TWI403557B - Resin composition for screen printing - Google Patents

Abstract

A resin combination for screen printing is characterized by comprising the following components as essential components: (A) 100 wt. parts of polyamic acid resin containing alkoxylsilicyl represented by the formular (1) (wherein, x is 3-valent organic group, Y is 2-valent organic group, Z is group represented by formula (2), R<1> is alkyl with 1-3 carbon atoms, R<2> is alkyl or alkoxy with 1-3 carbon atoms, a is an integer of 0-4, p is an integer of 1-100, q is an integer of 1-100), (B) 5-350wt. parts of spherical metal oxide fine particles with average particle size of 0.05 to 10 microns; and (C) an effective amount of organic solvent for dissolving the component(A). The invention can provide the resin composition for screen printing with good printing property, impossible cause mesh residual, leak, debubbling degradation, obtain uniform film thickness and excellent resin combination for screen printing having continuous forming property.

Description

Resin composition for screen printing

The present invention relates to a resin composition for screen printing.

The polyimide-based resin is applied as a heat-resistant material on the surface of the semiconductor to serve as a protective insulating film. However, as a method of forming a pattern on such a protective film, it is known to perform spin coating in a varnish state. A method of patterning, or a method of simultaneously patterning by screen printing. In the former method, for example, a varnish of polyamic acid is spin-coated on a wafer to form a protective film, and a photoresist is laminated thereon, and the photosensitive portion or the non-photosensitive portion is dissolved by exposure and development by ultraviolet light, and also A method of dissolving a protective film of the lower layer to form a pattern, or a method of using a photosensitive resin having a UV-sensitive portion of a polyimide-based resin itself, and exposing a photosensitive portion or a non-photosensitive portion by ultraviolet light exposure and development. Since ultraviolet light exposure is included in any case, the program becomes cumbersome, and from the viewpoint of shortening the program, the latter screen printing method is also desired.

However, conventional varnishes for screen printing may not achieve satisfactory results in terms of resolution, film flatness, and the like. As one of the reasons, in order to maintain the shape, an inorganic filler is added to the varnish to impart shake, and the mesh remains or bleeds, and the defoaming property is deteriorated. Further, in particular, when the film is formed, there are problems such as rapid evaporation of the solvent and lack of continuous moldability.

On the other hand, a semiconductor element such as a transistor, a diode, an IC, or an LSI is often sealed with a resin material such as an epoxy resin. However, when the semiconductor element is sealed with a resin material or the like, the resin element is invaded by the resin material. Water or ionic impurities often cause deterioration of semiconductor components. Therefore, as a countermeasure against this, there has been proposed a method in which a semiconductor element is coated and protected by a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties, and then sealed with a resin material. In particular, recently, the package system has become smaller and smaller, and the method of packaging the substrate has become the mainstream while the surface is encapsulated. The conventional epoxy resin composition cannot be sufficiently reliable. Moreover, since the solder is not lead-free in recent years, the solder reflow temperature is raised to 260 ° C, and when soldering is performed after moisture absorption in the package, an inappropriate situation occurs, such as a crack in the package, or even if there is no Cracking also reduces moisture resistance. In such applications, it has been strongly desired to develop a highly heat-resistant screen-printable protective film which is excellent in adhesion to a metal or a plastic material. However, the adhesion of the conventional polyimide resin to the copper foil is insufficient, and if it exceeds the glass transition temperature (Tg) of the cured film, the heat resistance of the resin is extremely lowered.

In view of the above, it is an object of the present invention to provide a screen printing resin which is excellent in screen printing property, does not cause cell residue or bleeding, deteriorates in defoaming property, and the like, and has a uniform film thickness and excellent continuous moldability. Composition.

Further, another object is to provide excellent adhesion to a substrate and a plastic material, to efficiently remove wafer moiré or thermal degradation due to thermal stress of a semiconductor package, and to provide a cured product excellent in heat resistance and used for semiconductor sealing. An epoxy resin molding material is an effective resin composition for screen printing as a protective film material when sealing a semiconductor.

