KR101269820B1 - Resin composition for screen printing - Google Patents

Abstract

The present invention (A) 100 parts by mass of an alkoxysilyl group-containing polyamic acid resin represented by the following formula (1),

(B) 5 to 350 parts by mass of spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 µm, and

(C) The organic solvent of the dissolution effective amount of resin of the said (A) component

It relates to a resin composition for screen printing, characterized in that as an essential component.

≪ Formula 1 >

로 표시되는 기이고, R⁴는 탄소수 1 내지 3의 알킬기이고, R⁵는 탄소수 1 내지 3의 알킬기 또는 알콕시기이고, a는 0 내지 4의 정수이고, p는 1 내지 300의 정수이고, q는 1 내지 300의 정수이고, r은 1 내지 100의 정 수이다.Wherein X is a tetravalent organic group, Y is a divalent organic group, and Z is

R ⁴ is an alkyl group having 1 to 3 carbon atoms, R ⁵ is an alkyl group or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q Is an integer from 1 to 300, r is an integer from 1 to 100.

According to the present invention, it is possible to provide a resin composition for screen printing that has good screen printability, obtains a uniform film thickness without causing mesh eye residues, smearing, deterioration of defoamability, and the like and also has excellent continuous moldability.

Resin composition for screen printing, polyamic acid resin, spherical metal oxide fine particles, organic solvent, epoxy resin, curing accelerator

Description

Resin composition for screen printing {RESIN COMPOSITION FOR SCREEN PRINTING}

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

Polyimide-based resin is a heat-resistant material is coated on the surface of the semiconductor and serves as a protective insulating film, a method of forming a pattern on the protective film, a method of patterning after spin coating in a varnish state, or by screen printing At the same time, a method of patterning is known. In the former method, a varnish such as polyamic acid is spin-coated on a wafer to form a protective film, and then a photoresist is laminated thereon to dissolve the photosensitive portion or the non-photosensitive portion by ultraviolet light exposure and development, and the lower protective film. The method of melt | dissolving and forming a pattern, or the method of melt | dissolving a photosensitive part or a non-photosensitive part by ultraviolet light exposure and image development using the photosensitive resin which made the polyimide resin itself have the ultraviolet-sensitive part, etc. are mentioned, for example. have. In any case, since the process becomes complicated including ultraviolet exposure, the latter screen printing method is desired also in terms of shortening the process. However, conventional screen printing varnishes did not necessarily obtain satisfactory results in resolution, film flatness, and the like. One of the reasons is the addition of an inorganic filler to the varnish for maintaining the shape, and the mesh eye residue, bleeding, and deterioration of defoaming properties due to the thixotropy. Moreover, especially when forming a thin film, there exists a problem that a volatility of a solvent is fast and it lacks continuous formability.

On the other hand, sealing of semiconductor devices such as transistors, diodes, ICs, LSIs, etc. with resin materials such as epoxy resins is frequently performed. However, when semiconductor devices are sealed with these resin materials, water or ionic impurities penetrated through the resin material Due to this, deterioration of the semiconductor device is often caused. Therefore, as a countermeasure, the method of covering and protecting a semiconductor element with polyimide-type resin excellent in heat resistance, an electrical characteristic, and a mechanical characteristic, and then sealing with a resin material was proposed. In particular, in recent years, packages have become smaller and thinner, and surface mounting has become mainstream in the method of mounting on a substrate, and sufficient reliability cannot be maintained with a conventional epoxy resin composition. In addition, the solder reflow temperature has been raised to 260 ° C due to the recent solderless soldering, and if soldering after package moisture absorption, there is a problem in that a crack occurs in the package or a defect in which moisture resistance is lowered even if cracks do not occur. Also in these uses, the development of the protective film which is excellent in adhesiveness with a metal or a plastic material, and which can screen-print with high heat resistance is desired. However, when the conventional polyimide resin does not have sufficient adhesive force to copper foil and exceeds the glass transition temperature (Tg) of a cured film, there existed a problem that the heat resistance of resin fell extremely.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a good screen printability, a uniform film thickness is obtained without causing mesh eye residues, bleeding, or deterioration of defoaming properties, and is also excellent in continuous formability. It is an object to provide a composition.

