JPH04366194A - Primer composition and semiconductor device - Google Patents

Abstract

PURPOSE:To provide a primer composition excellent in adhesion to metals and plastic materials, curing characteristics, heat resistance of its cured films and water resistance by mixing a specific polyimide compound with a silane coupling agent. CONSTITUTION:A polyimide compound which has a structural unit of formula I (wherein R is a group of formula II or III; R<1> is a divalent organic group; R<2> and R<3> are each a substituted or unsubstituted monovalent hydrocarbon group; Y is an oxygen atom or a divalent hydrocarbon group; n is 1-1,000; Z is a divalent organic group with an aromatic ring; X is a tetravalent organic group of formula IV, V or VI; and n is 1 or more) is mixed with a silane coupling agent (e.g. vinyltrimethoxysilane) of formula VII (wherein R<4> is an organic group having an amino, mercapto or glycidyl group; R<5> is a substituted or unsubstituted 1-6 C monovalent hydrocarbon group; M is a hydrolyzable atom or group; and a is 0, 1 or 2) to prepare a primer composition.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a primer composition useful for adhering molded articles such as thermosetting resin to the surface of molded articles made of various metal materials or plastics, and a semiconductor coated with this composition. Regarding equipment.

0002

[Prior art and problems to be solved by the invention] Conventionally,
2. Description of the Related Art In order to improve the surface properties of molded articles made of metals and plastics, it is known to form a hardened film of an organosilicon compound on their surfaces. However, there is a problem in that the adhesion between metals and organosilicon compounds is generally poor, except in combinations of organosilicon compounds having extremely limited chemical structures and certain metals.

[0003]Therefore, there is a need for the development of a good adhesion improver or primer composition that can improve the adhesion of both. (Japanese Patent Publication No. 54-28430), a composition consisting of a compound obtained by transesterifying a polyester or polyether polyol with an alkoxysilane and polyisocyanate (Japanese Patent Publication No. 48-41697), a composition containing methyl methacrylate as the main component Composition (Tokuko Sho 5)
2-138565), a primer composition containing an epoxyalkyltrialkoxysilane as a main component (Japanese Patent Publication No. 54-81378), an undercoating composition consisting of a certain type of silane and an acid anhydride (Japanese Patent Publication No. 15522-1982),
Japanese Patent Publication No. 55-99930) and a composition containing a co-hydrolyzate of two or more types of silanes and alkyl etherified methylol melamine as main components (Japanese Patent Publication No. 55-99930) have been proposed.

However, these methods all have the disadvantage that they cannot impart sufficiently satisfactory adhesion, hot water resistance, heat resistance, etc. to the object.

On the other hand, transistors, diodes, ICs
, LSI and other semiconductor devices are often sealed with resin materials such as epoxy resins. However, when semiconductor devices are sealed with these resin materials, water and ionic impurities that enter through the resin materials can cause damage. Deterioration of semiconductor devices is often caused.

As a countermeasure to this problem, a method has been proposed in which the semiconductor element is coated and protected with a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties, and then sealed with a resin material. In general, this polyimide resin can impart excellent properties such as heat resistance to objects, but since it is insoluble in solvents other than some high-boiling point organic solvents, it is usually difficult to use polyamic acid, which is its precursor. The conventional method is to dissolve it in an organic solvent, apply it onto a semiconductor element, and then heat cure it (imidize it) to form a film. but,
In forming a polyimide resin film using this method, heat treatment for converting polyamic acid into polyimide is performed for 300 min.
It takes a long time and at high temperatures above ℃. For this reason, in the above method, long-term heating at high temperatures is disadvantageous in the working process, especially from the viewpoint of energy saving. The acid will remain, and this polyamic acid will cause deterioration of properties such as moisture resistance and corrosion resistance of the polyimide resin. In particular, when a resin material is used as an insulating protective film for a semiconductor element, such a decrease in resin performance causes deterioration of the semiconductor element and shortens its lifespan, which is a major problem, so it is important to solve these problems. desired.

[0007]Furthermore, recently, as packages have become increasingly smaller and thinner, the surface mounting method has become mainstream as the mounting method on the board, and it has become impossible to maintain sufficient reliability with conventional epoxy resin compositions. . For example, if the package is soldered when it has absorbed moisture, there is a problem that the package will crack, or even if no cracks occur, the moisture resistance will deteriorate. Therefore, in this respect as well, there is a demand for the development of a high quality primer composition.