In order to achieve the above object, the inventors of the present invention conducted an intensive review and found that (A) an alkoxyalkylene group-containing polyamine oxime imine resin represented by the following formula (1), (B) average particle diameter a resin composition for screen printing which is a spherical metal oxide fine particle of 0.05 to 10 μm and (C) an organic solvent as an essential component, particularly containing the above components (A), (B), (C) and (D) The resin composition for screen printing having an epoxy resin having at least two epoxy groups in one molecule and (E) a curing accelerator is effective, and the present invention has been completed.

That is, the present invention provides the resin composition for screen printing shown below.

[1] A resin composition for screen printing characterized by having (A) a polyamidoximine resin containing an alkoxyalkyl group represented by the following formula (1); , (wherein X is a trivalent organic group, Y is a divalent organic group, and Z is a Z system. R ¹ is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms of R ² or an alkoxy group, a is an integer of 0 to 4, p is an integer of 1 to 100, and q is 1 to 100. Integer): 100 parts by mass, (B) spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 μm: 5 to 350 parts by mass, (C) organic solvent: a dissolved effective amount of the resin of the above component (A).

[2] A resin composition for screen printing comprising: (A) a polyamidoximine resin containing an alkoxyalkyl group represented by the following formula (1); (wherein X is a trivalent organic group, Y is a divalent organic group, and Z is a Z system. R ¹ is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms of R ² or an alkoxy group, a is an integer of 0 to 4, p is an integer of 1 to 100, and q is 1 to 100. (Integer), (B) spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 μm, (C) an organic solvent, (D) an epoxy resin having at least two epoxy groups in one molecule, and (E) hardening promotion Agent.

[3] The resin composition for screen printing according to [2], wherein the epoxy resin of the component (D) is a formula (2) (wherein, G represents a glycidyl group, R represents a hydrogen atom or a monovalent hydrocarbon group, and at least one of all R is a monovalent hydrocarbon group, and n is an integer of 0 or 1 or more).

The resin composition for screen printing according to any one of the above aspects, wherein the surface of the (B) metal oxide fine particles is a decazane and/or a decane coupling agent. deal with.

[5] The resin composition for screen printing according to [4], wherein the decazane is hexamethyldioxane.

[6] The resin composition for screen printing according to [4], wherein the decane coupling agent is one or more selected from the group consisting of an amine group, a glycidyl group, a thiol group, a ureido group, a hydroxyl group, an alkoxy group, and A compound selected from the active groups in the thiol group.

The resin composition for screen printing according to any one of the above aspects, wherein the component (B) contains 60 to 100% by mass of a true spherical vermiculite having an average particle diameter of 0.05 to 10 μm. .

[8] The resin composition for screen printing according to any one of [1] to [7], wherein an organic solvent having a boiling point of 200 ° C or higher is used as the component (C).

According to the present invention, it is possible to provide a resin composition for screen printing which is excellent in screen printing property, does not cause remnulation or bleed out of the mesh, deteriorates in defoaming property, and the like, and has a uniform film thickness and excellent continuous moldability. .

Moreover, it is excellent in adhesion to a substrate and a plastic material, and can effectively remove wafer moiré or thermal degradation due to thermal stress of a semiconductor package, and provide a cured product excellent in heat resistance, and an epoxy resin for semiconductor sealing is used. An effective resin composition for screen printing which is a protective film material when a molding material is used to seal a semiconductor.

Best form for implementing the invention

The invention is described in more detail below.

The essential component (A) of the present invention is an alkoxyalkylene group-containing polyamidoximine resin represented by the following formula (1).

(wherein X is a trivalent organic group, Y is a divalent organic group, and Z is a Z system. R ¹ is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms of R ² or an alkoxy group, a is an integer of 0 to 4, p is an integer of 1 to 100, and q is 1 to 100. Integer).

The alkoxyalkylene group-containing polyamidoximine resin can be obtained by reacting a polyamidoquinone imine resin having a carboxyl group and/or an acid anhydride group at a molecular terminal with an epoxy group-containing alkoxysilane compound. Got it.

The polyamidoximine resin used in the present invention has a mercaptoamine group and a quinone imine group in the molecular skeleton, and for example, it can be obtained by reacting a tricarboxylic acid with a diamine according to a usual method. In the X, the X is derived from the tricarboxylic acid and Y is derived from the diamine.