In addition, it has excellent adhesion to the substrate and plastic material, efficiently eliminates chip cracks and thermal deterioration due to thermal stress of the semiconductor package to provide a cured product excellent in heat resistance, and uses an epoxy resin molding material for semiconductor sealing. Another object is to provide a resin composition for screen printing effective as a protective film material when sealing a semiconductor.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective,

(A) an alkoxysilyl group-containing polyamic acid resin represented by the following formula (1), (B) spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 µm, and (C) a resin composition for screen printing, in which an organic solvent is an essential component, in particular ( The present invention is completed by discovering that the resin composition for screen printing containing an epoxy resin having two or more epoxy groups in the A), (B), (C) component, and (D) one molecule and (E) a curing accelerator is effective. It came to the following.

That is, this invention provides the following resin composition for screen printing.

[1] (A) 100 parts by mass of an alkoxysilyl group-containing polyamic acid resin represented by the following formula (1),

(B) 5 to 350 parts by mass of spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 µm, and

(C) The organic solvent of the dissolution effective amount of resin of the said (A) component

Resin composition for screen printing, comprising as an essential component.

로 표시되는 기이고, R⁴는 탄소수 1 내지 3의 알킬기이고, R⁵는 탄소수 1 내지 3의 알킬기 또는 알콕시기이고, a는 0 내지 4의 정수이고, p는 1 내지 300의 정수이고, q는 1 내지 300의 정수이고, r은 1 내지 100의 정수이다.Wherein X is a tetravalent organic group, Y is a divalent organic group, and Z is

R ⁴ is an alkyl group having 1 to 3 carbon atoms, R ⁵ is an alkyl group or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q Is an integer from 1 to 300, and r is an integer from 1 to 100.

[2] (A) an alkoxysilyl group-containing polyamic acid resin represented by Chemical Formula 1,

(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 two or more epoxy groups in one molecule, and

(E) curing accelerator

Resin composition for screen printing, containing.

[3] The resin composition for screen printing according to [2], wherein the epoxy resin of the component (D) is an epoxy resin represented by the following general formula (2).

In the formula, G is a glycidyl group, R represents a hydrogen atom or a monovalent hydrocarbon group, provided that at least one of all R is a monovalent hydrocarbon group, and n is 0 or an integer of 1 or more.

[4] The resin composition for screen printing according to any one of [1] to [3], wherein the surface of the metal oxide fine particles of the component (B) is treated with a silazane and / or a silane coupling agent.

[5] The resin composition for screen printing according to [4], wherein the silazanes are hexamethyldisilazane.

[6] The resin for screen printing according to [4], wherein the silane coupling agent is one kind or two or more kinds of compounds having an active group selected from amino group, glycidyl group, mercapto group, ureido group, hydroxy group and alkoxy group. Composition.

[7] The resin composition for screen printing according to any one of [1] to [6], wherein the component (B) contains 60 to 100 mass% of spherical silica 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 more is contained as the component (C).

Hereinafter, the present invention will be described in more detail.

Component (A) of the present invention is an alkoxysilyl group-containing polyamic acid resin represented by the following general formula (1).

≪ Formula 1 >

로 표시되는 기이고, R⁴는 탄소수 1 내지 3의 알킬기이고, R⁵는 탄소수 1 내지 3의 알킬기 또는 알콕시기이고, a는 0 내지 4의 정수이고, p는 1 내지 300의 정수이고, q는 1 내지 300의 정수이고, r은 1 내지 100의 정수이다.Wherein X is a tetravalent organic group, Y is a divalent organic group, and Z is

R ⁴ is an alkyl group having 1 to 3 carbon atoms, R ⁵ is an alkyl group or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q Is an integer from 1 to 300, and r is an integer from 1 to 100.

The alkoxysilyl group-containing polyamic acid resin is obtained by reacting a polyamic acid resin and an epoxy group-containing alkoxysilane compound.

The polyamic acid resin used by this invention is obtained by making tetracarboxylic dianhydride represented by following formula (4) and the diamine represented by following formula (5) react in the organic solvent in equimolar equivalence according to a conventional method.

However, X represents the same meaning as the above.

However, Y represents the same meaning as the above.

Here, when the example of the tetracarboxylic dianhydride represented by the said Formula (4) is shown concretely, it is represented by following formula (6)-19, etc., It is not limited to this. On the other hand, tetracarboxylic dianhydride of the formula (4) can be used one or two or more of the following if desired.

