Patent Application
20180051126
The present invention relates to a resin composition, a conductive resin composition, an adhesive, a conductive adhesive, a paste for forming electrodes, and a semiconductor device.
A resin composition is used as a sealing material or an adhesive for a wiring board, a circuit board, a circuit plate including multiple layers of wiring boards and circuit boards, a semiconductor chip, a coil, an electrical circuit, an automobile component, and the like. Such a resin composition is required to have heat resistance.
A resin composition having excellent heat resistance is widely known. For example, Patent Literature 1 discloses a polybenzoxazine-modified bismaleimide resin composition having excellent heat resistance, which includes benzoxazine and bismaleimide. Patent Literature 1 also discloses an example in which imidazole is contained as a curing accelerator.
Patent Literature 2 discloses a resin composition which includes a bismaleimide compound and a benzoxazine compound, as well as a triazine compound used as a curing accelerator. It is disclosed that such a resin composition has excellent heat resistance.
Patent Literature 1: JP-A-2012-97207
Patent Literature 2: JP-A-2014-227542
Here, when the resin composition is used, it is required to have high adhesive strength during heating as well as heat resistance. In particular, it is preferable that the change ratio in adhesive strength between during normal temperature and during heating (the change ratio of adhesive strength) be low.
An object of the present invention is to provide a resin composition, a conductive resin composition, an adhesive, a conductive adhesive, a paste for forming electrodes, and a semiconductor device, which have long-term heat resistance and a low change ratio of adhesive strength.
The present inventor found that a resin composition including a compound having in its molecule an OH group and any one of primary to tertiary amines, dicyandiamide, and bismaleimides has long-term heat resistance and a low change ratio of adhesive strength. The present invention has been accomplished based on these findings.
The present invention is a resin composition, a conductive resin composition, an adhesive, a conductive adhesive, a paste for forming electrodes, and a semiconductor device, which solve the above-described problems by having the following configurations.
[1] A resin composition including (A) a compound having in its molecule an OH group and any one of primary to tertiary amines, (B) dicyandiamide, and (C) bismaleimides.
[2] The resin composition according to the above-described [1], in which (A) is a compound having a benzoxazine backbone.
[3] The resin composition according to the above-described [1] or [2], in which (C) is liquid bismaleimides.
[4] The resin composition according to any one of the above-described [1] to [3], further including (D) a compound having in its molecule one or more epoxy groups, or cyanate ester.
[5] A conductive resin composition including the resin composition according to any one of the above-described [1] to [4], and a conductive filler.
[6] An adhesive including the resin composition according to any one of the above-described [1] to [4].
[7] A conductive adhesive including the conductive resin composition according to the above-described [5].
[8] A paste for forming electrodes including the conductive resin composition according to the above-described [5].
[9] A semiconductor device including: a cured product of the resin composition according to any one of the above-described [1] to [4]; a cured product of the conductive resin composition according to the above-described [5]; a cured product of the adhesive according to the above-described [6]; a cured product of the conductive adhesive according to the above-described [7]; or a cured product of the paste for forming electrodes according to the above-described [8].
The resin composition according to the present invention has long-term heat resistance and a low change ratio of adhesive strength.
The resin composition according to the present invention includes (A) a compound having in its molecule an OH group and any one of primary to tertiary amines, (B) dicyandiamide, and (C) bismaleimides.
As described herein, “normal temperature” refers to 20° C.±15° C. Being “liquid” refers to having fluidity at normal temperature. Being “solid” refers to not having fluidity at normal temperature. The “weight loss” is the change ratio of weight Y relative to weight X. Here, weight X is a weight of a cured product of the resin composition, and weight Y is a weight of the cured product which has been left to stand at a predetermined temperature for a predetermined period of time (for example, 200° C.×100 hours). Specifically, the weight loss is a value indicated by “weight loss=(|weight X−weight Y|/weight X)×100.” “Having long-term heat resistance” refers to being low in weight loss. “Adhesive strength” refers to strength with which the resin composition causes a certain object (for example, an alumina test piece) to be adhered. A “change ratio of adhesive strength” is a ratio between the adhesive strength during normal temperature and the adhesive strength during heating. Specifically, the change ratio of adhesive strength is a value indicated by “change ratio of adhesive strength=(|adhesive strength at 200° C.−adhesive strength at normal temperature|/adhesive strength at normal temperature)×100.” It can be said that the lower the change ratio of adhesive strength is, the higher heat resistance is.