Examples of the tricarboxylic acid include trimellitic acid and trimellitic anhydride.

Examples of the diamine include p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'- Bis(4-aminophenyl)propane, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, 1,4-bis(3-aminophenoxyl) Benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(p-aminophenylsulfonyl)benzene, 1,4-bis(m-aminophenylsulfonyl) Benzene, 1,4-bis(p-aminophenyl sulfide) benzene, 1,4-bis(m-aminophenyl sulfide) benzene, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-4-(4- Aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4-(4- Aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-di Methyl-4-(4-aminophenoxy)phenyl]ethane, bis[4-(4-aminophenoxy)phenyl]methane, bis[3-methyl-4-(4- Aminophenoxy)phenyl]methane, double [3 Chloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]methane, bis[4-(4 An aromatic ring-containing diamine such as -aminophenoxy)phenyl]anthracene or 2,2-bis[4-(4-aminophenoxy)phenyl]perfluoropropane, etc., preferably Phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1,4-bis(3-aminophenoxyl) Benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3- 4--4-(4-aminophenoxy)phenyl]propane and the like.

Moreover, in order to provide adhesiveness and flexibility to a base material, a helium oxide diamine can also be used as a diamine. Specifically, those shown by the following formulas (3) to (11) may be mentioned, but of course, they are not limited thereto. Further, these diamine compounds may be used singly or in combination of two or more kinds as needed.

In the method for producing the polyamidoximine resin, there may be mentioned a method such as a ruthenium chloride method, an isocyanate method, a direct polymerization method, or the like.

The reaction ratio of the above-mentioned raw material component must be such a ratio that the carboxyl group and/or the acid anhydride group remain at the molecular terminal, (the molar number of the amine group) / (the molar number of the carboxyl group + the acid anhydride group) = 0.80 to 0.99, preferably When it is less than 0.8, the toughness and flexibility of the cured film may be lowered, and if it exceeds 0.99, sufficient terminal carboxyl group and/or acid anhydride group may not be quantitatively obtained.

The molecular weight of the polyamidoximine resin is preferably 5,000 to 100,000 as a weight average molecular weight in terms of styrene in terms of GPC. When it is less than 5,000, the toughness and flexibility of the cured film may be lowered, and if it exceeds 100,000, the workability may be lowered due to high viscosity.

By using the terminal carboxyl group and/or the acid anhydride group of the polyamidoximine resin thus obtained, and the following formula (12) The epoxy group of the epoxy group-containing alkoxysilane compound is subjected to an addition reaction to obtain the following formula (1). The alkoxyalkylene group-containing polyamidoximine resin is shown.

Further, in the above formula, X, Y, Z and R ¹ , R ² , a, p, and q are as described above, but p and q are each independently an integer of 2 to 100, and particularly preferably 3 to 80. An integer, a is preferably 0, 1, 2 or 3.

Here, the reaction between the carboxyl group, the acid anhydride group and the epoxy group can be carried out according to a usual method, and when a carboxyl group remains at both ends of the molecular chain of the polyamidoximine resin, the carboxyl group can be When the epoxy group reacts above the ear and the carboxyl group remains at one end of the polyamidoximine resin and the acid anhydride group remains at the other end, the total of the carboxyl group and the acid anhydride group may be more than the molar amount. The epoxy group reacts. Further, the reaction temperature is 30 to 130 ° C, and the reaction time is about 1 to 10 hours, and if necessary, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N are preferably used. It is carried out with a solvent such as N-dimethylacetamide.

Commercially available products can be used as the component (A), and the commercial products are, for example, Compoceran H900-2, H901-2, H901-2D (manufactured by Arakawa Chemical Industries Co., Ltd.).

The component (B) is a spherical metal oxide fine particle having an average particle diameter of 0.05 to 10 μm. The spherical metal oxide fine particles preferably have a Wardell sphericity of 0.7 to 1.0.