The present invention was made in view of the above circumstances, and
Provided is a primer composition that provides a cured film with excellent adhesion to metal or plastic materials and excellent properties such as heat resistance and water resistance by heating and curing at a low temperature for a short time, and a semiconductor device coated with this composition. The purpose is to

[0009]

[Means and Effects for Solving the Problem] As a result of intensive studies to achieve the above object, the present inventors have found that a polyimide compound having a structural unit represented by the following general formula (1) and a polyimide compound having the following general formula (4) It has been found that a primer composition with excellent various properties can be obtained by using the silane coupling agent shown in the following.

0010

[Chemical formula 3]

That is, the ring-closing polyimide resin of formula (1) above is different from conventional polyimide resins which are insoluble in solvents other than some solvents such as phenol and N-methyl-2-pyrrolidone. ether type, ketone type,
It shows good solubility in cellosolve-based organic solvents, and therefore polyimide resin films can be formed from these low-boiling point solvent solutions by heating at low temperatures for a short time, significantly improving workability, saving energy, and reducing costs. We have found that this can be achieved and that it is preferable from a safety and health perspective. Furthermore, when the polyimide resin of formula (1) is used in combination with the silane coupling agent of formula (4) above, it will not be repelled by the surface of metal materials and plastic materials, and it will not be repelled by the surface of metal materials or plastic materials, and there will be no steps or slopes on the surface of the material. It is possible to form a coating film uniformly without pinholes, resulting in a film with superior adhesiveness than that of polyimide resin alone, and this film has excellent adhesion, heat resistance, electrical and mechanical properties. It has been found that the solder material has excellent properties such as moisture absorption and soldering properties. Therefore, the above primer composition is effective as a paint, dye, coating agent, undercoat for general molding materials, etc. In particular, the composition is applied to the surface and protected by a film formed by scattering the solvent. The inventors discovered that the semiconductor device produced by the inventors of the present invention has extremely high reliability and excellent moisture-absorbing soldering properties, which led to the development of the present invention.

Therefore, the present invention provides a primer composition comprising a polyimide compound of the above formula (1) and a silane coupling agent of the above formula (4), and a semiconductor device having a surface coated with this composition. I will provide a.

The present invention will be described in more detail below. The polyimide compound which is the first essential component of the present invention is represented by the following general formula (1).

[0014]

[C4]

A polyimide compound having the structural unit of the above formula (1) can be synthesized from a tetracarboxylic dianhydride and a diamine component.

[0016] Examples of the tetracarboxylic dianhydride include the following.

[0017]

[C5]

[0018] As the acid dianhydride, one of these types can be used alone or two or more types can be used in combination.

In addition, as the diamine component, silicone diamine represented by the following structural formula (5) and the following structural formula (6) are used.
) are preferably used.

[0020]

[C6]

Here, as the divalent organic group R1 in the above formula (5), those having 1 to 18 carbon atoms, particularly 1 to 7 carbon atoms are preferably used, and examples thereof include organic groups having the following structure.

[0022]

[C7]

Furthermore, as the unsubstituted or substituted monovalent hydrocarbon group for R2 and R3, those having 1 to 18 carbon atoms, particularly 1 to 8 carbon atoms, are preferably used, such as methyl group, ethyl group, propyl group, butyl group, etc. Alkyl groups such as cyclohexyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups and tolyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, or some or all of the hydrogen atoms of these groups are replaced with halogen atoms, etc. Examples include a chloromethyl group substituted with , a 3,3,3-trifluoropropyl group, and the like.

Further, in the above formula (5), Y is an oxygen atom or a divalent hydrocarbon group, and as the divalent hydrocarbon group, those having 10 or less carbon atoms, particularly 1 to 6 carbon atoms are preferably used. , for example, a group having the following structure.

[0025]

[Chemical formula 8]

Specific examples of the diamine represented by the above formula (5) include diaminosiloxanes having the following structure when Y is an oxygen atom.

[0027]

[Chemical formula 9]

Furthermore, when Y is a divalent organic group,
For example, silicone diamine with the following structure can be mentioned,
It is not limited to these.

[0029]

[Chemical formula 10]

[0030]

[Chemical formula 11]

Next, another component, the above formula (6)
Specific examples of the ether diamine include, but are not limited to, the following.

[0032]

[Chemical formula 12]

The above-mentioned tetracarboxylic dianhydride component and diamine component are preferably blended in an equivalent ratio of 0.9 to 1.1, particularly 0.95 to 1.05.

