JP5245474B2 - Resin composition for screen printing - Google Patents

Description

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

  Polyimide materials are widely used for adhesives, sheet materials, sealing materials and the like because of their excellent heat resistance. For example, the semiconductor surface is coated as a heat-resistant material and plays a role as a protective insulating film. As a method of forming a pattern on these protective films, a method of patterning after spin coating in a varnish state, or A method of patterning simultaneously with coating by screen printing 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 film is laminated thereon to dissolve the photosensitive or non-photosensitive part by ultraviolet light exposure and development. At the same time, the photosensitive layer or non-photosensitive portion is dissolved by ultraviolet light exposure and development using a method in which the underlying protective film is dissolved to form a pattern, or a photosensitive resin in which the polyimide resin itself has an ultraviolet sensitive portion. And the like. In any case, since the process involves complicated steps including ultraviolet exposure, the latter screen printing method is desired from the viewpoint of shortening the process. However, conventional screen printing varnishes do not always give satisfactory results in terms of resolution, film flatness, and the like. As one of the reasons, for maintaining the shape, there are mesh residuals and blurring due to the addition of an inorganic filler to the varnish and imparting thixotropy, deterioration of foam removal properties, and the like. In particular, when a thin film is formed, there is a problem that the solvent volatilizes quickly and the continuous formability is poor.

  Furthermore, when a polyimide-based material is used as a protective film for a semiconductor element, it is applied directly to the semiconductor element or through an insulating film, and then cured to form a protective film made of a polyimide resin, and molding of an epoxy resin or the like. These packages are sealed with materials, but these packages have different expansion coefficients of components such as elements, substrates, and sealing materials. Therefore, thermal stress occurs during heat cycle and solder reflow in the subsequent process, and the chip Problems such as cracks and thermal degradation have occurred. For this reason, the polyimide resin protective film is required to absorb stress due to high adhesiveness with these materials and low elastic modulus. However, when an inorganic filler or the like is added to the resin in order to impart printability as described above, there is a problem that all of the above characteristics are deteriorated.

  As a countermeasure, a proposal has been made to reduce the elastic modulus by introducing a siloxane bond into the polyimide resin skeleton, but as a result, the glass transition temperature (Tg) of the cured film is lowered, and the heat resistance of the resin There was a problem of falling. JP-A-3-189127 (Patent Document 1) and JP-A-4-264003 (Patent Document 2) all propose siloxane-modified polyamideimides. However, these resins have problems in that the adhesive strength to the copper foil is not sufficient, the glass transition temperature (Tg) of the cured film is lowered, and the heat resistance of the resin is lowered.

On the other hand, polyamide-based and / or polyimide-based sheet materials and paste materials are used for recent die bonding or lead frame bonding, but materials that can be printed and have adhesiveness, heat resistance and low elastic modulus are desired. Has been.
Furthermore, Japanese Patent No. 3819057 (Patent Document 3) discloses a resin composition for printing using a polyimide silicone resin and an epoxy resin in combination. This polyimide silicone resin is a portion in which repeating units are arranged at random. Since a polyimide silicone resin having no blocking structure is used, a printing resin composition having a low elastic modulus cannot be obtained.
Japanese Patent Laid-Open No. 3-189127 JP-A-4-264003 Japanese Patent No. 3819057

  An object of the present invention is to provide a polyimide-based screen printing resin composition that is excellent in adhesiveness and heat resistance and has a low elastic modulus so as to eliminate the above-mentioned drawbacks.

  As a result of intensive studies to achieve the above object, the present inventor, in combination with spherical metal oxide fine particles, and epoxy resin and its curing agent, are combined with the partial block polyimide-polysiloxane copolymer described later. Thus, it has been found that a polyimide-based resin composition for screen printing that gives a screen printed film having high adhesion, high heat resistance, and low elastic modulus can be obtained, and the present invention has been made.

（式中、Ｘは芳香族環又は脂肪族環を含む４価の有機基の１種又は２種以上、Ｙ₁は２価の有機基、Ｙ₂は下記構造式（３）で示される２価の有機基であり、Ｙ₃は下記構造式（９’）で示される２価の有機基である。基Ｙ₁、Ｙ₂、Ｙ₃の合計に対するＹ₂のモル比は、Ｙ₂／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０．０１〜０．８０であり、基Ｙ₁、Ｙ₂、Ｙ₃の合計に対するＹ₃のモル比は、Ｙ₃／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０．０１〜０．９９である。ｋは１〜５０の自然数、ｍは１〜５０の自然数、ｊは１〜５０の自然数である。）