Here, the so-called "Hua Duo sphericity" (refer to the Handbook of Chemical Engineering, issued by Maruzen Co., Ltd.) is to spheronize the particle (the diameter of a circle equal to the projected area of the particle) / (the projection of the particle) The index measured by the diameter of the smallest circle attached to it. The closer the index is to 1.0, the closer it is to the particles of the true sphere. The spherical sphericity of the spherical metal oxide fine particles of the present invention is preferably from 0.9 to 1.0, particularly preferably from 0.95 to 1.0. When the sphericity of the Waldorf is less than 0.7, the amount of the component (B) increases, and the shake of the composition increases.

From the viewpoint of the low shake, it is preferable that the component (B) contains 60 to 100% by mass (particularly 80 to 100% by mass of spherical spherical metal oxide fine particles of spherical metal oxide fine particles. In this specification, "true spherical" also includes the concept of a slightly distorted sphere with a Hudson sphericity in the range of 0.95~1.

In addition, the "average particle diameter" means "volume average particle diameter", and is measured, for example, by a laser diffraction scattering type particle size distribution measuring apparatus (trade name: LA910) manufactured by Shiroshima Seisakusho Co., Ltd., in an automated manner.

The average particle diameter of the spherical metal oxide fine particles is preferably from 0.05 to 5 μm, more preferably from 0.1 to 5 μm. Further, the spherical metal oxide fine particles are preferably true spherical metal oxide fine particles.

The spherical metal oxide fine particles may be fine particles of one type of metal oxide, or may be fine particles of two or more kinds of metal oxides (that is, composite oxides). Specific examples of the oxide of one kind of metal include oxides of metals such as lanthanum, aluminum, magnesium, zirconium, and titanium, such as vermiculite (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and titanium oxide (TiO). ₂ ), zirconium dioxide (ZrO ₂ ) and the like. Specific examples of the composite oxide include composite oxides of the above metals, such as vermiculite-alumina composite oxide, vermiculite-titanium dioxide composite oxide, vermiculite-zirconia composite oxide, vermiculite-oxidation. Two-component composite oxide such as magnesium composite oxide or alumina-magnesia composite oxide, or vermiculite-alumina-magnesia composite oxide, vermiculite-alumina-titanium dioxide composite oxide, vermiculite-titanium dioxide a three-component composite oxide such as a magnesium oxide composite oxide. In the example of the spherical metal oxide fine particles, it is preferable that the spherical fine particles, particularly the spherical fine particles, have the main component (that is, 60 to 100% by mass).

The spherical metal oxide fine particles may be produced by any means, but are preferably metal oxide fine particles obtained by burning a metal. The metal oxide fine particles obtained by burning the metal can be composed of a metal powder of cerium, aluminum, magnesium, zirconium, titanium or the like in an atmosphere containing a carrier gas and oxygen (3Al _{2 ).} O ₃ .2SiO ₂ ~2Al ₂ O ₃ .SiO ₂ ) aluminum powder and barium powder, magnesium powder and aluminum powder of spinel composition (MgAl ₂ O ₄ ), and composition of cordierite (2MgO.2Al ₂ The aluminum powder of O ₃ .5 SiO ₂ ) is burned with a metal powder mixture such as magnesium powder or cerium powder to form a chemical flame, and a metal such as vermiculite, alumina, titania or zirconia is obtained in the chemical flame. Microparticles (especially ultrafine particles) of oxides or composite oxides. Among the metal oxide fine particles obtained by burning these metals, it is preferable to contain spherical or particularly spherical fine particles of the fine particles as a main component (that is, 60 to 100% by mass).

The spherical metal oxide fine particles are not necessarily subjected to surface treatment, but are preferably treated with a surface treated with a decane and/or a decane coupling agent.

The decane alkane is, for example, a decazane such as hexamethyldioxane (HMDS) or hexaphenyldioxane or a combination of two or more of these. Among these, from the viewpoint of suppressing the aggregation of the vermiculite, the acidic vermiculite tends to be alkaline, the affinity for the organic substance is improved, the uniformity is improved, and the stability of the resin of the component (A) is improved. Preferred is hexamethyldioxane.