As the diamine represented by the formula (5), p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenyl sulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthio Ether) benzene, 1,4-bis (m-aminophenylthioether) benzene, 2,2-bis [4- (4-aminophenoxy) 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-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophen ) Phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5- Dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoro Aromatic ring-containing diamines such as propane; and the like, preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [3-methyl-4- (4-aminophenoxy) phenyl] propane and the like.

Moreover, siloxane diamine can be used as a diamine in order to provide adhesiveness and flexibility to a base material.

Specifically, the thing shown by following formula (20-28) etc. can be illustrated, Of course, it is not limited to this. Moreover, these diamine compounds can also be used individually by 1 type if desired, and can also be used in combination of 2 or more type.

Regarding the production reaction of the polyamic acid resin, for example, the starting material described above is dissolved in a solvent in an inert atmosphere, and is usually reacted at 80 ° C. or lower, preferably 0 to 40 ° C. to synthesize a polyamic acid resin. The organic solvent used for the reaction may not be capable of completely dissolving the starting material as long as it is inert to the polyamic acid obtained. For example, tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylform Amides and dimethylsulfoxides, and are preferably aprotic polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents can be used 1 type or in combination or 2 or more types.

On the other hand, in order to adjust the molecular weight of resin, dicarboxylic acid anhydrides, such as maleic anhydride and phthalic anhydride, and / or monoamines, such as aniline and n-butylamine, can be added. However, the addition amount of dicarboxylic anhydride is 0-2 mass parts normally per 100 mass parts of dicarboxylic dianhydride, and the addition amount of monoamine is 0-2 mass parts normally per 100 mass parts of diamine.

As for the molecular weight of polyamic-acid resin, about 3,000-100,000 are preferable as a weight average molecular weight by polystyrene conversion in GPC. When the said molecular weight is less than 3,000, the toughness and flexibility of a cured film will fall, and when it exceeds 100,000, workability may fall because of high viscosity.

The alkoxysilyl group-containing polyamic acid resin represented by the following general formula (1) can be obtained by adding the epoxy group of the epoxy group-containing alkoxysilane compound represented by the following formula (29) to the carboxyl group of the polyamic acid resin thus obtained.

≪ Formula 1 >

로 표시되는 기이고, R⁴는 탄소수 1 내지 3의 알킬기이고, R⁵는 탄소수 1 내지 3의 알킬기 또는 알콕시기이고, a는 0 내지 4의 정수이고, p는 1 내지 300의 정수이고, q는 1 내지 300의 정수이고, r은 1 내지 100의 정수이다.Wherein X is a tetravalent organic group, Y is a divalent organic group, and Z is

R ⁴ is an alkyl group having 1 to 3 carbon atoms, R ⁵ is an alkyl group or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q Is an integer from 1 to 300, and r is an integer from 1 to 100.

In the above formula, X, Y, Z, R ¹ , R ² , a, p, q and r are as described above, but p and q are each independently an integer of 1 to 300, in particular of 2 to 200 It is preferable that it is an integer, r is an integer of 1-100, in particular, it is preferable that it is an integer of 2-80, and it is preferable that a is 0, 1, 2 or 3.

Moreover, reaction of the said carboxyl group and an epoxy group can be performed according to a conventional method, reaction temperature is 30-130 degreeC, reaction time is about 1 to 10 hours, and can be performed using the solvent at the time of polyamic-acid resin synthesis as needed. . On the other hand, the amount of use (molar ratio) of the epoxy group-containing alkoxysilane compound of the formula is that the reaction between the carboxyl group in the raw material polyamic acid resin and the epoxy group in the silane compound of formula 29 proceeds quantitatively (i.e. In the premise, the compound of Formula 1 is used in an amount capable of forming.

A commercial item can be used as said alkoxy silyl group containing polyamic-acid resin, Composeran H801D, H850D (made by Arakawa Chemical Industries, Ltd.) etc. are mentioned as a commercial item.

In addition, the polyamic acid resin which does not contain an alkoxy silyl group can be used in combination with the said alkoxy silyl group containing polyamic acid resin. As said polyamic acid resin, it is obtained by making tetracarboxylic dianhydride and diamine react in the equimolar equivalence in the organic solvent substantially in the same manner as the polyamic acid resin illustrated as a raw material of the said (A) component. Examples of the tetracarboxylic dianhydride and the diamine include the same specific examples as the general formulas (4) and (5).

(B) component is spherical metal oxide fine particle whose average particle diameter is 0.05-10 micrometers. As these spherical metal oxide fine particles, those having a sphericity of Wadell of 0.7 to 1.0 are preferable.