Examples of the compound having in its molecule an OH group and any one of primary to tertiary amines may include a compound having a benzoxazine backbone, and aminophenols. From the viewpoint of long-term heat resistance, a compound having a benzoxazine backbone, such as benzoxazine as a highly heat resistant resin, is preferable. It is noted that as described herein, “having in its molecule an OH group” includes not only having in its molecule an OH group itself, like phenols, but also having in its molecule an OH group through ring opening, like benzoxazine.
Dicyandiamide (“DICY”) is an amide compound represented by H2N—CNH—NH—CN. Dicyandiamide acts as a curing agent to bismaleimides when synthesizing the resin composition according to the present invention. Also, dicyandiamide acts as a catalyst in the reaction between the compound having in its molecule an OH group and any one of primary to tertiary amines, and bismaleimides. Dicyandiamide is a compound widely used in industrial applications, and is excellent in adhesiveness, heat resistance, and the like.
Examples of bismaleimides may include N,N′-(4,4′-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidephenyl)methane, m-phenylene bismaleimide (N,N′-1,3-phenylene bismaleimide), 1,6-bismaleimide hexane, 1,2-bismaleimide ethane (N,N′-ethylenedimaleimide), N,N′-(1,2-phenylene)bismaleimide, N,N′-1,4-phenylene dimaleimide, N,N′-(sulfonyldi-p-phenylene)dimaleimide, and N,N′-[3,3′-(1,3-phenylenedioxy)diphenyl]bismaleimide.
The bismaleimides in the present invention include solid bismaleimides. However, liquid bismaleimides are more preferable. Solid bismaleimides generally have low solubility to organic solvents. Therefore, when solid bismaleimides are used, a large amount of organic solvents needs to be used for dilution. However, in this case, solvents volatilize during curing, causing formation of a void, which leads to the decrease of adhesive strength and the occurrence of cracks. In order to prevent this, a method of dispersing solid bismaleimides in the resin composition using a roll mill or the like can be also adopted. However, this method causes the viscosity of the resin composition to increase. On the other hand, the resin composition containing liquid bismaleimides has low viscosity. Therefore, workability when using the resin composition improves.
Also, dimer acid-modified bismaleimides can be used. Examples of dimer acid-modified bismaleimides include BMI-1500 and BMI-1700 as liquid bismaleimides, and BMI-3000 as solid bismaleimides (all are manufactured by Designer molecules Inc.). The use of dimer acid-modified bismaleimides enables the elastic modulus of the resin composition to be suppressed low. It is considered that this is because dimer acid-modified bismaleimides have a reactive maleimide group only at both terminals, and therefore do not have a crosslinkable reactive group in its molecular chain. In a cured product of such a resin composition, cracks are unlikely to occur.
The resin composition according to the present invention can be manufactured by mixing (A) a compound having in its molecule an OH group and any one of primary to tertiary amines, (B) dicyandiamide, and (C) bismaleimides. The manufacturing method of the resin composition is not particularly limited, as long as a composition in which the above-described components are uniformly mixed can be obtained.
The resin composition according to the present invention may include (D) a compound having in its molecule one or more epoxy groups, or cyanate ester.
An example of the compound having in its molecule one or more epoxy groups includes epoxy resin. Examples of epoxy resin may include bisphenol A-type epoxy resin, brominated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, Novolac-type epoxy resin, alicyclic epoxy resin, naphthalene-type epoxy resin, ether-based epoxy resin, polyether-based epoxy resin, oxirane ring-containing polybutadiene, and silicone epoxy copolymer resin.
Also, examples of liquid epoxy resin may include bisphenol A-type epoxy resin having an average molecular weight of approximately 400 or less, branched multifunctional bisphenol A-type epoxy resin such as p-glycidyloxyphenyl dimethyl tris bisphenol A diglycidyl ether, bisphenol F-type epoxy resin, phenol Novolac-type epoxy resin having approximately 570 or less, alicyclic epoxy resin such as vinyl(3,4-cyclohexene)dioxide, 3,4-epoxy cyclohexyl carboxylic acid (3,4-epoxy cyclohexyl)methyl, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, and 2-(3,4-epoxycyclohexyl)5,1-spiro(3,4-epoxycyclohexyl)-m-dioxane, biphenyl-type epoxy resin such as 3,3′,5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl, glycidyl ester-type epoxy resin such as diglycidyl hexahydrophthalate, diglycidyl 3-methylhexahydrophthalate, and diglycidyl hexahydroterephthalate, glycidyl amine-type epoxy resin such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, and tetraglycidyl bis(aminomethyl)cyclohexane, hydantoin-type epoxy resin such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin, and naphthalene ring-containing epoxy resin. Also, epoxy resin having a silicone backbone such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane can be used. Further examples may include diepoxide compounds such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol glycidyl ether, and neopentyl glycol diglycidyl ether, and triepoxide compounds such as trimethylol propane triglycidyl ether and glycerin triglycidyl ether.