The above decane coupling agent is, for example, a compound having at least one reactive group (reactive organic functional group) selected from the group consisting of an amine group, a glycidyl group, a thiol group, a ureido group, a hydroxyl group, and an alkoxy group, or Combination (eg, a combination of an alkoxy group with other reactive functional groups). Specific examples of the decane coupling agent include epoxy functional groups such as γ-glycidoxypropyltriethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. An amine group containing an amino alkoxydecane, an aminopropyl triethoxy decane, a ureidopropyl triethoxy decane, an N-phenylaminopropyl trimethoxy decane, or the like An alkyl alkoxy oxane such as oxydecane, phenyltrimethoxydecane, etc., alkyl alkoxydecane, octadecyltrimethoxydecane, etc., vinyltrimethoxydecane, allyltrimethyl An alkenyl alkoxysilane such as an oxoxane or an organoalkyloxane having a mercapto functional group such as γ-mercaptopropyltrimethoxydecane.

Further, as a processing method, a conventional method can be employed.

Commercially available products include, for example, Admafine SE series and SC series of ADMATECHS Co., Ltd. as the spherical metal oxide fine particles.

The component (B) may be used alone or in combination of two or more. The amount of the component (B) is preferably 5 to 350 parts by mass, preferably 5 for 100 parts by mass of the component (A). ~300 parts by mass, more preferably 10 to 200 parts by mass. When the amount is less than 5 parts by mass, good screen printing properties are not obtained, and if it exceeds 350 parts by mass, the inherent adhesion of the resin of the component (A) to the substrate is impaired.

In the resin composition for screen printing of the present invention, by using the spherical metal oxide fine particles of the present component, the amount of the above-mentioned compounding amount can be reduced, and the formed pattern does not cause the mesh to remain, bleed or peel off. A uniform film thickness can be obtained by deterioration of foaming property or the like.

In addition, as the metal oxide powder, a molten metal oxide powder, a metal oxide fracture product, or a fumed metal oxide (smoke metal oxide) may be used in combination within a range that does not impair the above effects. Spherical oxide powder. The combined ratio of the non-spherical metal oxide powder is 25 parts by mass or less (0 to 25 parts by mass), particularly preferably 20%, per 100 parts by mass of the spherical metal oxide powder of the component (B). The following parts (0 to 20 parts by mass).

Among the organic solvents of the component (C), those which partially or completely dissolve the component (A) can be used. Specific examples of the component (C) include tetrahydrofuran and 1,4-diene. Alkane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Formamide, dimethyl hydrazine, 1,3-dimethyl-2-imidazolidinone, etc., preferably an aprotic polar solvent, particularly preferably N-methylpyrrolidone, N-vinylpyrrolidine Ketone, cyclohexanone, γ-butyrolactone and 1,3-dimethyl-2-imidazolidinone.

When the cured film formed by the composition of the present invention is a film of 20 μm or less, it is particularly preferable to use an organic solvent having a boiling point of 200 ° C or more in order not to impair the continuous moldability of screen printing. The organic solvent having a boiling point of 200 ° C or higher may be, for example, γ-butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone or 1,3-dimethyl-2-imidazolidinone.

Further, the component (C) may be used alone or in combination of two or more.

The compounding amount of the component (C) is an effective amount for dissolving the component (A), and the amount of the solid component is usually 10 to 80% by mass, particularly preferably 20 to 70% by mass.

In the resin composition for screen printing of the present invention, (D) an epoxy resin and (E) a curing accelerator may be further blended.

The epoxy resin having at least two epoxy groups in one molecule of the component (D) of the present invention is not particularly limited, and a preferred example is an epoxy resin represented by the following formula (2).

(wherein G represents a glycidyl group, R represents a hydrogen atom or a monovalent hydrocarbon group, and at least one of all R is a monovalent hydrocarbon group, and n is 0 or an integer of 1 or more).

Here, the monovalent hydrocarbon represented by R is preferably an unsubstituted or substituted monovalent hydrocarbon group such as an alkyl group or an aryl group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include a methyl group and an ethyl group. A propyl group, a butyl group, a tributyl group, a phenyl group or the like is taken as a representative.