Here, "Wadel's spherical shape" (see the Chemical Engineering Manual, published by Maruzen Kabuki Kaisha) means the spherical shape of the particle (diameter of the same circle as the projected area of the particle) / (minimum circle circumscribed on the particle projection) Diameter, which is closer to 1.0, means that the particles are closer to the spherical sphere.

As for the spherical metal oxide fine particles of this invention, it is preferable that the sphericity degree of a wadel is more preferably 0.9-1.0, and especially preferably 0.95-1.0. If the spherical degree of the wadel is less than 0.7, the thixotropy of the composition may increase when the amount of the (B) component is increased.

From the viewpoint of low thixotropy, as the component (B), spherical metal oxide fine particles containing 60 to 100% by mass, particularly 80 to 100% by mass, of spherical metal oxide fine particles are preferable. On the other hand, in the present specification, "spherical" is a concept including a slightly modified sphere having a sphericity of 0.95 to 1.

In addition, "average particle diameter" means "volume average particle diameter", For example, it measures by the automated method by the laser diffraction scattering type particle size distribution measuring apparatus (brand name: LA910) by Horiba Corporation. can do.

The average particle diameter of spherical metal oxide fine particles becomes like this. Preferably it is 0.05-5 micrometers, More preferably, it is 0.1-5 micrometers. In addition, the spherical metal oxide fine particles are preferably spherical metal oxide fine particles.

The spherical metal oxide fine particles may be fine particles of one kind of metal oxide, or may be fine particles of two or more kinds of metal oxides (ie, complex oxides). Specific examples of one metal oxide include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), and zirconia (ZrO ₂ ), which are oxides of metals such as silicon, aluminum, magnesium, zirconium, and titanium. ), And the like. Specific examples of the composite oxide include two-component composite oxides such as silica-alumina composite oxide, silica-titania composite oxide, silica-zirconia composite oxide, silica-magnesia composite oxide, and alumina-magnesia composite oxide. And three-component complex oxides such as silica-alumina-magnesia composite oxide, silica-alumina-titania composite oxide, and silica-titania-magnesia composite oxide. Among the examples of these spherical metal oxide fine particles, those having spherical, especially spherical silica fine particles as a main component (that is, containing 60 to 100 mass%) are preferable.

Spherical metal oxide fine particles may be optionally prepared, but metal oxide fine particles obtained by burning a metal are preferable. Metal oxide fine particles obtained by burning this metal include metal powders such as silicon, aluminum, magnesium, zirconium and titanium; Mullite composition (3Al ₂ O ₃ · 2SiO ₂ to 2Al ₂ O ₃ · SiO ₂₎ an aluminum powder and silicon powder in combination; Magnesium powder and aluminum powder combined with a spinel composition (MgAl ₂ O ₄ ); Aluminum powder, magnesium powder and silicon powder combined with cogelite composition (2MgO.2Al ₂ O ₃ .5SiO ₂ ); A metal powder mixture such as this is combusted together with a carrier gas in an atmosphere containing oxygen to form a chemical flame, and an oxide or a complex oxide of one metal such as silica, alumina, titania, zirconia, etc., is used in the chemical flame. Particulates (particularly ultrafine particles) can be obtained. Among the metal oxide fine particles obtained by burning these metals, it is preferable to have spherical, especially spherical silica fine particles as a main component (that is, containing 60 to 100 mass%).

The spherical metal oxide fine particles need not be surface treated, but the surface is preferably treated with silazanes and / or silane coupling agents.

The silazanes are, for example, silazanes such as hexamethyldisilazane (HMDS) and hexaphenyldisilazane, or a combination of two or more thereof. Among these, hexamethyldisilazane suppresses agglomeration of silica and inclines acidic silica to basicity, thereby improving affinity for organics, improving uniformity, and improving stability of component (A) to resins. It is preferable at the point of improving.

The silane coupling agent is, for example, a compound having one or more active groups (reactive organic functional groups) selected from the group consisting of amino groups, glycidyl groups, mercapto groups, ureido groups, hydroxy groups and alkoxy groups, or combinations thereof (for example , Alkoxy group and other reactive functional groups). Specific examples of the silane coupling agent include epoxy functional group-containing organoalkoxysilanes and aminopropyltriethoxy such as γ-glycidoxypropyltriethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Arylalkoxysilanes such as amino functional group-containing organoalkoxysilanes such as silane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and phenyltrimethoxysilane, methyltrimethoxysilane, octadecyltri Alkenyl alkoxysilanes, such as alkyl alkoxysilanes, such as a methoxysilane, vinyltrimethoxysilane, and allyl trimethoxysilane, mercapto functional group containing organoalkoxysilane, such as (gamma) -mercaptopropyl trimethoxysilane, etc. are mentioned. Can be.

