical initiator to the resin composition of the present invention and irradiating it with ultraviolet rays. The obtained film-shaped composition,
Since it is manufactured by UV curing, it is not only a solvent-free system, it can easily be made from very thin to thick film,
Since there is little exotherm during curing, it is possible to add a heat activated catalyst prior to curing. Further, if necessary, a masking film can be used to selectively form a film of only a part of the composition.

The resin composition of the present invention becomes a film because the compound (c) is radically polymerized and polymerized by irradiating it with ultraviolet rays. The film is sandwiched between two objects to be bonded and heated, whereby the curing reaction of the compounds (a) and (b) proceeds to exert an adhesive force. The heating temperature at this time is 150 to 25
0 ° C. is suitable, and the heating time is 10 seconds to 10 hours. These conditions can be controlled in a wide range by the amount and type of curing agent and the catalyst.

The thickness of the film composition or film adhesive is preferably 0.01 to 10 mm.
If it is less than 0.01 mm, the adhesive strength and mechanical strength when functioning as an adhesive are poor, while if it exceeds 10 mm,
This is because ultraviolet rays do not reach and it is difficult to form a uniform film. The film adhesive of the present invention can be used for applications to which an epoxy adhesive can be applied. Specifically, it can be applied to metals, glass, plastics, ceramics and the like.

Further, although the film composition of the present invention can be used as an ordinary adhesive, it has a small amount of impurity ions and is excellent in heat resistance. Suitable for use as an anisotropic conductive adhesive film. In addition, the composition of the present invention can be used as a structural material for aircraft or a FRP material. Incidentally, the composition of the present invention, depending on the application, a tackifier, a coupling agent, an antioxidant, a viscosity modifier,
It is preferable to add a filler or the like.

[0037]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. In addition,
In the following example, book 1, book 2, ... and ratio 1, book 2, ...
Although the following description is used, the former is an example of the present invention (for example, present 1 is the present invention example 1), and the latter is a comparative example (for example, ratio 1 is comparative example 1).
It is for explaining. Example 1 In this example, the results of examining the necessary conditions for the compound (b) are shown.

Epoxy resin (DER 332 made by Dow Chemical Co. having an epoxy equivalent of about 175) was added with an equivalent amount of the amine compound shown in Table 1 below and mixed and dissolved to form a uniform mixture. Obtained. Composition 5 in which 38 g of this mixture was mixed with 12 g of 2-hydroxy-3-phenoxypropyl acrylate (Aronix (trademark) M-5700 manufactured by Toagosei Kagaku Kogyo Co., Ltd.)
0 grams was left at room temperature (23 ° C) for 20 hours. After standing, gelled one is NG, non-gelled one is O
It was evaluated as K. From the evaluation results shown in Table 1 below, it is understood that all amines evaluated as OK are represented by the general formula (1).

Table 1 Examples of storage stability of DER-332 + M5700 + various amine compounds (b) at room temperature Amine compound (b) Evaluation ratio 1 Diethylenetetramine NG ratio 2 Triethylenetetramine NG ratio 3 m-Xylylenediamine NG ratio 4 m -Phenylenediamine NG ratio 5 2,4-toluenediamine NG ──────────────────────────────────── 1 4,4'-diaminodiphenylmethane OK main 2 4,4'-diaminodiphenylsulfone OK main 3 9,9'-bis (4-aminophenyl) fluorene OK main 4 9,9'-bis (3-chloro-4- Aminophenyl) fluorene OK This 5 3,3′-dichloro-4,4′-diaminodiphenylmethane OK This 6 3,3′-dimethyl-4,4′-diami In 5,5'-diethyl-diphenylmethane OK Example 2 This example shows the results of investigation on the requirements of the compound (c).