Further, in the epoxy resin of the formula (2), n is an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 20, particularly 0 or an integer of 1 to 10, and an epoxy resin of the formula (2). It may also be a mixture of epoxy resins having different values of n. In this case, in order to increase the glass transition temperature of the cured product as much as possible, it is preferable to select that 70% by mass or less (preferably 60% by mass or less) of n is 0, and the average value of n indicating the average degree of polymerization is 1 An epoxy resin having a molecular weight distribution in the range of ~3. Here, when n = 0 is contained more than 70% by mass, the glass transition temperature may be lowered.

Specific examples of the epoxy resin of the above formula (2) are the following formulas (13) to (15).

(where t-Bu represents the third butyl group, OG represents , n is as described above (the same applies hereinafter).

In the present invention, in addition to the epoxy resin of the above formula (2), other epoxy resins such as bisphenol A type epoxy resin, novolac type epoxy resin, grease cyclic epoxy resin, shrinkage may be appropriately combined. A glycerin type epoxy resin or an epoxy resin represented by the following formulas (16) to (18).

Further, a brominated epoxy resin for flame retardation can be used. Examples of the brominated epoxy resin include the following formulas (19) and (20).

These epoxy resins can be used singly or in combination of two or more. Further, the amount of the epoxy resin used is preferably 1 to 150 parts by mass, more preferably 2 to 100 parts by mass, per 100 parts by mass of the alkoxyalkylene group-containing polyamidoximine resin. When the amount is less than 1 part by mass, the adhesive strength of the cured product to the substrate is not obtained. On the other hand, when it exceeds 150 parts by mass, the heat resistance of the cured product may be lowered.

In this case, the epoxy resin of the above formula (2) is 1 to 100% by mass, particularly preferably 5 to 100% by mass, based on the total amount of the epoxy resin.

The hardening accelerator of the component (E) of the present invention is not particularly limited, but from the viewpoint of high reactivity of the alkoxyalkylene group-containing polyamidoximine resin and the epoxy resin, the amine-based contact is preferred. Media. As an amine-based catalyst, it can be combined with 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethyl One or two or more of these may be used as the imidazole derivative such as imidazole. It is particularly preferable to use an imidazole compound of the following formula (21), and by using the imidazole compound having such a structure, it is possible to impart high heat resistance, high moisture resistance, and high adhesion to the cured product.

(wherein, Ph represents a phenyl group).

As another hardening accelerator, a phosphine-based catalyst, specifically, triphenylphosphine, triphenylsulfonium triphenyl borate, tetraphenylphosphonium tetraphenyl borate or the following formula (22) can be used. compound of.

(In the formula, R ³ to R ^{10 are,} for example, a halogen atom such as a hydrogen atom, fluorine, bromine or iodine; an alkyl group having 1 to 8 carbon atoms; an alkenyl group having 2 to 8 carbon atoms; and an alkene having 2 to 8 carbon atoms. The base, the alkoxy group having 1 to 8 carbon atoms, a trifluoromethyl group, a phenyl group, etc., all of which may be the same or different).

The amount of the hardening accelerator of the component (E) is preferably in the total amount of 100 parts by mass of the alkoxyalkyl group-containing polyamidoximine resin (A) and the epoxy resin (D). 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass. When the amount is less than 0.001 part by mass, the curing may not be performed in a short period of time, and if it exceeds 20 parts by mass, the composition may be inferior in storage stability.

In the composition of the present invention, in addition to the above components (A) to (E), for example, an antioxidant, a thermal stabilizer, a conductive filler, a pigment, a dye, or the like may be added according to the purpose, without impairing the effects of the present invention. Coloring agent, etc.

The composition of the present invention can be prepared by mixing the above components (A) to (C), or (A) to (E) components, and optionally other components, according to a usual method. Specifically, for example, a mixing mill equipped with a stirring device and a heating device, a three-roller, a ball mill, a planetary mixer, or the like can be used. Further, two or more types of such mixing devices may be combined as appropriate.

A method of applying the above composition to the surface of a substrate such as a tantalum wafer (screen printing method): first, covering the surface of the substrate with a mask having an opening portion having a desired pattern, and putting the composition into the scraping The ink blade portion is then moved by the squeegee, and the composition is pressed to move on the mask, and the composition is filled in the opening portion of the mask member (filling step), and then the mask is removed, and The surface of the above substrate forms a pattern of the composition. The hardening of the composition thus formed is, for example, solidified at a low temperature (for example, one-stage or two-stage hardening temperature) at a low temperature of room temperature (20 ° C ± 5 ° C) to 200 ° C, and may be further 200 as needed. Curing (post-cure) at a high temperature of ~350 °C. Furthermore, the post-cure time is usually 0.1 to 20 hours.