In addition, a well-known method can be employ | adopted as a processing method.

As spherical metal oxide microparticles | fine-particles, the commercially available admaphine SE series, SC series, etc. are mentioned as a commercial item.

(B) A component can be used individually by 1 type and can also use 2 or more types together, The compounding quantity of (B) component is 5-350 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-300 It is 10 mass parts, More preferably, it is 10-200 mass parts. When this compounding quantity is less than 5 mass parts, favorable screen printability may not be obtained, and when it exceeds 350 mass parts, adhesiveness with the base material which is the original characteristic of resin of (A) component may be impaired.

In the resin composition for screen printing of the present invention, by using spherical metal oxide fine particles of the present component, it is possible to suppress thixotropy low even in the blending amount, and the formed pattern does not cause deterioration of mesh eye residues, bleeding, defoaming, etc. Uniform film thickness is obtained.

On the other hand, as the metal oxide powder, non-spherical oxide powders such as molten metal oxide powder, metal oxide crushed matter, aerosol metal oxide (fumed metal oxide) and the like can be used in combination without affecting the above effects. The combined ratio of the non-spherical metal oxide powder is preferably 25 parts by mass or less (0 to 25 parts by mass), particularly 20 parts by mass or less (0 to 20 parts by mass) with respect to 100 parts by mass of the spherical metal oxide powder of the component (B). Do.

As the organic solvent of the component (C), those which can partially or completely dissolve the resin of the component (A) can be used.

Specific examples of the component (C) include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone, N, N -Dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, and the like, and are preferably aprotic polar solvents, particularly preferably N- Methylpyrrolidone, N-vinylpyrrolidone, cyclohexanone, γ-butyrolactone and 1,3-dimethyl-2-imidazolidinone.

When the cured film formed from the composition of this invention is a thin film of 20 micrometers or less, it is preferable to use together the organic solvent whose boiling point is 200 degreeC or more especially in order not to impair the continuous formability by screen printing. As an organic solvent whose boiling point is 200 degreeC or more, (gamma) -butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone, and 1, 3- dimethyl- 2-imidazolidinone are mentioned, for example. .

In addition, (C) component may be used individually by 1 type and may use 2 or more types together.

The compounding quantity of (C) component is an effective amount which can melt | dissolve the said (A) component, Usually, it is preferable that it is an amount which makes solid amount 10-80 mass%, especially 20-70 mass%.

(D) epoxy resin and (E) hardening accelerator can be mix | blended with the resin composition for screen printing of this invention further.

Although the epoxy resin which has two or more epoxy groups in 1 molecule of (D) component of this invention does not have a restriction | limiting in particular, The epoxy resin represented by following General formula (2) is mentioned as a preferable example.

<Formula 2>

In the formula, G is a glycidyl group, R represents a hydrogen atom or a monovalent hydrocarbon group, provided that at least one of all R is a monovalent hydrocarbon group, and n is 0 or an integer of 1 or more.

Here, as the monovalent hydrocarbon represented by R, an unsubstituted or substituted monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms, in particular having 1 to 6 carbon atoms, an aryl group is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, t -Butyl group, a phenyl group, etc. are mentioned as a typical thing.

Further, in the epoxy resin of the formula (2), n is 0 or an integer of 1 or more, preferably n or an integer of 1 to 20, in particular 0 or an integer of 1 to 10, the epoxy resin of the formula (2) is a different value of n It may be a mixture of epoxy resins. In this case, in order to make the glass transition temperature of hardened | cured material as high as possible, it is 70 mass% or less, preferably 60 mass% or less that n is 0, and the average value of n which shows average polymerization degree is the molecular weight in the range of 1-3. It is preferable to select an epoxy resin having a distribution. Here, when containing more than 70 mass% of n = 0, glass transition temperature may fall.

Specific examples of the epoxy resin of Formula 2 may include the following Formulas 30 to 32.

를 나타내고, n은 상기한 바와 같다(이하, 동일).Wherein t-Bu is a t-butyl group, and OG is

And n is as described above (hereinafter same).