（式中、Ｒ¹は炭素原子数３〜９の２価の有機基、Ｒ²及びＲ³は各々独立に炭素原子数１〜８の非置換又は置換の１価炭化水素基、ｎは１〜１５０の整数である。）

（式中、Ｒは独立に水素原子、ハロゲン原子、又は置換もしくは非置換の炭素数１〜８の１価炭化水素基を示す。ｋは１〜５の自然数である。）
（Ｂ）表面がシランカップリング剤で処理された平均粒子径が０．０５〜１０μｍの球状金属酸化物微粒子：（Ａ）成分１００質量部に対して５〜３５０質量部、
（Ｃ）有機溶剤、
（Ｄ）１分子中に少なくとも２個のエポキシ基を有するエポキシ樹脂、
（Ｅ）上記エポキシ樹脂の硬化剤：（Ｄ）成分の硬化有効量
を含有してなり、（Ｄ）及び（Ｅ）成分の合計量が（Ａ）成分１００質量部に対して１〜９００質量部であることを特徴とするスクリーン印刷用樹脂組成物。
［ＩＩ］上記シランカップリング剤が、アミノ基、グリシジル基、メルカプト基、ウレイド基、ヒドロキシ基、アルコキシ基、メルカプト基から選択される活性基を有する化合物の１種以上であることを特徴とする［Ｉ］記載のスクリーン印刷用樹脂組成物。
［ＩＩＩ］（Ｂ）成分が、平均粒子径０．０５〜１０μｍの真球状シリカを６０〜１００質量％含有することを特徴とする［Ｉ］又は［ＩＩ］記載のスクリーン印刷用樹脂組成物。
［ＩＶ］（Ｃ）成分として、沸点２００℃以上の有機溶剤を含有することを特徴とする［Ｉ］乃至［ＩＩＩ］のいずれかに記載のスクリーン印刷用樹脂組成物。
［Ｖ］（Ｃ）成分が、（Ａ）成分１００質量部に対して１０〜５００質量部であることを特徴とする［Ｉ］乃至［ＩＶ］のいずれかに記載のスクリーン印刷用樹脂組成物。
That is, the present invention provides the following resin composition for screen printing.
[I] (A) a partial block polyimide-polysiloxane copolymer having a repeating unit represented by the following structural formulas (2) and (8) and capable of containing a repeating unit represented by the following structural formula (1);

(In the formula, X is one or more of tetravalent organic groups including an aromatic ring or an aliphatic ring, Y ₁ is a divalent organic group, and Y ₂ is ₂ represented by the following structural formula (3). Y ₃ is a divalent organic group represented by the following structural formula (9 ′) The molar ratio of Y _{2 to} the sum of the groups Y ₁ , Y ₂ , Y ₃ is Y ₂ / _{(Y 1 + Y 2 + Y} 3) = a .01 to .80, group Y _1, Y _2, the molar ratio of Y ₃ to the sum of Y _{3 is, Y 3 / (Y 1 +} Y 2 + Y 3) = (K is a natural number from 1 to 50, m is a natural number from 1 to 50, and j is a natural number from 1 to 50.)

Wherein R ¹ is a divalent organic group having 3 to 9 carbon atoms, R ² and R ³ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 It is an integer of ~ 150.)

(In the formula, R independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. K is a natural number of 1 to 5.)
(B) Spherical metal oxide fine particles whose surface is treated with a silane coupling agent and having an average particle diameter of 0.05 to 10 μm: 5 to 350 parts by mass with respect to 100 parts by mass of component (A),
(C) an organic solvent,
(D) an epoxy resin having at least two epoxy groups in one molecule;
(E) Curing agent for the above epoxy resin: It contains a curing effective amount of the component (D), and the total amount of the components (D) and (E) is 1 to 900 masses per 100 parts by mass of the component (A). A resin composition for screen printing, which is a part.
[II] The silane coupling agent is one or more compounds having an active group selected from an amino group, a glycidyl group, a mercapto group, a ureido group, a hydroxy group, an alkoxy group, and a mercapto group. [I] Symbol mounting for screen printing resin composition.
[III] (B) component, characterized by containing a spherical silica having an average particle diameter of 0.05 to 10 [mu] m 60 to 100 [wt% [I] or [II] Symbol mounting for screen printing resin composition .
[IV] The resin composition for screen printing according to any one of [I] to [ III ], which contains an organic solvent having a boiling point of 200 ° C. or higher as the component (C).
The resin composition for screen printing according to any one of [I] to [ IV ], wherein the component [V] (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the component (A). .

  The present invention provides a polyimide-based screen printing resin composition that solves the above-mentioned problems in printing materials and provides good performance with high adhesion, high heat resistance, and low elastic modulus.