The pattern formed by the screen printing method using the resin composition of the present invention has a high resolution, does not cause residual or bleed of the mesh, and deteriorates the defoaming property, and a uniform film thickness can be obtained. In addition, since it is excellent in continuous moldability, it can be used for a bonding protective film of a bonding film, a protective film, a junction of a diode, a transistor, or the like on a surface of a semiconductor element suitable for wafer level, and α-line shielding of VLSI. Film, interlayer insulating film, ion implantation mask, etc., and conformal coating of printed circuit board, alignment film of liquid crystal surface element, protective film of glass fiber, surface protection film of solar cell or conductive mixed with conductive filler A wide range of resin compositions for screen printing formed by formation of a film or the like.

When the resin composition for screen printing of the present invention is used as a protective film for the above-described semiconductor element or the like, the semiconductor element and/or the lead frame are coated by screen printing, and the film is heat-hardened, for example, to a thickness of 0.1~. A film of about 100 μm. After the cured film is formed under the above-described curing conditions, the epoxy resin molding material for semiconductor sealing is molded, and the epoxy resin molding material for semiconductor sealing and the substrate (for example, inorganic materials such as Ni, Ag, Cu, Si, SiO _{2 ,} etc.) can be improved. Adhesion of the substrate). In the semiconductor device thus obtained, no cracks in the epoxy resin molding material for semiconductor encapsulation and an inorganic substrate such as Ni, Ag, Cu, Si, SiO ₂ or the like are observed in the solder reflow after moisture absorption. ) stripping, but for those with high reliability.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto.

First, each component of the resin composition for screen printing was prepared as follows.

Resin composition for screen printing

(a) Base Resin Resin Solution A: A solution of a 40% resin-containing alkoxyalkylene group-containing polyamidoximine resin (Compoceran H900-2: manufactured by Arakawa Chemical Industries Co., Ltd.).

Resin solution B: A solution of a 40% resin-containing alkoxyalkylene group-containing polyamidoximine resin (Compoceran H901-2: manufactured by Arakawa Chemical Industries Co., Ltd.).

Resin solution C (synthesis example): In a flask equipped with a stirrer, a thermometer, and a nitrogen gas replacement device, 32.22 g (0.10 mol) of 3,3',4,4'-biphenyl group as tetracarboxylic dianhydride was charged. Tetracarboxylic dianhydride and 35 g of N-methyl-2-pyrrolidone, in which the temperature of the reaction system is not more than 50 ° C, and the dropwise addition is made up of 2.49 g (0.01 mol%). 1, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldioxane of diamine and 18.02 g (0.09 mol) of 4,4'-diaminodiphenyl A solution in which the ether was dissolved in 20 g of N-methyl-2-pyrrolidone. After completion of the dropwise addition, the mixture was further stirred at room temperature for 12 hours to promote the reaction to obtain a yellow-brown transparent polyamic acid resin solution. The viscosity of this solution is 250Pa. S, the resin solid content is 50.1% by mass. This was taken as the resin solution C.

[Chem. 19] (b) Epoxy resin Softening point: 85 ° C, epoxy equivalent: 214 (n = 0: 59 mass%, n = 1: 24 mass%, n = 2: 8 mass%, others: 9 mass%) Softening point: 79 ° C, epoxy equivalent: 165 (n = 0: 54 mass%, n = 1: 31 mass%, n = 2: 9 mass%, others: 6 mass%) (3) bisphenol A type ( Epikote 1001: manufactured by JER) Softening point: 64 ° C, epoxy equivalent: 450 (c) Hardening accelerator 2-methyl-4,5-dihydroxymethylimidazole (2PHZ) (d) filler (1) The globular vermiculite particles (Admafine SC2500-SE: manufactured by ADMATECHS) have an average particle diameter of 0.5 μm (2) oxonite (AEROSILR 972: manufactured by Japan AEROSIL Co., Ltd., particle shape is amorphous) (e) Organic solvent N -methyl-2-pyrrolidone (NMP) 1,3-dimethyl-2-imidazolidinone (DMI)

The components (a) to (e) described above were uniformly mixed so as to have the composition (unit parts by mass) shown in Table 1, to obtain a paste resin composition. The evaluation of the obtained composition was as follows. The results are shown in Table 1.