In the present invention, in addition to the epoxy resin of the formula (2), other epoxy resins, for example, bisphenol A epoxy resin, novolak-type epoxy resin, alicyclic epoxy resin, glycidyl-type epoxy resin, or the following formula 33 to 35 The epoxy resin represented by can be combined suitably.

It is also possible to use brominated epoxy resins for flame retardant. The brominated epoxy resins include the following formulas (36) and (37).

These epoxy resins can be used individually or in mixture of 2 or more types. Moreover, 1-150 mass parts is preferable with respect to 100 mass parts of alkoxy silyl group containing polyamic-acid resin, and, as for the usage-amount of these epoxy resins, More preferably, it is 2-100 mass parts. If it is less than 1 mass part, the adhesive strength with respect to the base material of hardened | cured material will not be obtained. On the other hand, if it exceeds 150 mass parts, the heat resistance of hardened | cured material may fall.

In this case, it is preferable that the epoxy resin of the said Formula (2) is 1-100 mass%, especially 5-100 mass% in an epoxy resin whole quantity.

Although the hardening accelerator of (E) component of this invention does not have a restriction | limiting in particular, From an aspect of the high reactivity of the said alkoxy silyl group containing polyamic acid resin and an epoxy resin, an amine catalyst is preferable. As the amine catalyst, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethyl are Imidazole derivatives, such as midazole, etc. can be mix | blended, Among these, 1 type, or 2 or more types can be used. Especially preferably, by using the imidazole compound of the following formula (38), by using the imidazole compound having such a structure, it is possible to impart high heat resistance, high moisture resistance and high adhesion of the cured product.

In the formula, Ph represents a phenyl group.

As another hardening accelerator, a phosphorus catalyst, specifically triphenylphosphine, triphenylphosphonium triphenyl borate, tetraphenylphosphonium tetraphenyl borate, or the compound shown by following formula (39) can also be used.

In formula, R <^3> -R <^10> is a hydrogen atom, a halogen atom, such as fluorine, bromine, iodine, a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C1-C8 An alkoxy group, a trifluoromethyl group, a phenyl group, etc. are mentioned, All substituents may be same or different.

As for the usage-amount of the hardening accelerator of this (E) component, 0.001-20 mass parts is preferable with respect to 100 mass parts of total amounts of an alkoxy silyl group containing polyamic-acid resin (A) and an epoxy resin (D), More preferably, it is 0.01-10 mass It is wealth. If it is less than 0.001 mass part, it may not be hardened in a short time, and when it exceeds 20 mass parts, the storage stability of a composition may run short.

In addition to the components (A) to (E), the composition of the present invention includes, for example, coloring agents such as antioxidants, heat stabilizers, conductive fillers, pigments, dyes, and the like within the range of not impairing the effects of the present invention. Can be added accordingly.

The composition of this invention can mix and manufacture the above-mentioned (A)-(C) component, (A)-(E) component, and the other component contained as needed by a conventional method. Specifically, for example, a mill equipped with a stirring device and a heating device, three rolls, a ball mill, a planetary mixer, or the like can be used. Moreover, these mixing devices can also be used in combination of 2 or more types as appropriate.

In the method of applying the composition to a substrate surface such as a silicon wafer (screen printing method), first, the surface of the substrate is covered with a mask having an opening of a required pattern, the composition is introduced into the squeegee portion, and then the squeegee is moved. The mask phase is moved while pressing the composition, the composition is filled in the opening of the masking member (filling step), and then the mask is removed, thereby forming a pattern of the composition on the surface of the substrate. The curing of the composition thus formed is carried out stepwise (for example, at one or two or more curing temperatures) at a low temperature of, for example, room temperature (20 ° C. ± 5 ° C.) to 200 ° C., and further if necessary. This is achieved by performing high temperature curing (postcure) at 200 to 350 ° C. On the other hand, 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 high resolution, and a uniform film thickness is obtained without causing mesh eye residues, bleeding, or deterioration of defoaming properties. Furthermore, because of its excellent continuous formability, printed circuit boards are used in addition to junction protective films of passivation films, passivation films, diodes, and transistors on the surface of semiconductor elements at the wafer level, α-ray shield films of VLSIs, interlayer insulating films, ion implantation masks, and the like. It can be used over a wide range as a resin composition for screen printing suitable for formation of the conformal coating, the alignment film of a liquid crystal surface element, the protective film of glass fiber, the surface protective film of a solar cell, or the electrically conductive film which mix | blended the conductive filler.