（式中、Ｘは芳香族環又は脂肪族環を含む４価の有機基の１種又は２種以上、Ｙ₁は２価の有機基（但し、下記構造式（３）で示される２価の有機基及びエポキシ基との反応性を有する官能基を持つ２価の有機基Ｙ₃を除く）、Ｙ₂は下記構造式（３）で示される２価の有機基であり、Ｙ₃はエポキシ基との反応性を有する官能性基を持つ２価の有機基である。<Ｉ>の場合、Ｙ₂がモル比でＹ₂／（Ｙ₁＋Ｙ₂）＝０．０１〜０．８０、<ＩＩ>の場合、Ｙ₂はモル比でＹ₂／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０．０１〜０．８０、Ｙ₃はモル比でＹ₃／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０．０１〜０．９９である。ｋは１〜５０の自然数であり、ｍは１〜５０の自然数であり、ｊは１〜５０の自然数である。）

（式中、Ｒ¹は炭素原子数３〜９の２価の有機基、Ｒ²及びＲ³は各々独立に炭素原子数１〜８の非置換又は置換の１価炭化水素基、ｎは１〜１５０の整数である。）
（Ｂ）平均粒子径が０．０５〜１０μｍの球状金属酸化物微粒子、
（Ｃ）有機溶剤、
（Ｄ）１分子中に少なくとも２個のエポキシ基を有するエポキシ樹脂、
（Ｅ）上記エポキシ樹脂の硬化剤
を必須成分として含有する。 The screen printing resin composition of the present invention comprises (A) a repeating unit <I> represented by the following structural formulas (1) and (2), or a repeating unit represented by the following structural formulas (2) and (8): Optionally, a partially block polyimide-polysiloxane copolymer having a repeating unit <II> represented by the following structural formula (1):

(In the formula, X is one or more of tetravalent organic groups containing an aromatic ring or an aliphatic ring, Y ₁ is a divalent organic group (provided that the divalent is represented by the following structural formula (3)) excluding a divalent organic group Y ₃ having a functional group) having reactivity with an organic group and an epoxy group, Y ₂ is a divalent organic group represented by the following structural formula (3), Y ₃ is It is a divalent organic group having a functional group having reactivity with an epoxy group, and in the case of <I>, Y ₂ is a molar ratio of Y ₂ / (Y ₁ + Y ₂ ) = 0.01 to 0.80. , <II>, Y ₂ is a molar ratio of Y ₂ / (Y ₁ + Y ₂ + Y ₃ ) = 0.01 to 0.80, Y ₃ is a molar ratio of Y ₃ / (Y ₁ + Y ₂ + Y ₃ ) = 0.01 to 0.99, k is a natural number of 1 to 50, m is a natural number of 1 to 50, and j is a natural number of 1 to 50.)

Wherein R ¹ is a divalent organic group having 3 to 9 carbon atoms, R ² and R ³ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 It is an integer of ~ 150.)
(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;
(E) The epoxy resin curing agent is contained as an essential component.

（式中、Ｘ，Ｙ₁，Ｙ₂，ｋ，ｍは上記に同じ。）
で示されるジアミン化合物から選ばれる１種あるいは２種以上と、下記一般式（６）及び（７） (A) Component Among the above components (A), the partial block polyimide-polysiloxane copolymer having a repeating unit <I> is represented by the following general formulas (4) and (5).

(In the formula, X, Y ₁ , Y ₂ , k and m are the same as above.)
And one or more selected from the diamine compounds represented by the following general formulas (6) and (7)

（式中、Ｘ，Ｙ₁，Ｙ₂，ｋ，ｍは上記に同じ。）
で示されるテトラカルボン酸二無水物あるいはこの前駆体であるテトラカルボン酸又はそのエステル誘導体から選ばれる１種あるいは２種以上とを略等モルで反応させることによって合成することができる。

(In the formula, X, Y ₁ , Y ₂ , k and m are the same as above.)
It can synthesize | combine by making 1 type or 2 types or more chosen from tetracarboxylic dianhydride shown by these, or the tetracarboxylic acid which is this precursor, or its ester derivative by substantially equimolar.

（但し、Ｘは上記と同様の意味を示す。）
で表されるテトラカルボン酸二無水物と、下記構造式（１２）： In this case, the polyimide oligomer represented by the general formulas (4) and (6) has the following structural formula (11):

(However, X has the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following structural formula (12):

（但し、Ｙ₁は上記と同様の意味を示す。）
で表されるジアミンとを所定のモル比で有機溶剤中で反応させることによってポリアミック酸樹脂を得た後、常法により脱水、閉環することで得られる。具体的には一般式（４）の末端アミンのオリゴマーについては、モル比で（ｐ）モルのテトラカルボン酸二無水物（１１）と（ｐ＋１）モルのジアミン（１２）を用い、一般式（６）の末端酸無水物のオリゴマーについては、モル比で（ｑ＋１）モルのテトラカルボン酸二無水物（１１）と（ｑ）モルのジアミン（１２）を用いる。ここでｐは１以上の自然数、ｑは１以上の自然数である。

(However, Y ₁ has the same meaning as described above.)
It is obtained by dehydrating and ring-closing by a conventional method after obtaining a polyamic acid resin by reacting with a diamine represented by the formula (1) in an organic solvent at a predetermined molar ratio. Specifically, for the terminal amine oligomer of general formula (4), (p) moles of tetracarboxylic dianhydride (11) and (p + 1) moles of diamine (12) are used in a molar ratio. For the terminal acid anhydride oligomer of 6), (q + 1) moles of tetracarboxylic dianhydride (11) and (q) moles of diamine (12) are used in a molar ratio. Here, p is a natural number of 1 or more, and q is a natural number of 1 or more.