Examples of solid epoxy resin may include orthocresol Novolac-type epoxy resin, phenol Novolac-type epoxy resin, naphthol Novolac-type epoxy resin, modified phenol-type epoxy resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, glycidyl amine-type epoxy resin, biphenyl-type epoxy resin, bisphenol A-type epoxy resin, biphenyl aralkyl-type epoxy resin, bisphenol F-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, aliphatic-type epoxy resin, stilbene-type epoxy resin, and bisphenol A Novolac-type epoxy resin, which have a high molecular weight.
One kind of epoxy resin can be used alone. Alternatively, two or more kinds of epoxy resin can be mixed and used. Also, dimer acid-modified epoxy resin can be used. An example of dimer acid-modified epoxy resin may include jER871 (manufactured by Mitsubishi Chemical Corporation). The use of dimer acid-modified epoxy resin enables the elastic modulus of the resin composition to be suppressed low. In a cured product of such a resin composition, cracks are unlikely to occur.
A conductive material such as a conductive filler may be added to the resin composition, so that the resin composition has conductivity. Examples of the conductive filler may include an Ag filler, an AgSn filler, and an alloy filler thereof. From the viewpoint of conductivity, the conductive material is preferably 19 to 65% by volume (equivalent to 70 to 95% by weight for an Ag filler or the like having a specific gravity of approximately 10), and further preferably 23 to 48% by volume (equivalent to 75 to 90% by weight for an Ag filler or the like having a specific gravity of approximately 10). The resin composition having conductivity (conductive resin composition) is used when an electrical connection is required in a circuit board, an electrical circuit, and the like. Also, a thermally conductive material such as Ag and alumina may be added to the resin composition, so that the resin composition has thermal conductivity. The resin composition having thermal conductivity is used when the heat from a chip or a substrate is required to be released. Furthermore, a silica filler or a silicone powder may be added as a filling material to the resin composition. The addition of the filling material such as the silicone powder leads to lowering of elasticity. Also, an additive or the like such as a silane coupling agent may be contained as necessary, within the range that does not impair the effects of the present invention.
The resin composition according to the present invention can be used as an adhesive. An adhesive is used for bonding to a circuit of an electronic component, or as a die attacher which bonds a semiconductor element and another semiconductor element, and/or as a die attacher which bonds a semiconductor element and a support member for mounting the semiconductor element. When the adhesive is a conductive adhesive, it can be used as an alternative to solder. Also, a semiconductor device has a structure in which a semiconductor element and another semiconductor element are bonded together, and/or a structure in which a semiconductor element and a support member for mounting the semiconductor element are bonded together. A semiconductor device which includes a cured product of the resin composition according to the present invention or a cured product of the adhesive according to the present invention is excellent in reliability at a high temperature of 200° C.
The long-term heat resistance, adhesive strength (normal temperature and 200° C.), and the like of the resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 6 described below were calculated.
As (A) a compound having in its molecule an OH group and any one of primary to tertiary amines (hereinafter, sometimes referred to as an “(A) component”), there was used a 66% solution prepared by diluting “F-a type benzoxazine” or “P-d type benzoxazine” (both manufactured by Shikoku Chemicals Corporation) with butyl carbitol acetate (hereinafter, sometimes referred to as “BCA”).
As (B) dicyandiamide (hereinafter, sometimes referred to as a “(B) component”), any one of the followings was used.
Also, in Comparative Examples, any one of the following catalysts or curing agents was used instead of the (B) component (indicated as (B′) in Table 1).
As (C) bismaleimides (hereinafter, sometimes referred to as a “(C) component”), any one of the followings was used.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” and 0.15 parts of “BMI.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition a.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition b.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-1700.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition c.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-3000.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition d.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3842,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition e.
Into a container, there were poured 3 parts (solid content: 2 parts) of a 66% solution of “F-a type benzoxazine,” 0.6 parts of “EH-3636AS,” and 1.5 parts of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition f.