DER-332 used in Example 1 above was replaced with 4,4'-diaminodiphenyl sulfone (DDS, manufactured by Ciba-Geigy) or 9,9'-bis (3-chloro-4-aminophenyl) as an epoxy resin. Fluorene (CA
F, manufactured by 3M Co., Ltd.), 30 parts by weight of various (meth) acrylates shown in Table 2 below and 100 parts by weight of the resulting mixture, and a photoradical initiator.
-Hydroxy-2-methyl-1-phenylpropane-1
-On (Merck Japan KK, Dulcure (trademark) D
1173) 0.06 parts by weight were mixed. The resin composition thus obtained was sandwiched between two polyethylene terephthalate films coated with a release coating so as to have a thickness of 0.5 mm, and was irradiated with 37 mW / cm ² ultraviolet rays from a high pressure mercury lamp for 1 minute. The condition of the obtained film is shown in Table 2 below. The second
In the table, the case where a uniform transparent film was obtained after curing was OK, and the case where a nonuniform opaque film was obtained was N.
Denote by G. In addition, in this Table 2, the solubility parameter S of various (meth) acrylates calculated by the Fedors method (RFFedors, Polym.Eng.Sci., 14, 147 (1974))
The value of P is also shown. From the results shown in Table 2, in order to obtain a uniform film, the SP value of (meth) acrylate was 9.
It is clear that it is a necessary condition that it is 2 or more and 12.4 or less.

[0041]Table 2 Compatibility of various acrylates or methacrylates (c) with DDS and CAF Acrylate or An example Methacrylate (c) SP value DDS CAF Ratio 6 t-Butyl Acrylate 8.5 NG NG Ratio 7 2-Ethylhexyl Acrylate 8.6 NG NG Ratio 8 Isooctyl Acrylate 8.6 NG NG Ratio 9 Isobornyl Acrylate 8.7 NG NG Ratio 10 Ethyl Acrylate 8.9 NG NG ratio 11 cyclohexyl methacrylate 8.9 NG NG ratio 12 cyclohexyl acrylate 8.9 NG NG ratio 13 2-hydroxyethyl acrylate 12.5 NG NG ─────────────────── ──────────────── Present 7 Dicyclopentanyl methacrylate 9.3 OK OK Present 8 Dicyclopentanyl acrylate 9.3 OK OK Present 9 R-551^a) 10.3 OK OK This 10 phenoxy acrylate 10.5 OK OK This 11 methacrylic acid 10.7 OK OK This 12 M-5700 11.9 OK OK This 13 M-315^b) 11.9 OK OKBook 14 90727A ^C) 12.0 OK OK a) Bisphenol A type Epo manufactured by Nippon Kayaku Co., Ltd.
Xydiacrylate b) Toa Gosei Chemical Co., Ltd., tris (acryloxy)
Ethyl) isocyanurate c) Okamura Oil Co., Ltd., o-[(2-hydroxy-3
-Acryloyloxy) propyloxy] phenylphe
NoorExample 3 In this example, the amount of compound (c) added was investigated.
The results are shown below.

The resin composition as described in Table 3 below.
67 weight of DER-332 (epoxy resin) as a product
Parts, DDS (diamine) 33 parts by weight, M-5700
2 to 120 parts by weight of (acrylate), and dark
A (trademark) D1173 (photo radical initiator) 0.01
~ 0.24 parts by weight, 37mW / from high pressure mercury lamp
cm ²0.2mm thick film with 1 minute UV irradiation
It was created. Each film at 180 ℃ for 2 hours
Cured to comply with ASTM D-1002-1964
The tensile shear and peel adhesions were measured by the method.
The measurement results obtained are shown in Table 3 below. Compound (c)
50kgf / cm is added²More shear adhesive strength can be obtained
Conditions are preferable, and 100 parts by weight or less is preferable. on the other hand,
When the addition amount of the compound (c) is 2 parts by weight or less, the amount of the compound before heat curing is
The film has a small cohesive force and is difficult to handle.
Incomplete).

Table 3 Adhesive strength of DER-332 + DDS + M-5700 film Composition (parts by weight) Shearing adhesive strength Peeling adhesive example DER-332 DDS M-5700 D1173 (kgf / cm ² ) (kgf / 25mm) book 15 67 33 5 0.01 150 2.4 pcs 16 67 33 10 0.02 140 2.1 pcs 17 67 33 20 0.04 100 0.9 pcs 18 67 33 40 0.08 70 0.8 pcs 19 67 33 80 0.16 50 0.5 pcs 20 67 33 120 0.24 40 0.5 Example 4 In this example The results obtained by examining the effect of addition of the compounds (d) and (e) are shown below.