In this case, X is preferably a tetravalent organic group containing 1 to 4 aromatic or aliphatic ring structures selected from a benzene ring, naphthalene ring, cyclohexane ring, and bicyclopentadiene ring. Y ₁ is preferably a divalent aromatic ring-containing diamine residue containing 1 to 4 aromatic ring structures selected from a benzene ring and a naphthalene ring.

等であるが、これらに限定されるものではない。なお、上記式（１１）のテトラカルボン酸二無水物は所望により上記のものの１種単独で又は２種以上を用いてもよい。 Here, when the example of the tetracarboxylic dianhydride represented by the said Formula (11) is shown concretely,

However, it is not limited to these. In addition, the tetracarboxylic dianhydride of the above formula (11) may be used alone or in combination of two or more as desired.

  Specific examples of the diamine represented by the above formula (12) are p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2 ′. -Bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-amino) Phenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthioether) benzene, 1,4- Bis (m-aminophenylthioether) benzene, 2,2-bis [4- (4-aminophenoxy) pheny ] 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-aminophenoxy) phenyl] methane, bis [3 -Methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenyl) Noxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane, and other aromatic ring-containing diamines. 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. Of course, it is not limited to these. These diamine compounds can also be used alone or in combination of two or more as desired.

  As a specific example of the polyimide oligomer formation reaction, the above starting materials are dissolved in a solvent under an inert atmosphere, and are usually reacted at 80 ° C. or lower, preferably 0 to 60 ° C., to form a polyamic acid oligomer. Is synthesized. Further, a method of synthesizing a target polyimide oligomer by dehydrating and ring-closing the acid amide portion of the polyamic acid oligomer by raising the temperature of the obtained polyamic acid oligomer to usually 100 to 250 ° C., preferably 150 to 200 ° C. Taken. At this time, it is desirable to use an azeotropic dehydrating agent such as toluene or xylene in order to facilitate the dehydration ring closure. Alternatively, an acetic anhydride / pyridine mixed solution can be added to the polyamic acid oligomer solution, and then the resulting solution can be heated to about 50 ° C. to perform imidization.

  The organic solvent used in the above reaction may not be one that can completely dissolve the starting material as long as it is inert to the resulting polyamic acid and polyimide. Examples include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide, preferably aprotic Polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

  The polyimide oligomer thus obtained often has a molecular weight distribution, and k in the formulas (4) and (6) is a natural number of 1 to 50, preferably 2 to 50, more preferably 3 to 45, Preferably it is a natural number of 4-40. The proportion of k being 2 or less is 50 mol% or less, preferably 40 mol% or less. If k exceeds 50, the compatibility with the oligomer having a siloxane skeleton is deteriorated and the film is not uniform. On the other hand, if the ratio of 2 or less is 50% or more, the effect of low elasticity and high heat resistance due to partial blocking may be reduced.

（但し、Ｘは上記と同様の意味を示す。）
で表されるテトラカルボン酸二無水物と、下記構造式（１３）：

（但し、Ｒ¹，Ｒ²，Ｒ³及びｎは前記の通りである）
で表されるシロキサンジアミンとを所定のモル比で有機溶剤中で反応させることによってポリアミック酸樹脂を得た後、常法により脱水、閉環することで得られる。具体的には一般式（５）の末端アミンのオリゴマーについては、モル比で（ｒ）モルのテトラカルボン酸二無水物（１１）と（ｒ＋１）モルのジアミン（１３）を用い、一般式（７）の末端酸無水物のオリゴマーについては、モル比で（ｓ＋１）モルのテトラカルボン酸二無水物（１１）と（ｓ）モルのジアミン（１３）を用いる。ここでｒは１以上の自然数、ｓは１以上の自然数である。 The polyimide oligomer represented by the general formulas (5) and (7) has the following structural formula (11):

(However, X has the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following structural formula (13):

(However, R ¹ , R ² , R ³ and n are as described above)
It is obtained by dehydrating and ring-closing by a conventional method after obtaining a polyamic acid resin by reacting with a siloxane diamine represented by the formula (I) in an organic solvent at a predetermined molar ratio. Specifically, for the terminal amine oligomer of the general formula (5), a molar ratio of (r) moles of tetracarboxylic dianhydride (11) and (r + 1) moles of diamine (13) is used. For the terminal acid anhydride oligomer of 7), (s + 1) moles of tetracarboxylic dianhydride (11) and (s) moles of diamine (13) are used in a molar ratio. Here, r is a natural number of 1 or more, and s is a natural number of 1 or more.