Into a container, there were poured 4 parts (solid content: 2.66 parts) of a 66% solution of “F-a type benzoxazine,” 0.6 parts of “EH-3636AS,” 1.5 parts of “BMI,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition g.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “P-d type benzoxazine,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition h.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.1 parts of “2PHZ-PW,” and 1 part of “BMI.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition α.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.1 parts of “2PHZ-PW,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition β.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.1 parts of “2P4MHZ-PW,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition γ.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 1 part of “YH-307,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition δ.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 1 part of “DDH,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition E.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.1 parts of “AL-M,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition
The long-term heat resistance was calculated as follows. First, similarly to the measurement of curing properties, the resin composition was cured thereby to prepare a plate-like cured film. Then, the weight of the cured film was measured. Next, the cured film was left to stand in an oven (“DF411” manufactured by Yamato Scientific Co., Ltd.) set at 200° C. for 100 hours. Then, the weight of the cured film which has been left to stand was measured. Then, the weight loss was calculated based on the weight of the cured film before having been left to stand and the weight of the cured film after having been left to stand.
In the calculation results, the weight loss of less than 8% was evaluated as “Good,” indicting excellent long-term heat resistance. The weight loss of 8 to 12% was evaluated as “Fair.” Furthermore, the weight loss of 12% or more was evaluated as “Poor.”
Using a #200 mesh screen mask having openings of 1.5-mm square×25, the resin composition was applied onto a 20-mm square alumina substrate. Then, there was prepared a test piece having ten 3.2 mm×1.6 mm-size alumina chips mounted on ten of the 25 print patterns. Next, the resin composition was cured in the curing condition of “200° C. in temperature, 30 minutes.” The shear strength of this test piece was measured using a strength tester (Model No. 1605HTP, manufactured by Aikoh Engineering Co., Ltd.), thereby to calculate adhesive strength at normal temperature.
In the measurement results, the adhesive strength of 30 N/mm2 or more was evaluated as “Good,” the adhesive strength of 30 to 20 N/mm2 was evaluated as “Fair,” and the adhesive strength of less than 20 N/mm2 was evaluated as “Poor.”
Also, the above-described test piece having been cured in the curing condition of “200° C. in temperature, 30 minutes” was heated on a hot plate at 200° C. for one minute or more. In this state, the shear strength of this test piece was measured using a strength tester (same as the above). Thus, the adhesive strength at 200° C. (adhesive strength during heating) was calculated.
In the measurement results, the adhesive strength of 7 N/mm2 or more was evaluated as “Good,” the adhesive strength of 7 to 5 N/mm2 was evaluated as “Fair,” and the adhesive strength of less than 5 N/mm2 was evaluated as “Poor.”
Furthermore, the change ratio of adhesive strength in the resin composition was calculated based on the value of adhesive strength at normal temperature and the value of adhesive strength at 200° C.
In the calculation results, the change ratio of less than 85% was evaluated as “Good,” and the change ratio of 85% or more was evaluated as “Poor.”
In the comprehensive evaluation of the above-described measurement and calculation results, the resin composition was evaluated as “Excellent” when all results were “Good,” “Good” when one of the results was “Fair,” and “Poor” when one or more of the results were “Poor.” The resin composition evaluated as “Excellent” or “Good” in the comprehensive evaluation is the resin composition according to the present invention.
As indicated in Table 1, there was obtained the result that the resin compositions according to Examples 1 to 8 also have excellent long-term heat resistance.
Furthermore, there was obtained the result that the resin compositions according to Examples 1 to 8 have roughly high adhesive strength during heating and a low change ratio of adhesive strength, compared to the resin compositions according to Comparative Examples 1 to 6. It is noted that, as obvious from Example 6, there was obtained the result that long-term heat resistance, adhesive strength during heating, and a change ratio of adhesive strength are not influenced by variation of the ratios of the (A) to (C) components. Also, as obvious from Example 7, the use of a combination of solid bismaleimides and liquid bismaleimides as the (C) component further improved adhesive strength. Also, as obvious from Example 8, similar effects were obtained even when benzoxazine which is different from that of other examples was used as the (A) component.
On the other hand, in Comparative Examples 1 to 6 in which a substance other than dicyandiamide was used instead of the (B) component, the resin composition which satisfies all the criteria of long-term heat resistance and a change ratio of adhesive strength was not obtained. In particular, the change ratios of adhesive strength in all of Comparative Examples were lower than the criterion. As obvious from this result, a ternary system (a system including three components of the (A) to (C) components) in which dicyandiamide is used as a catalyst (and a curing agent) has high adhesive strength during heating, and can suppress a change ratio of adhesive strength to be low.