Evaluation method

(a) Viscosity The viscosity at 23 ° C was measured using a digital viscometer (manufactured by BROOKFIELD, trade name: DV-II+).

(b) Screen printing using a screen printing machine (manufactured by CWPRICE CO. INC., trade name: MODEL MC212) and screen mask (325 mesh, milk thickness: 15 μm, mesh thickness: 35 μm) . The provision of the mask, the filling of the composition of the doctor blade, and the removal of the mask were regarded as one molding step, and after 100 consecutive moldings, the deterioration of the pattern shape was confirmed. Then, it was exposed to an oven at 100 ° C for 0.5 hour, followed by exposure at 250 ° C for 4 hours to cause hardening. For the obtained pattern, the bleeding of the mesh, the foam, and the edge of the pattern were observed.

(c) Adhesiveness after moisture absorption The resin composition was applied to various samples shown in Table 1, and after hardening, at 175 ° C, 6865 kPa (70 kg/cm ² ), and a molding time of 90 seconds. An epoxy resin composition (KMC3580CA: manufactured by Shin-Etsu Chemical Co., Ltd.) was molded into a cylindrical shape having a bottom area of 10 mm ² and a height of 3 mm, and post-cured at 180 ° C for 4 hours. This was placed in an atmosphere of 85 ° C / 85% RH for 168 hours, and after IR reflux at 260 ° C, the peeling force of the molded article and various samples was measured by a push-pull gauge.

(d) Crack resistance of thermal cycle. A crucible wafer of 9.0 mm × 4.5 mm × 0.5 mm size was attached to a 14PIN-IC frame (42 alloy), and then the resin composition shown in Table 1 was applied to harden. Thereafter, the epoxy resin composition was molded at 175 ° C for 90 seconds, and after curing at 180 ° C for 4 hours, the thermal cycle of -50 ° C, 30 minutes to 180 ° C, and 30 minutes was repeated, and 1,000 cycles were measured. The rate of resin cracking.

It can be confirmed from Table 1 that the examples have a tendency to lower the viscosity and are excellent in printability as compared with the comparative examples. Further, the adhesion after moisture absorption and the crack resistance of the heat cycle are excellent.

Claims (6)

A resin composition for screen printing comprising: (A) a polyamidoximine resin containing an alkoxyalkyl group represented by the following formula (1); (wherein X is a trivalent organic group, Y is a divalent organic group, and Z is a Z system. R ¹ is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms of R ² or an alkoxy group, a is an integer of 0 to 4, p is an integer of 1 to 100, and q is 1 to 100. (Integer), (B) spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 μm, (C) an organic solvent, and (D) an epoxy resin represented by the following formula (2). (wherein G represents a glycidyl group, R represents a hydrogen atom or a monovalent hydrocarbon group, at least one of all R is a monovalent hydrocarbon group, n is an integer of 0 or 1 or more), and (E) a curing accelerator. The resin composition for screen printing according to the first aspect of the invention, wherein the surface of the (B) metal oxide fine particles is treated with a decane alkane and/or a decane coupling agent. The resin composition for screen printing according to the second aspect of the invention, wherein the decazane is hexamethyldioxane. The resin composition for screen printing according to the second aspect of the invention, wherein the decane coupling agent is one or more selected from the group consisting of an amine group, a glycidyl group, a thiol group, a urea group, a hydroxyl group, and an alkoxy group. The selected reactive group of compounds. The resin composition for screen printing according to any one of claims 1 to 4, wherein the component (B) contains 60 to 100% by mass of a true spherical vermiculite having an average particle diameter of 0.05 to 10 μm. The resin composition for screen printing according to any one of claims 1 to 4, wherein an organic solvent having a boiling point of 200 ° C or higher is used as the component (C).