When using the resin composition for screen printing of this invention as a protective film, such as the said semiconductor element, it is apply | coated to a semiconductor element and / or a lead frame by screen printing, and this heat-hardens, for example, the film of about 0.1-100 micrometers in thickness can be formed. Can be. After curing a film by the curing conditions, by molding a molding epoxy resin composition for semiconductor sealing material semiconductor sealing epoxy resin molding material for the substrate (for example, Ni, Ag, Cu, Si, SiO _2, such as the substrate of the inorganic) The adhesiveness with can be improved. In the semiconductor device thus obtained, cracks of the epoxy resin molding material for semiconductor sealing and peeling from the substrate (for example, inorganic substrates such as Ni, Ag, Cu, Si, and SiO ₂ ) are not observed in the solder reflow after moisture absorption. The reliability is high.

<Examples>

Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to this.

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

Resin composition component for screen printing

(A) Base resin

Resin Solution A:

An alkoxysilyl group-containing polyamic acid resin solution (Composecean H801D: manufactured by Arakawa Chemical Industries, Ltd.) was manufactured from a resin component 25%.

Resin Solution B:

An alkoxysilyl group-containing polyamic acid resin solution (Composecean H850D: manufactured by Arakawa Chemical Industries, Ltd.) was manufactured from a resin component 25%.

Resin solution C (synthesis example):

32.22 g (0.10 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and N-methyl-2 as tetracarboxylic dianhydride in a flask equipped with a stirrer, a thermometer and a nitrogen replacement device Add 35 g of pyrrolidone, which is 2.49 g (0.01 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane as diamine and 4,4'-dia A solution in which 18.02 g (0.09 mol) of minodiphenyl ether was dissolved in 20 g of N-methyl-2-pyrrolidone was slowly added dropwise while adjusting the temperature of the reaction system not to exceed 50 ° C. After completion of the dropwise addition, the mixture was further stirred at room temperature for 12 hours to promote the reaction, thereby obtaining a yellowish-brown transparent polyamic acid resin solution. The viscosity of this solution was 250 Pa.s, and the resin solid content was 50.1 mass%. Let this be the resin solution C.

(B) epoxy resin

(One)

Softening point: 85 ℃, Epoxy equivalent: 214

(n = 0:59 mass%, n = 1:24 mass%, n = 2: 8 mass%, other: 9 mass%)

(2)

Softening point: 79 ℃, Epoxy equivalent: 165

(n = 0: 54 mass%, n = 1: 31 mass%, n = 2: 9 mass%, other: 6 mass%)

(3) Bisphenol A type (Epikote 1001: manufactured by JER Corporation)

Softening point: 64 ℃, Epoxy equivalent: 450

(C) curing accelerator

2-methyl-4,5-dihydroxymethylimidazole (2PHZ)

(D) fillers

(1) Spherical silica fine particles (Admafine SC2500-SE: manufactured by Admatech Co., Ltd.)

(2) Fumed silica (AEROSIL R972: manufactured by Nippon Aerosil Co., Ltd., particle shape is amorphous)

(E) Organic solvent

N-methyl-2-pyrrolidone (NMP)

1,3-dimethyl-2-imidazolidinone (DMI)

The component of said (a)-(e) was mixed uniformly so that it might become the composition (unit is a mass part) shown in Table 1, and the paste resin composition was obtained. The obtained composition was evaluated as follows. The results are shown in Table 1.

Assessment Methods

(A) Viscosity

The viscosity in 23 degreeC was measured using the digital viscometer (The Brookfield company make, brand name: DV-II +).

(B) screen printability

The screen printing machine (C.W. PRICE CO. INC. Make, brand name: MODEL MC212) and the screen mask (325 mesh, emulsion thickness: 15 micrometers, mesh thickness: 35 micrometers) were performed. Deterioration of the pattern shape after 100 times of continuous molding was confirmed by setting a mask, filling a composition by squeegee, and removing a mask as one shaping | molding process. Thereafter, curing was performed by exposure in an oven at 100 ° C. for 0.5 hours, followed by 250 hours at 250 ° C., and bleeding of the mesh eyes, foaming and pattern edges was observed for the obtained pattern.