等のアリーレン基、これらを組み合わせたアルキレン・アリーレン基、

等のオキシアリーレン基やこれらを組み合わせた、

等のオキシアルキレン・アリーレン基等の、エーテル酸素原子を含んでもよい２価炭化水素基が挙げられる。 Here, specific examples of the tetracarboxylic dianhydride represented by the above formula (11) are as described above.
In the siloxane diamine (or α, ω-diaminosiloxane) represented by the general formula (13), examples of the divalent organic group having 3 to 9 carbon atoms represented by R ¹ include:

Arylene groups such as alkylene arylene groups combining these,

Oxyarylene groups such as

And a divalent hydrocarbon group which may contain an ether oxygen atom, such as an oxyalkylene / arylene group.

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ² and R ³ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl Alkyl groups such as 2-ethylhexyl and octyl, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl and hexenyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenylethyl, etc. A group in which some or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with halogen atoms such as fluorine, bromine and chlorine, such as a chloromethyl group, a bromoethyl group, and a 3,3,3-trifluoropropyl group Halogen substituted alkyl groups such as methyl group and phenyl group are preferred. Arbitrariness. n is an integer of 1-150, preferably an integer of 1-120, more preferably an integer of 1-100.

等が挙げられるが、これらに限定されるものではない。これらの上記式（１３）で表されるジアミノシロキサン化合物は所望により１種単独でも２種以上の組み合わせでも使用することができる。 As an example of the siloxane diamine represented by the general formula (13), specifically,

However, it is not limited to these. These diaminosiloxane compounds represented by the above formula (13) can be used alone or in combination of two or more as desired.

Specific examples of the formation reaction of the polyimide oligomer are as described above, and the above-mentioned organic solvents can be used.
The polyimide oligomer thus obtained often has a molecular weight distribution, and m in the formulas (5) and (7) is a natural number of 1 to 50, preferably 2 to 50, more preferably 3 to 45, Preferably it is a natural number of 4-40. The ratio in which m is 2 or less is 50 mol% or less, preferably 40 mol% or less. When m exceeds 50, the compatibility with the oligomer having no siloxane skeleton is deteriorated and the film is not uniform. On the other hand, if the ratio of 2 or less exceeds 50%, the effects of low elasticity and high heat resistance due to partial blocking may be reduced.

  The target partial block polyimide-polysiloxane copolymer is represented by one or more selected from diamine compounds represented by general formula (4) or (5), and represented by general formula (6) or (7). It can be synthesized by reacting one or more selected from tetracarboxylic dianhydride or tetracarboxylic acid which is a precursor thereof or an ester derivative thereof in an approximately equimolar amount. A specific example of the polyimide formation reaction is the same as in the case of the polyimide oligomer generation described above, and the above-mentioned organic solvent can be used.

In the partial block polyimide-polysiloxane copolymer <I> of the present invention, Y _{2 as} a siloxane component is Y ₂ / (Y ₁ + Y ₂ ) = 0.01 to 0.80 in molar ratio, preferably 0.02 to 0.70. If it is less than 0.01, the effect of imparting low elasticity is poor, and if it exceeds 0.80, a decrease in heat resistance and an increase in moisture permeability are observed.

  Furthermore, in addition to the repeating unit represented by the structural formula (2), the introduction of the repeating unit represented by the following structural formula (8) allows the polyimide-polyimide having a functional group reactive with an epoxy group. Siloxane copolymer <II> can be obtained. In this case, in addition to the repeating unit represented by the above structural formula (2) and the following structural formula (8), the repeating unit represented by the above structural formula (1) can be arbitrarily introduced as required.

（式中、Ｘは芳香族環又は脂肪族環を含む４価の有機基の１種又は２種以上、Ｙ₃はエポキシ基と反応性を有する官能基を持つ２価の有機基である。Ｙ₂はモル比でＹ₂／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０．０１〜０．８０であり、Ｙ₃はモル比でＹ₃／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０．０１〜０．９９である。更に、Ｙ₁はモル比でＹ₁／（Ｙ₁＋Ｙ₂＋Ｙ₃）＝０〜０．９８である。ｊは１〜５０の自然数である。）

(In the formula, X is one or more of tetravalent organic groups including an aromatic ring or an aliphatic ring, and Y ₃ is a divalent organic group having a functional group reactive with an epoxy group. Y ₂ is a molar ratio of Y ₂ / (Y ₁ + Y ₂ + Y ₃ ) = 0.01 to 0.80, and Y ₃ is a molar ratio of Y ₃ / (Y ₁ + Y ₂ + Y ₃ ) = 0.01 to Y ₁ is a molar ratio of Y ₁ / (Y ₁ + Y ₂ + Y ₃ ) = 0 to 0.98, and j is a natural number of 1 to 50.)