The long-term heat resistance, adhesive strength (normal temperature and 200° C.), and the like of the resin compositions obtained in Examples 9 to 12 and Comparative Example 7 described below were calculated.
As the (A) component, a 66% solution prepared by diluting “F-a type benzoxazine” with BCA was used. As the (B) component, “EH-3636AS” was used. Also, in Comparative Examples, “2PHZ-PW” was used instead of the (B) component (indicated as (B′) in Table 2). As the (C) component, “BMI-1500” was used.
As an additive, any one of the followings was used.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” and 12 parts of an “Ag filler.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition i.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” and 0.1 parts of a “silicone powder.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition j.
Into a container, there were poured 1.33 parts of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” 12 parts of an “Ag filler,” and 0.1 parts of a “silicone powder.” Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition k.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” 12 parts of an “Ag filler,” and 0.05 parts of a “silane coupling agent.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition 1.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.1 parts of ““2PHZ-PW”,” 1 part of “BMI-1500,” and 12 parts of an “Ag filler.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition η.
It is noted that the measurement method of long-term heat resistance is the same as that in Example 1 described above.
As indicated in Table 2, there was obtained the result that even when an additive was added, the resin composition including dicyandiamide as the (B) component has both long-term heat resistance and a low change ratio of adhesive strength. In particular, even when a large amount of a conductive filler is contained, these effects can be obtained. Therefore, the adhesive according to the present invention is extraordinarily useful as a conductive adhesive.
The long-term heat resistance, adhesive strength (normal temperature and 200° C.), and the like of the resin compositions obtained in Comparative Examples 8 to 10 described below were calculated. Then, the results were compared to the result of Example 2.
In Comparative Examples, any one of the followings (indicated as (A′) in Table 3) was used instead of the (A) component (F-a type benzoxazine) used in Example 2.
As the (B) component, “EH-3636AS” was used. As the (C) component, “BMI-1500” was used.
Into a container, there were poured 2.66 parts (solid content: 1.33 parts) of a 50% solution of “H-4,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition θ.
Into a container, there were poured 2.66 parts (solid content: 1.33 parts) of a 50% solution of “MEH-7500,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition ι.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “MEH-8005,” 0.3 parts of “EH-3636AS,” and 1 part of “BMI-1500.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition κ.
It is noted that the measurement method of long-term heat resistance is the same as that in Example 1 or the like described above.
As indicated in Table 3, there was obtained the result that when a compound having in its molecule only an OH group (a compound not having any one of primary to tertiary amines), such as phenolic resin, is used, there is not obtained a resin composition which satisfies all the criteria. In particular, the adhesive strength at 200° C. and the change ratio of adhesive strength were lower than the evaluation criteria in all Comparative Examples.
The long-term heat resistance, adhesive strength (normal temperature and 200° C.), and the like of the resin compositions obtained in Examples 13 to 17 and Comparative Examples 11 to 15 described below were calculated.
As the (A) component, a 66% solution prepared by diluting “F-a type benzoxazine” with BCA was used. As the (B) component, “EH-3636AS” or “EH-3842” was used. Also, in some of Comparative Examples, “DDH” was used instead of the (B) component (indicated as (B′) in Table 4). As the (C) component, “BMI-1500” was used. As an additive, an Ag filler was used.
As the (D) component, any one of the followings was used.
Into a container, there were poured 1.33 parts of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” 0.5 parts of “EXA-835LV,” and 0.5 parts of “jER871.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition m.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” and 1 part of “EXA-835LV.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition n.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” and 1 part of “jER871.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition o.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” and 1 part of “Lecy.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition p.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 1 part of “BMI1500,” 1 part of “jER871,” and 12 parts of an “Ag filler.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition q.
It is noted that in Examples 13 to 16, the different (D) components are added to the components of Example 2. Also, in Example 17, the (D) component (jER871) and an Ag filler are added to the components of Example 2.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” and 1 part of “EXA-835LV.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition λ.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3842,” and 1 part of “EXA-835LV.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition μ.
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 1 part of “BMI-1500,” and 1 part of “EXA-835LV.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition ν.
Into a container, there were poured 0.3 parts of “EH-3636AS,” 1 part of “BMI-1500,” and 1 part of “EXA-835LV” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition ξ.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 1 part of “DDH,” 1 part of “BMI-1500,” and 1 part of “EXA-835LV.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition o.