[0034] When polymerizing a polyimide resin using the above-mentioned components and blending ratio, it can be carried out according to a known method. For example, predetermined amounts of the above tetracarboxylic dianhydride component and diamine component are mixed with N-methyl-2-pyrrolidone, N,
It is charged into a polar organic solvent such as N'-dimethylformamide or N,N'-dimethylacetamide, and reacted at a low temperature of 0 to 60°C to synthesize a polyamic acid resin, which is a precursor of a polyimide resin. Without isolating this polyamic acid resin, by subsequently heating the solution to a temperature range of 100 to 200°C, preferably 140 to 180°C, a dehydration ring-closing reaction proceeds to the acid amide portion of the polyamic acid, and the desired purpose is achieved. A polyimide resin can be synthesized. Further, in order to allow this dehydration ring-closing reaction to proceed completely within a short time, it is preferable to use an azeotropic dehydration solvent such as toluene or xylene in combination. The progress of this polymerization reaction is determined by the change in the characteristic absorption band of the imide group in the infrared absorption spectrum (Japanese Patent Publication No. 57-41330).
It can be detected by After the imidization by dehydration and ring closure is completed, the reaction solution is cooled, reprecipitated by pouring it into methanol, and dried to obtain the polyimide resin according to the present invention.

The polyimide resin obtained by these series of operations can be prepared by using a low boiling point organic solvent, that is, a ketone solvent such as cyclohexanone or acetophenone, an ether solvent such as tetrahydrofuran, 1,4-dioxane, or diglyme, as described above. Shows good solubility in cellosolve solvents. Therefore, as described below, the composition of the present invention is used after being dissolved in an organic solvent, and as the organic solvent, one type of these organic solvents can be used alone or two or more types can be used in combination.

The primer composition of the present invention contains a silane coupling agent in addition to the above-mentioned polyimide resin.

[0037] Here, the silane coupling agent is a compound represented by the following general formula (4).

[0038]

[Chemical formula 13]

Here, the hydrolyzable group represented by M includes, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, an ethoxyethoxy group; an acetoxy group, a propionoxy group,
Acyloxy groups such as butyroyloxy group, benzoyloxy group; isopropenyloxy group, isobutenyloxy group,
Alkenyloxy groups such as 1-ethyl-2-methylvinyloxy group; iminoxy groups such as dimethylketoxime group, methylethylketoxime group, diethylketoxime group, cyclopentanoxime group, cyclohexanoxime group;
Amino groups such as N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N,N-dimethylamino group, N,N-diethylamino group, cyclohexylamino group; N-methyl Acetamide group, N-
Amide groups such as ethylacetamide group and N-methylbenzamide group; N,N-dimethylaminooxy group, N,N-
Aminooxy groups such as diethylaminooxy groups can be mentioned.

Specific examples of the silane coupling agent of formula (4) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyldimethylmonomethoxysilane, and vinyltrimethoxysilane. Acetoxysilane, vinyltris(tert-butylperoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3
-Mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-thiomethacrylatepropyltrimethoxysilane, 3-methacrylamidopropylmethyldiethoxy Examples include silane, 3-thiometaacrylatepropylmethyldimethoxysilane, and the like. Among these, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane are particularly preferred. These silane coupling agents may be used alone or in combination of two or more. It is also possible to use hydrolysates of these silane coupling agents.

In the primer composition of the present invention, the blending amounts of the polyimide compound of formula (1) and the silane coupling agent of formula (4) described above are appropriately selected depending on the working conditions, etc., but usually the polyimide compound is 2-80 of the whole thing
% by weight, preferably 10 to 50% by weight,
The silane coupling agent is 20 to 98% by weight of the entire composition.
, particularly preferably 50 to 90% by weight. If the polyimide compound is less than 2% by weight or the silane coupling agent is more than 98% by weight, the strength of the formed film will be weak and the primer layer may be prone to cohesive failure.
If the content of the polyimide compound exceeds 80% by weight or the content of the silane coupling agent is less than 20% by weight, the adhesiveness may become weak. It is believed that this decrease in adhesive strength is due to a decrease in the amount of the silane coupling agent blended and a decrease in the content of reactive alkoxy groups present in the silane coupling agent.