As shown in Table 4 below, 67 parts by weight of DER-332 (epoxy resin), 33 parts by weight of DDS (diamine), M-5700 as a resin composition.
(Acrylate) 10 to 80 parts by weight, Dulcure (trademark) D1173 0.02 to 0.16 parts by weight, and further acrylic acid (AA) (main 21 to main 30) or methacrylic acid (MA) (main 31). ) Or glycidyl acrylate (GA) (main 32) and mix it with a high pressure mercury lamp.
Ultraviolet rays of mW / cm ² were irradiated for 1 minute to form a film having a thickness of 0.2 mm. After curing each film at 180 ° C. for 2 hours, the tensile shear adhesive strength and the peel adhesive strength were measured in the same manner as in Example 3 above. The measurement results obtained are shown in Table 4 below. Table 4 DER-332 + DDS + M- 5700 + adhesive strength composition of AA such as a film (parts by weight) shear adhesion peel adhesion Example DER-332 DDS M-5700 D1173 AA (kgf / cm 2) (kgf / 25mm) the 21 67 33 10 0.02 0 140 2.1 pieces 22 67 33 10 0.02 0.3 180 1.6 pieces 23 67 33 20 0.04 0 100 0.9 pieces 24 67 33 20 0.04 0.6 170 1.5 pieces 25 67 33 20 0.04 1.2 130 0.9 pieces 26 67 33 20 0.04 2.4 60 1.2 pieces 27 67 33 40 0.08 0 70 0.8 pcs 28 67 33 40 0.08 1.2 200 1.8 pcs 29 67 33 80 0.16 0 50 0.5 pcs 30 67 33 80 0.16 2.4 100 1.0 pcs 31 67 33 20 0.04 0.6 (MA) 190 2.2 pcs 32 67 33 20 0.04 0.6 (GA) 190 1.7 Example 5 (Main 33) In this example, a film was prepared in which salicylic acid was dispersed as a compound that enhances the reactivity of amine in the film composition. That is, DER-332 / DDS / M-5700 / D-1173 used in Book 31 of Example 4 above.
To the composition of /MA=67/33/20/0.04/0.6, 2 parts by weight of salicylic acid was added at room temperature to make a dispersion state, and then UV curing was performed in the same manner as in Example 3 above.
The film thus obtained was placed on a hot plate at 170 ° C., and the time until tackiness disappeared (tack free time) was measured to be about 5 minutes. On the other hand, the tack free time of the film containing no salicylic acid was about 15 minutes. Example 6 This example shows that high heat resistance is obtained after thermosetting a resin composition of the present invention having a composition as described in Table 5 below. The glass transition temperature Tg used for evaluation of heat resistance was measured using a dynamic viscoelasticity measuring device RSA2 manufactured by Rheometrics. Complex Young's modulus when 0.1% bending strain is applied to the measurement sample
^* E was measured and the temperature at which the peak value of E2 was exhibited was taken as Tg.

^* E = E1 + iE2 The measurement conditions are as follows: sample shape: width 5 mm × length 40 mm × thickness 1.3 mm strip temperature range: room temperature to 250 ° C. heating rate: 5 ° C. / 2.5 minutes Frequency: 3 Hz The obtained results are shown in Table 5 below.

Table 5 Example composition (parts by weight) Tg (° C) book 34 DER332 DDS M-5700 R551 D1173 185 67 33 8 2 0.05 book 35 DER332 FEP ^a) CAF DPMA ^b) MAc ^c) D1173 195 35 19 46 5 0.5 0.03 pcs 36 DER332 FEP OTBAF ^d) DPMA MAc D1173 196 37 20 43 5 0.5 0.03 pcs 37 DER332 FEP OTBAF M-5700 GMA ^e) D1173 190 38 20 42 10 10 0.3 a) FEP: Nippon Steel Chemical Co., Ltd. Fluorene epoxy resin: ESF-300 (trademark) b) DPMA: Hitachi Chemical Co., Ltd., dicyclobetanyl methacrylate: FA-513M (trademark) c) MAc: Mitsubishi Rayon Co., Ltd., methacrylic acid d) OTBAF: USA 3M, 9,9'-bis (3-
Methyl-4-aminophenyl) fluorene e) GMA: manufactured by Mitsubishi Rayon Co., Ltd., glycidyl methacrylate: ACRYESTR-G (trademark) Example 7 In this example, conductive particles were added to the film-shaped composition of the present invention. The anisotropic conductive adhesive film will be described.