It is noted that the measurement method of long-term heat resistance is the same as that in Example 1 described above.
As indicated in Table 4, there was obtained the result that, compared with the ternary system according to the above-described Examples, the resin composition having a quaternary system in which epoxy resin or cyanate ester is added (a system including four components of the (A) to (D) components) satisfies all the evaluation criteria. On the other hand, in Comparative Examples, at least the change ratio of adhesive strength was lower than the evaluation criterion. It is noted that the adhesive strength value at 200° C. of Comparative Example 11 is closer to those of Examples. However, cracks had occurred in the obtained cured product. Consequently, the resin composition according to Comparative Example 11 was not able to withstand the use as an adhesive. It is considered that since the resin composition having a rigid molecular structure, like Comparative Example 11, is brittle, cracks are likely to occur.
The adhesive strength when the curing temperature and the curing time were varied was measured for the resin compositions according to Example 3 and Example 15.
Specifically, the resin compositions having similar compositions to those of Example 3 and Example 15 were cured at prescribed temperatures (175° C., 200° C., 225° C., and 250° C.) and for prescribed times (15 minutes, 30 minutes, 45 minutes, 60 minutes, and 90 minutes). Then, adhesive strength at normal temperature was measured for each of the obtained cured products. The measurement method used was similar to that in Example 1 or the like. Also, whether or not the resin composition had been cured was determined according to the change of adhesive strength. When the adhesive strength changes to a large extent, a crosslinking reaction is proceeding. That is, it is considered that the resin composition is not completely cured. On the other hand, when the adhesive strength hardly changes (when saturated), it is considered that the resin composition has been cured.
The viscosity was calculated for the resin compositions obtained in Example 2 and Example 18.
The viscosity of the resin composition before curing was measured using an EHD-type viscometer (3° cone/R 9.7 manufactured by Toki Sangyo Co., Ltd.).
Into a container, there were poured 2 parts (solid content: 1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” and 0.5 parts of “BMI.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition r.
As indicated in Table 5, the amount of bismaleimides used in Example 2 in which liquid bismaleimides were used is twice that in Example 18. In spite of such a fact, there was obtained the result that Example 2 is low in viscosity.
The conductivity and printing performance were calculated for the resin compositions obtained in Example 9 and Example 19.
Into a container, there were poured 2 parts (solid content:1.33 parts) of a 66% solution of “F-a type benzoxazine,” 0.3 parts of “EH-3636AS,” 0.5 parts of “BMI,” and 12 parts of an “Ag filler.” The mixture was hand-stirred. Thereafter, the obtained product was dispersed using a triple roll mill, thereby to prepare a resin composition s.
The resin composition was spread on a screen mask (emulsion thickness: 20 μm, #200 mesh, pattern dimension: 1 mm×71 mm), thereby to perform screen printing on an alumina substrate. Then, the resin composition was left to stand at 200° C. for 30 minutes for curing. Thus, a test piece was obtained. The resistance value and film thickness of the obtained test piece were measured using a digital multimeter and a surface roughness tester. Then, the specific resistance value of the cured resin composition was calculated.
In the measurement results, the specific resistance value of 1×10−3 Ω·cm or less was evaluated as “Good.”
The resin composition was spread on a metal mask having a thickness of 70 μm and a pattern dimension of 1.6×0.9 mm. Next, stencil printing was performed with the resin composition on an alumina substrate using a metal squeegee. Then, the resin composition was left to stand at 200° C. for 30 minutes for curing.
The presence or absence of rubbing on a pattern of the cured coated film was visually inspected.
In the measurement results, the coated film without rubbing was evaluated as “Good.” The coated film with rubbing only on the periphery of a pattern was evaluated as “Fair”.
As illustrated in Table 6, it became obvious that both of the resin compositions according to Example 9 and Example 19 can have sufficient conductivity. Furthermore, the viscosity of the resin composition can be lowered when liquid bismaleimides are used (Example 9) than when solid bismaleimides are used (Example 19). Therefore, there was obtained the result that even when a conductive filler is added, printing performance is excellent.
As obvious from Examples and Comparative Examples described above, the resin composition including (A) a compound having in its molecule an OH group and any one of primary to tertiary amines, (B) dicyandiamide, and (C) bismaleimides has long-term heat resistance and a low change ratio of adhesive strength.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-071468 | Mar 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/059843 | 3/28/2016 | WO | 00 |