The primer composition of the present invention can be diluted with the above-mentioned low boiling point organic solvent and can be used as a solution of various concentrations. Primer concentration: 20% by weight
It is preferably at most 10% by weight or less, particularly preferably at most 10% by weight. Furthermore, when applying the primer to an object, it is desirable that the thickness of the primer film be 10 μm or less, particularly 5 μm or less.

[0043] The primer composition can be applied to various substrates by brushing, penetrating, roll coating, spraying, etc. depending on the application. In addition, when forming a protective film on a semiconductor element, after coating the composition on the semiconductor element by spin coating, dripping from a dispenser, or other known coating method, apply an organic solvent at 150°C to 180°C. An extremely simple, low-temperature, short-time process that evaporates with heat treatment for 1 to 2 hours creates a uniform protective film for the primer layer, which has excellent adhesion to elements and wiring, heat resistance, electrical properties, mechanical properties, and moisture-absorbing soldering properties. Moreover, it can be formed without pinholes.

The primer composition of the present invention can form a strong cured film on the surface of a molded article made of metal or plastic.
For example, aluminum, iron, zinc, tin, silver, gold, copper, nickel, stainless steel, chromium copper, silicon copper, copper-nickel alloy, etc. Also, as plastics, for example, epoxy resin, ABS resin (acrylonitrile-butadiene-
Examples include styrene copolymer resin), PBT resin (polybutylene terephthalate resin), PPS resin (polyphenylene sulfide resin), DAP resin (diallyl phthalate resin), nylon, styrene resin, melamine resin, polyester resin, and polycarbonate resin. The composition of the present invention has particularly high adhesion to metals such as iron, copper, and nickel, and is therefore extremely useful as a primer for adhering cured epoxy resin molding materials to the surfaces of these metals.

[0045]

[Effects of the Invention] As explained above, the primer composition of the present invention is useful in forming a strong hardened film on the surface of molded products made of metal materials or plastics, and is effective in modifying the surfaces of these products. Especially when used for semiconductor devices, a cured film with excellent heat resistance, electrical, mechanical properties, moisture-absorbing soldering properties, and adhesive properties can be uniformly applied to semiconductor devices without pinholes by simple operation using low-temperature and short-time heat treatment. Compared to conventional methods for producing polyimide resin films that require heat treatment at high temperatures and for long periods of time, this method enables significant energy savings, and its industrial value is extremely large. Therefore, the composition of the present invention can be applied to paints, dyes,
It is effective as a coating agent, an undercoat for general molding materials, etc., and is particularly useful for semiconductors.

[0046]

[Examples] The present invention will be specifically explained below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[Synthesis Example 1]...Polyimide resin A stirrer,
2,2-bis(3,4-
Benzenedicarboxylic acid anhydride) perfluoropropane 4.4 g (0.01 mol) and 3,3',4,4'-
Biphenyltetracarboxylic dianhydride 26.5g (0.
09 mol) and 400 g of N-methyl-2-pyrrolidone as a solvent, and bis(
3-Aminopropyl)tetramethyldisiloxane19.
8 g (0.08 mol) and 8.2 g (0.02 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
A solution of N-methyl-2-pyrrolidone (mol) was gradually added dropwise while controlling the temperature of the reaction system so as not to exceed 50°C. After the addition was completed, the mixture was further stirred at room temperature for 10 hours.
Next, after attaching a reflux condenser with a water receiver to the flask, 30 g of xylene was added, and the reaction system was heated to 160 ° C.
The reaction was carried out while maintaining the temperature at 160° C. for 4 hours to obtain a yellowish brown transparent polyimide resin solution. In addition, 3.4 g of water was produced as a by-product in this reaction. Next, the polyimide resin solution was poured into methanol and reprecipitated to obtain a resin. This resin was dried under reduced pressure at 60°C for 24 hours, and polyimide resin 5
2.6g was isolated.

When the infrared absorption spectrum of this polyimide resin was observed, no absorption based on polyamic acid was observed, but absorption based on imide groups was confirmed at 1780 cm -1 and 1720 cm -1 .

[Synthesis Example 2] 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used as the tetracarboxylic dianhydride component of polyimide resin B, and diamine As a component, 2.6 g (0.0
67.1 g of polyimide resin was prepared in the same manner as in Synthesis Example 1 except that 36.9 g (0.09 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl)propane were used. Obtained.