(C) Adhesiveness after moisture absorption

After apply | coating and hardening a resin composition to the various test pieces of Table 1, an epoxy resin composition (KMC3580CA: Shin-Etsu Chemical Co., Ltd. product) was made into 175 degreeC and 6865 kPa in the cylindrical shape of 10 mm <^2> of height, 3 mm in height. (70 kg / cm <2>) and it shape | molded on the conditions of 90 second of molding time, and it hardened | cured after 180 hours at 180 degreeC. This was left to stand in the atmosphere of 85 degreeC / 85% RH for 168 hours, and also the peel force of the molded object and various test pieces was measured by the push pull gauge after 260 degreeC and IR reflow.

(D) Crack resistance by heat cycle

A silicon chip having a size of 9.0 mm x 4.5 mm x 0.5 mm was bonded to a 14PIN-IC frame (alloy 42), and then the resin composition shown in Table 1 was applied and cured, and then the epoxy resin composition was 175 ° C. After molding for 90 seconds, curing at 180 ° C. for 4 hours, the heat cycle of −50 ° C., 30 minutes to 180 ° C., and 30 minutes was repeated, and the resin crack generation rate after 1,000 cycles was measured.

From Table 1, the Example can confirm that a viscosity is suppressed suitably compared with the comparative example and is excellent also in printability. Moreover, it can be confirmed that it is excellent also in the adhesiveness after moisture absorption and the crack tolerance by a heat cycle.

According to the present invention, it is possible to provide a resin composition for screen printing that has good screen printability, obtains a uniform film thickness without causing mesh eye residues, smearing, deterioration of defoamability, and the like and also has excellent continuous moldability.

In addition, it has excellent adhesion to the substrate and plastic material, efficiently eliminates chip cracks and thermal deterioration due to thermal stress of the semiconductor package to provide a cured product excellent in heat resistance, and uses an epoxy resin molding material for semiconductor sealing. To provide a resin composition for screen printing that is effective as a protective film material when sealing a semiconductor.

Claims (8)

(A) 100 parts by mass of an alkoxysilyl group-containing polyamic acid resin represented by the following formula (1), (B) 5 to 350 parts by mass of spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 µm, and (C) tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, gamma-in an amount of 10 to 80 mass% of solid content capable of dissolving the resin of the component (A). Butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone At least one organic solvent selected from Resin composition for screen printing, comprising as an essential component. &Lt; Formula 1 >

Wherein X is a tetravalent organic group, Y is a divalent organic group, and Z is

R ⁴ is an alkyl group having 1 to 3 carbon atoms, R ⁵ is an alkyl group or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q Is an integer from 1 to 300, and r is an integer from 1 to 100. (A) an alkoxysilyl group-containing polyamic acid resin represented by the following formula (1), (B) spherical metal oxide fine particles having an average particle diameter of 0.05 to 10 µm, (C) tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone and N- in an amount of 10 to 80 mass% of solid content At least one organic solvent selected from vinylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, (D) an epoxy resin having two or more epoxy groups in one molecule, and (E) curing accelerator Resin composition for screen printing, containing. &Lt; Formula 1 >

Wherein X is a tetravalent organic group, Y is a divalent organic group, and Z is

R ⁴ is an alkyl group having 1 to 3 carbon atoms, R ⁵ is an alkyl group or alkoxy group having 1 to 3 carbon atoms, a is an integer of 0 to 4, p is an integer of 1 to 300, q Is an integer from 1 to 300, and r is an integer from 1 to 100. The resin composition for screen printing according to claim 2, wherein the epoxy resin of the component (D) is an epoxy resin represented by the following general formula (2). <Formula 2>

In the formula, G is a glycidyl group, R represents a hydrogen atom or a monovalent hydrocarbon group, provided that at least one of all R is a monovalent hydrocarbon group, and n is 0 or an integer of 1 or more. The resin composition for screen printing according to any one of claims 1 to 3, wherein the surface of the metal oxide fine particles of the component (B) is treated with silazanes and / or a silane coupling agent. The resin composition for screen printing according to claim 4, wherein the silazanes are hexamethyldisilazane. The resin composition for screen printing according to claim 4, wherein the silane coupling agent is one kind or two or more kinds of compounds having an active group selected from amino group, glycidyl group, mercapto group, ureido group, hydroxy group and alkoxy group. The resin composition for screen printing according to any one of claims 1 to 3, wherein the component (B) contains 60 to 100% by mass of spherical silica 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 3, wherein an organic solvent having a boiling point of 200 ° C or higher is contained as the component (C).