（式中、Ｘ，Ｙ₃，ｊは上記に同じ。）
で示されるジアミン化合物、並びに、任意に上記一般式（４）で示されるジアミン化合物とから選ばれる１種あるいは２種以上と、上記一般式（７）で示されるテトラカルボン酸二無水物あるいはこの前駆体であるテトラカルボン酸又はそのエステル誘導体、並びに、任意に上記一般式（６）で示されるテトラカルボン酸二無水物あるいはこの前駆体であるテトラカルボン酸又はそのエステル誘導体とから選ばれる１種あるいは２種以上とを略等モルで反応させることによって合成することができる。 The polyimide-polysiloxane copolymer <II> of the present invention has the above general formula (5) and the following formula (10).

(In the formula, X, Y ₃ and j are the same as above.)
And one or more selected from the diamine compound represented by the general formula (4) and a tetracarboxylic dianhydride represented by the general formula (7) or One kind selected from a tetracarboxylic acid or an ester derivative thereof as a precursor, and a tetracarboxylic dianhydride optionally represented by the general formula (6) or a tetracarboxylic acid or an ester derivative thereof as a precursor Or it can synthesize | combine by making 2 or more types react by substantially equimolar.

（但し、Ｘは上記と同様の意味を示す。）
で表されるテトラカルボン酸二無水物と、下記構造式（１４）

（但し、Ｙ₃は上記と同様の意味を示す）
で表されるジアミンとを、所定のモル比で有機溶剤中で反応させることによってポリアミック酸樹脂を得た後、常法により脱水、閉環することで得られる。 The polyimide oligomer represented by the general formula (10) has the following structural formula (11):

(However, X has the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following structural formula (14):

(However, Y ₃ has the same meaning as above.)
It is obtained by dehydrating and ring-closing by a conventional method after obtaining a polyamic acid resin by reacting in a predetermined molar ratio with an organic solvent.

（式中、Ｒは独立に水素原子、ハロゲン原子、又は置換もしくは非置換の炭素数１〜８の１価炭化水素基を示す。ハロゲン原子としては、フッ素、臭素、ヨウ素等が挙げられ、１価炭化水素基としては、アルキル基、アルケニル基、アルキニル基、アリール基や、これらの基の水素原子の一部又は全部がフッ素原子等のハロゲン原子で置換された基が挙げられ、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチル、ヘキシル、シクロヘキシル、ビニル、アリル、プロペニル、ヘキセニル、フェニル、トリフルオロメチル等を例示することができる。ｋは１〜５の自然数である。）
で表されるフェノール性水酸基を有するジアミンが好ましいが、これらに限定されるものではない。また、これらのジアミン化合物も所望により１種単独でも２種以上の組み合わせとしても使用することができる。 When the example of the diamine represented by the said Formula (14) is shown concretely,

(In the formula, R independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the halogen atom include fluorine, bromine and iodine. Examples of the valent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom. Propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, vinyl, allyl, propenyl, hexenyl, phenyl, trifluoromethyl, etc. k is a natural number of 1-5. )
Although the diamine which has the phenolic hydroxyl group represented by these is preferable, it is not limited to these. These diamine compounds can also be used alone or in combination of two or more as desired.

  Specifically, (t) moles of tetracarboxylic dianhydride (11) and (t + 1) moles of diamine (14) are used in a molar ratio. Here, t is a natural number of 1 or more.

  As a specific example of the production reaction of the polyimide oligomer (10), a diamine component having a phenolic hydroxyl group is dispersed or dissolved in the above-mentioned organic solvent in advance in a reaction vessel, and the acid dianhydride component is used as an organic solvent. It is preferable to carry out by heating the dissolved or dispersed solution at low temperature after dropping and stirring. When a diamine having a phenolic hydroxyl group is dropped under conditions where the acid dianhydride is rich, in addition to the amide formation reaction by the reaction of the carboxylic acid and the amine, an esterification reaction by the reaction of the carboxylic acid and the phenolic hydroxyl group also occurs simultaneously. Therefore, it crosslinks in three dimensions and gels. Since this gelled product has an ester bond structure, it undergoes a hydrolysis reaction under high-temperature and high-humidity conditions, lowers the molecular weight, and causes a decrease in moisture resistance reliability.

  The polyimide oligomer thus obtained often has a molecular weight distribution, and j in the formula (10) is a natural number of 1 to 50, preferably 2 to 50, more preferably 3 to 45, still more preferably 4. It is a natural number of ~ 40. The ratio in which j is 2 or less is 50 mol% or less, and preferably 40 mol% or less. When j exceeds 50, the compatibility with the acid anhydride-terminated oligomer is deteriorated, and the film is not uniform. On the other hand, if the ratio of 2 or less exceeds 50%, the effect of low elasticity and high heat resistance due to partial blocking may be reduced.