[Synthesis Example 3]...Polyimide resin C stirrer,
2,2-bis(3,4-
4.4 g (0.01 mol) of benzenedicarboxylic acid anhydride) perfluoropropane and 3,3',4,4'-
Biphenyltetracarboxylic dianhydride 26.5g (0.
09 mol) and 400 g of N-methyl-2-pyrrolidone as a solvent, and 1,2 as a diamine component were charged.
-bis(γ-aminopropyldimethylsilyl)ethane 2
0.8 g (0.08 mol) and 2,2-bis[4-(4-
Aminophenoxy)phenyl]propane 8.2g (0.
69 g of a solution of N-methyl-2-pyrrolidone (02 mol) was gradually added dropwise while controlling the temperature of the reaction system so as not to exceed 50°C. After the dropwise addition was completed, the reaction system was further stirred at room temperature for 10 hours, and then a reflux condenser with a water receiver was attached to the flask, 30 g of xylene was added, and the reaction system was heated to 160°C.
The temperature was raised to 160°C for 4 hours to react.
A transparent yellow-brown polyimide resin solution was obtained. In addition, 3.4 g of water was produced as a by-product in this reaction. Next, the polyimide resin solution was poured into methanol and reprecipitated to obtain a resin. This resin was dried under reduced pressure at 60° C. for 24 hours to isolate 52.8 g of polyimide resin.

When the infrared absorption spectrum of this polyimide resin was observed, no absorption based on polyamic acid was observed, but absorption based on imide groups was confirmed at 1780 cm -1 and 1720 cm -1 .

Further, this polyimide resin was soluble in tetrahydrofuran, 1,4-dioxane, cyclohexanone, and acetophenone.

[Synthesis Example 4] 13.3 g (0.03 mol) of 2,2-bis(3,4-benzenedicarboxylic anhydride) perfluoropropane as the tetracarboxylic dianhydride component of polyimide resin D and 3, 3', 4, 4'-
Biphenyltetracarboxylic dianhydride 20.6g (0.
07 mol) and 15.6 mol of 1,2-bis(γ-aminopropyldimethylsilyl)ethane as the diamine component.
Polyimide resin 54.g (0.06 mol) and 11.7 g (0.04 mol) of 1,4-bis(4-aminophenoxy)benzene were prepared in the same manner as in Synthesis Example 1.
1g was obtained.

The obtained polyimide resin was soluble in any of the following solvents: tetrahydrofuran, 1,4-dioxane, cyclohexanone, and acetophenone.

[Synthesis Example 5] Polyimide resin E 13.3 g (0.03 mol) of 2,2-bis(3,4-benzenedicarboxylic acid anhydride) perfluoropropane as the tetracarboxylic dianhydride component and 3, 3', 4, 4'-
22.6 g of benzophenone tetracarboxylic dianhydride (
0.07 mol) and 1,2- as the diamine component.
Bis(γ-aminopropyldimethylsilyl)ethane2.
6 g (0.01 mol) and 36.9 g (0.0 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane
9 mol), 68.9 g of polyimide resin was obtained by the same operation as in Synthesis Example 1.

The obtained polyimide resin was soluble in any of the following solvents: tetrahydrofuran, 1,4-dioxane, cyclohexanone, and acetophenone.

[Synthesis Example 6] Polyimide resin F (ring-opening polyimide resin) 2,2-bis(
4.4 g (0.01 mol) of 3,4-benzenedicarboxylic acid anhydride) perfluoropropane and 3,3',4
, 4'-biphenyltetracarboxylic dianhydride 26.5
g (0.09 mol), and N-methyl-2- as a solvent.
400 g of pyrrolidone was charged, and 19.8 g (0.08 mol) of bis(3-aminopropyl)tetramethyldisiloxane and 2,2-bis[4-(
8.2 g of 4-aminophenoxy)phenyl propane (
A solution of N-methyl-2-pyrrolidone containing 0.02 mol) was gradually added dropwise while controlling the temperature of the reaction system so as not to exceed 50°C. After the addition was completed, the mixture was further stirred at room temperature for 10 hours to obtain a yellowish brown polyimide resin solution. Then,
The polyimide resin solution was poured into methanol and reprecipitated to obtain a resin. This resin was dried under reduced pressure at 60° C. for 24 hours to isolate 56 g of polyimide resin.

When the infrared absorption spectrum of this polyimide resin was observed, it was found that the absorption due to polyamic acid was 2.
It was confirmed at 900 cm-1 and 3100 cm-1.