An adhesive composition having the composition set forth in Table 6 below was prepared. a) Q-1010: Dow Chemical Co., bisphenol A epoxy resin (epoxy equivalent = about 186): Qua
trex 1010 (trademark) b) PKHC: made by Phenoxy Associates, thermoplastic phenoxy resin To the obtained adhesive composition, conductive particles, a coupling agent or a catalyst in the amounts shown in Table 7 below were added.

[0048] Table 7 conductive particles, coupling agents, additives added component present 38 present 39 ratio 14 gold-plated polymer particles ^{a catalyst) 12 15 12 A-187 b} ) 2.2 2 2.2 2E4M c) - - 4 .3 Salicylic Acid 5--Acetylacetonate Cobalt-5- a) Gold-plated polymer particles: manufactured by Nippon Chemical Industry Co., Ltd., Bright 20GNR4,6EH (trademark) b) A-187 manufactured by Nippon Unicar Co., Ltd., 3-glycid Oxypropyltrimethoxysilane (silane coupling agent) c) 2E4M: 2-ethyl-4-methylimidazole
1/2 triflate The composition obtained in the present 38 to 39 is irradiated with 37 mW / cm ² ultraviolet rays from a high pressure mercury lamp for 1 minute to give a thickness of 50 μm.
m film was made. With respect to the composition obtained in the ratio 14, a 50% toluene / acetone solution was prepared and dried in an oven at 80 ° C. for 10 minutes to form a film having a thickness of 20 μm. When the characteristics of the obtained anisotropic conductive adhesive film were evaluated with respect to the items shown in Table 8 below, the same results as shown in Table 8 were obtained.

Table 8 Characteristic measurement items of anisotropic conductive adhesive film 38 38 39 ratio 14 Adhesion at room temperature ^a) Yes Yes No Room temperature flexibility ^b) Yes Yes Yes Time to lose flexibility 5 Day 20 day 5 day Glass transition temperature Tg (° C) 187 190 102, 182 a) Tackiness was used to evaluate the tackiness. b) The softness was evaluated by measuring a film having a thickness of 50 μm of 180.
It was based on a bending test.

Further, the contact resistance value (Ω) of each anisotropic conductive adhesive film was measured. Anisotropic conductive adhesive film is sandwiched between a flip chip (3M, US chip, bumped chip) and an ITO glass substrate (surface resistance: 30Ω), and a load of 15 kg / cm ² is applied at a temperature of 180 ° C.
It crimped for 80 seconds. During the preparation of this sample, book 38 to book 39
Although almost no foaming was observed in No. 4, foaming was found at the time of pressure bonding because the ratio 14 included the solvent coating step. Moreover, although peeling was not found in the peripheral portion of the sample in the book 38 to the book 39, in the ratio 14,
Peeling spots were found on the periphery of the sample. 8 samples
The contact resistance value (Ω) with time was measured by exposing it to 0 ° C. and 95% RH heat and humidity resistance test conditions. The contact resistance was measured with a tester by a four-terminal method at a current of 10 μA. The measurement results obtained are shown in Table 9 below.

Table 9 Change in contact resistance value (Ω) at 80 ° C./95% RH Measurement timing 38 mains 39 ratio 14 initial 5 2 2 24 hours later 3 3 2 168 hours later 5 3 4 500 hours later 6 3 9 Furthermore, for this 39 and ratio 14 samples, 100
The sample was exposed to the gas phase thermal shock test conditions of ° C (30 minutes) /-45 ° C (30 minutes) and the change with time of the contact resistance value (Ω) was measured in the same manner as above. The measurement results obtained are shown in Table 10 below.