  The target polyimide-polysiloxane copolymer having a functional group reactive to an epoxy group is represented by the diamine compound represented by general formula (10) and general formula (5), and optionally represented by general formula (4). One or two or more selected from diamine compounds, tetracarboxylic dianhydride represented by the general formula (7), or a precursor thereof, a tetracarboxylic acid or an ester derivative thereof, and optionally a general formula ( It can be synthesized by reacting one or more selected from the tetracarboxylic dianhydride shown in 6) or a tetracarboxylic acid or an ester derivative thereof as a precursor thereof in an approximately equimolar amount. A specific example of the polyimide formation reaction is the same as that in the case of the polyimide oligomer generation described above, and the organic solvent to be used can be the same as that described above.

  In particular, when using a polyimide oligomer having a phenolic hydroxyl group, a terminal amine oligomer having a phenolic hydroxyl group is previously dispersed or dissolved in the organic solvent in the reaction vessel, and the terminal acid dianhydride component is dissolved or dispersed in the solvent. In view of reducing esterification reaction by phenolic hydroxyl group and acid anhydride group, which is a side reaction, it is preferable to perform heating by dropping and stirring at low temperature.

Y _{2 which} is a siloxane component in the polyimide-polysiloxane copolymer of the present invention is Y ₂ / (Y ₁ + Y ₂ ) = 0.01 to 0.80 in terms of molar ratio, preferably 0.02 to 0.8. 70. If it is less than 0.01, the effect of imparting low elasticity is poor, and if it exceeds 0.80, a decrease in heat resistance and an increase in moisture permeability are observed. Further, Y ₃ having a reactive functional group in the epoxy group _{Y 3 / (Y 1 + Y} 2 + Y 3) in a molar ratio is 0.01 to 0.99, preferably 0.02 to 0.95 is there. If it is less than 0.01, the effect of imparting a network structure having a functional group reactive to an epoxy group as a crosslinking point is poor, and if it exceeds 0.99, it is difficult to achieve low elasticity, which is not preferable. Further, Y ₁ / (Y ₁ + Y ₂ + Y ₃ ) is 0 to 0.98, preferably 0.01 to 0.95.

  By introducing functional groups reactive to the epoxy group locally into the polyimide-polysiloxane copolymer, low elasticity can be maintained even when a network structure is formed with the reactive functional group of the epoxy group as a crosslinking point. Is possible.

  Particularly, the phenolic hydroxyl group-containing polyimide-polysiloxane copolymer of the present invention is a diamine having a phenolic hydroxyl group in an aromatic ring such as a benzene ring or a naphthalene ring different from an aromatic ring such as a benzene ring to which an amino group is bonded. A resin composition in which an epoxy resin having two or more glycidyl groups and preferably a curing agent are blended with the resin has a low elastic modulus and is excellent in adhesiveness and reliability. If this resin composition is applied as a varnish on a support substrate, a film having excellent adhesion to a copper foil or the like can be obtained.

  In addition, it is preferable that the polystyrene conversion weight average molecular weight by the gel permeation chromatography (GPC) of the partial block polyimide-polysiloxane copolymer of (A) component which concerns on this invention is 1000-500000, It is preferable that it is 3000-400000.

Component (B) The component (B) is spherical metal oxide fine particles having an average particle size of 0.05 to 10 μm. The spherical metal oxide fine particles preferably have a Wadel sphericity of 0.7 to 1.0.
Here, “Wadell's sphericity” (see Chemical Engineering Handbook, published by Maruzen Co., Ltd.) is the sphericity of a particle ((diameter of circle equal to the projected area of the particle) / (minimum circumscribing the projected image of the particle) It is an index measured by (diameter of circle), and the closer this index is to 1.0, the closer the particle is to a true sphere. In the present invention, it is desirable that the spherical metal oxide fine particles have a true spherical shape having a Wadel sphericity of more preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0. When the sphericity of the Wardel is less than 0.7, the thixotropy of the composition may increase when the filling amount of the component (B) increases.

  The “average particle size” means “volume average particle size”, and is measured by an automated method using, for example, a laser diffraction scattering type particle size distribution analyzer (trade name: LA910) manufactured by Horiba, Ltd. can do.

  The average particle diameter of the spherical metal oxide fine particles is preferably 0.05 to 5 μm, more preferably 0.1 to 5 μm. The spherical metal oxide fine particles are preferably true spherical metal oxide fine particles. From the viewpoint of low thixotropic properties, the component (B) is preferably spherical metal oxide fine particles containing 60 to 100% by mass, particularly 80 to 100% by mass of true spherical metal oxide fine particles. In the present specification, “true sphere” is a concept including a slightly distorted sphere having a sphericity in the range of 0.95 to 1.