[Examples/Comparative Examples] As shown in Tables 1, 2, and 3, 18 types of primer compositions were prepared by blending the polyimide resin obtained in the above synthesis example and the following silane coupling agent.

Using the obtained primer composition, Table 1,
After applying the primer to the various base materials shown in 2 and 3 (dipping method), it was cured at 150°C for 1 hour, and then an epoxy resin molding material (KMC165VA: manufactured by Shin-Etsu Chemical Co., Ltd.) was applied at 175°C at 70 kg/cm2. A molded product was obtained. In addition, a primer composition was applied to the semiconductor element, and after curing at 150°C for 1 hour, an epoxy resin molding material (KMC165VA) was applied at 175°C at 70 kg/cm.
2 to obtain a molded product (see FIG. 1). The following tests were conducted on the obtained molded product. The results are shown in Tables 1 and 2.
Also listed in 3. Adhesion After applying primer to various test pieces shown in Tables 1, 2, and 3, the diameter was 15 mm and the height was 5 m.
A cylindrical molded product of 500 m was molded at 175°C, 70kg/cm2, and a molding time of 2 minutes, and after post-curing at 180°C for 4 hours, the peel force between the molded product and various test pieces was measured using a push-pull gauge. . Crack resistance due to heat cycle A silicon chip with a size of 9.0 mm x 4.5 mm x 0.5 mm was adhered to a 14PIN-IC frame (42 alloy), and then the primer compositions shown in Tables 1, 2, and 3 were applied. After coating, the epoxy resin composition is molded under 17 conditions.
After molding at 5°C for 2 minutes and post-curing at 180°C for 4 hours, thermal cycles of -50°C for 30 minutes to 180°C for 30 minutes were repeated, and the resin crack occurrence rate after 1000 cycles was measured. A moisture-resistant 4DRAM chip is adhered to a 20-PIN SOJ frame, and then a primer composition is applied to the silicon chip surface and the back side of the die pad (see Figure 1), and then an epoxy resin composition is molded on this under molding conditions of 175°C for 3 minutes. 180
Post-cure was performed at ℃ for 4 hours. This is 121℃/10
After being left in a 0% RH atmosphere for 24 hours and absorbing moisture, it was heated to 215°C.
Immerse it in a solder bath for 10 seconds and then heat it to 121℃/100%
The aluminum wiring disconnection rate was measured when the aluminum wiring was left in an RH atmosphere for 300 hours. Solder crackability after moisture absorption 60pin QFP (size 20mm x 14mm, resin thickness under die hard 0.7mm, die pad size 10mm x
After applying the primer composition to the back surface of the die pad (see Figure 1), an epoxy resin composition was applied to it under molding conditions 1.
It was molded at 75°C for 3 minutes and post-cured at 180°C for 4 hours. This package was left in an atmosphere of 85°C/85% RH for 24 hours to absorb moisture, and then
It was immersed in a 15°C solder bath for 10 seconds. The crack generation defect rate of the package that occurs at this time was investigated (number of tests n = 1
0). Silane coupling agent: (Both Shin-Etsu Chemical Co., Ltd.)
) KBM403...3-glycidoxypropyltrimethoxysilane KBM503...3-methacryloxypropyltrimethoxysilane KBM603...N-(2-aminoethyl)3-aminopropyltrimethoxysilane KBM803...・3-mercaptopropyltrimethoxysilane KBE903...3-aminopropyltriethoxysilane KBM303...2-(3,4-epoxycyclohexylethyl)trimethoxysilane KBE402...3-glycidoxypropylmethyldiethoxy silane

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

From the above results, it is clear that the primer composition of the present invention has excellent adhesion to various metal materials and various plastics, and is effective in modifying their surfaces. In addition, when applied to semiconductor elements, improvements in crack resistance, moisture resistance, and moisture absorption soldering properties were observed, and low-temperature, short-time heat treatment using the primer composition of the present invention can be used as a cost reduction measure in the semiconductor manufacturing process. It can be said to be extremely effective.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing a resin-sealed semiconductor device according to an embodiment of the present invention.

[Explanation of symbols]

1 Silicon chip 2 Die pad 3 Lead frame 4 Bonding wire 5 Resin sealant 6 Primer composition

Claims (2)

[Claims] 1. A primer composition comprising a polyimide compound having a structural unit represented by the following general formula (1) and a silane coupling agent represented by the following general formula (4). [Chemical formula 1] [Chemical formula 2] 2. A semiconductor device coated with the primer composition according to claim 1.