Table 10 Change in contact resistance value (Ω) in thermal shock test Measurement timing This 39 ratio 14 Initial 2 2 After 24 hours (24 cycles) 3 10 168 hours (168 cycles) 3 12 After 500 hours (500) Cycle) 320 As can be understood from the above measurement results, the stability of the contact resistance value was almost the same in all examples.

[0053]

INDUSTRIAL APPLICABILITY The epoxy-acrylic resin composition of the present invention, as a film before thermosetting, can be formed by (a) ultraviolet irradiation, and (b) requires a solvent and a heating step for film formation. When formed into a film, the film has good compatibility of (c) constituents, (d) uniform overall, (e) excellent reactivity and potential, and (f) workability. Is good, (g) it is heat-curable, and (h) there is no problem of syneresis.

Further, this resin composition has a high (i) Tg as a film after thermosetting, specifically, 150
At a temperature of not less than 0 ° C, (j) high toughness and (k) low hygroscopicity. Since the film-shaped composition of the present invention has good compatibility with its constituent components, it can be a uniform film-shaped composition even in a wide range of film thickness. Furthermore, it has a slight surface tackiness, and when it is used as an adhesive, etc., positioning and temporary fixing are easy and workability is further improved.

Further, the anisotropic conductive adhesive film provided by the present invention can be produced without solvent, has tackiness, can be quickly cured, has no foaming, has a high Tg of the cured product, and causes peeling. It is difficult and has excellent resistance stability.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tomio Sakurai, 3-8-8 Minamihashimoto, Sagamihara-shi, Kanagawa Sumitomo 3M Limited

Claims (11)

[Claims] 1. An epoxy resin (a) (hereinafter referred to as "compound (a)"), (b) a compound represented by the following general formula (1): (In the formula, R ¹ is —CR ³ ₂ — (wherein R ³ independently represents CF ₃ , H, CH ₃ or cyclohexyl),
—SO ₂ — or a divalent fluorene group represented by the following formula: embedded image R ² is independently H, Cl, CH ₃ , C ₂ H ₅ or C ₃
It is H _7. ) Has an aromatic amine (hereinafter referred to as "compound (b)") and (c) one or more acryloyl groups and / or methacryloyl groups in the molecule, and its solubility parameter is 9.2 to 12. Epoxy-comprising compound No. 4 (hereinafter referred to as "compound (c)")
Acrylic resin composition. 2. The amount of the compound (b) is 0.5 to 2 gram equivalent to 1 gram equivalent of the compound (a), and the amount of the compound (c) is the compounds (a) and (b). The epoxy-acrylic resin composition according to claim 1, which is 5 to 100 parts by weight with respect to a total amount of 100 parts by weight. 3. The epoxy according to claim 1, which contains a compound (hereinafter referred to as “compound (d)”) having at least one acryloyl group and / or methacryloyl group and at least one carboxyl group in the molecule. -Acrylic resin composition. 4. The epoxy according to claim 1, which contains a compound having at least one acryloyl group and / or methacryloyl group and at least one epoxy group in the molecule (hereinafter referred to as “compound (e)”). -Acrylic resin composition. 5. The content of at least one of the compound (d) and / or (e) is 0.3 based on 100 parts by weight of the total amount of the compound (a) and the compound (b).
The epoxy-acrylic resin composition according to claim 3, which is ˜50 parts by weight. 6. The epoxy-acrylic resin composition according to claim 1, which contains a solid catalyst (f) that enhances the reactivity of the compound (b). 7. The method according to claim 6, wherein the content of the solid catalyst (f) is 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the compound (a) and the compound (b). Epoxy-acrylic resin composition. 8. The epoxy-acrylic resin composition according to claim 1, which further contains conductive particles (g). 9. The conductive particles (g) are contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the compounds (a), (b) and (c). 8. The epoxy-acrylic resin composition according to item 8. 10. A film-shaped resin composition obtained by polymerizing the epoxy-acrylic resin composition according to any one of claims 1 to 9 by ultraviolet irradiation to form a film. 11. An epoxy-acrylic resin cured product obtained by heating and curing the film-shaped resin composition according to claim 10.