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

The spherical metal oxide fine particles may be produced in any way, but metal oxide fine particles obtained by burning a metal are preferred. The metal oxide fine particles obtained by burning this metal are prepared in a metal powder such as silicon, aluminum, magnesium, zirconium, titanium; mullite composition (3Al ₂ O ₃ .2SiO _{2 to} 2Al ₂ O ₃ .SiO ₂ ). Aluminum powder and silicon powder prepared; Magnesium powder and aluminum powder prepared in spinel composition (MgAl ₂ O ₄ ); Aluminum powder, magnesium powder and silicon powder prepared in cordierite composition (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ); A metal flame mixture is burned in an atmosphere containing oxygen together with a carrier gas to form a chemical flame, and an oxide or composite of one kind of metal such as silica, alumina, titania, zirconia or the like in the chemical flame Fine oxide particles (particularly ultrafine particles) can be obtained. Among the metal oxide fine particles obtained by burning these metals, those containing spherical, particularly true spherical silica fine particles as the main component (that is, containing 60 to 100% by mass) are preferable.

  The spherical metal oxide fine particles need not be surface-treated, but those having a surface treated with silazanes and / or a silane coupling agent are preferred.

  Examples of the silazanes include silazanes such as hexamethyldisilazane (HMDS) and hexaphenyldisilazane, or combinations of two or more thereof. Among these, hexamethyldisilazane suppresses the aggregation of silica, tilts acidic silica to basic, improves affinity to organic matter and improves uniformity, and stability of component (A) to resin It is preferable in terms of improving the quality.

  The silane coupling agent is, for example, a compound having at least one active group (reactive organic functional group) selected from the group consisting of amino group, glycidyl group, mercapto group, ureido group, hydroxy group and alkoxy group, or A combination thereof (for example, a combination of an alkoxy group and another reactive functional group). Specific examples of the silane coupling agent include epoxy functional group-containing organoalkoxysilanes such as γ-glycidoxypropyltriethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and aminopropyltriethoxysilane. Aminofunctional group-containing organoalkoxysilanes such as ureidopropyltriethoxysilane and N-phenylaminopropyltrimethoxysilane, arylalkoxysilanes such as phenyltrimethoxysilane, alkylalkoxysilanes such as methyltrimethoxysilane and octadecyltrimethoxysilane , Alkenylalkoxysilanes such as vinyltrimethoxysilane and allyltrimethoxysilane, and mercaptofunctional group-containing organoalkoxysilanes such as γ-mercaptopropyltrimethoxysilane Etc. The.

  Examples of the spherical metal oxide fine particles include Admafine SE series and SC series manufactured by Admatechs Co., Ltd. as commercially available products.

  (B) The compounding quantity of a component is 5-350 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-300 mass parts, More preferably, it is 10-200 mass parts. When the blending amount is less than 5 parts by mass, good screen printability may not be obtained, and when it exceeds 350 parts by mass, it is a basic characteristic of the resin of component (A). Adhesiveness with the material may be impaired.

The resin composition for screen printing of the present invention can suppress the thixotropic property even at the above blending amount by using the spherical metal oxide fine particles of the component (B), and the formed pattern has a mesh residue. Thus, a uniform film thickness can be obtained without causing blurring, deterioration of bubble removal properties, or the like.
In addition, (B) component may be used individually by 1 type, or may use 2 or more types together.

  Use of non-spherical oxide powders such as molten metal oxide powders, crushed metal oxides, and fumed metal oxides (fumed metal oxides) as long as the above effects are not impaired as metal oxide powders Can do. The combined use ratio of the non-spherical metal oxide powder is 25 parts by mass or less (0 to 25 parts by mass), particularly 20 parts by mass or less (0 to 20 parts per 100 parts by mass of the spherical metal oxide powder of the component (B). Part by mass).

(C) Component (C) The organic solvent of a component can use what can melt | dissolve the resin of (A) component partially or completely. Specific examples of the component (C) include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone, N, N-dimethylacetamide, N, N-dimethyl. Formamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone and the like, preferably aprotic polar solvents, particularly preferably N-methylpyrrolidone, N-vinylpyrrolidone, cyclohexanone, γ-butyrolactone and 1, 3-dimethyl-2-imidazolidinone.

In the case where the cured film formed from the composition of the present invention is a thin film having a thickness 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 continuous formability by screen printing. Examples of the organic solvent having a boiling point of 200 ° C. or higher include γ-butyrolactone, N-methylpyrrolidone, N-vinylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
In addition, (C) component may be used individually by 1 type, or may use 2 or more types together.

  (C) The usage-amount of the organic solvent of a component is 10-500 mass parts normally with respect to 100 mass parts of (A) component, Preferably it can be about 20-400 mass parts. When the amount of the organic solvent of component (C) is less than 10 parts by mass, the viscosity of the composition may be remarkably increased, and screen printability may be deteriorated. Workability may be reduced.

(D) component There is no restriction | limiting in particular in the epoxy resin which has at least 2 epoxy group in 1 molecule (D) used by this invention. For example, glycidyl ether of phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolac, cresol novolac, glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc. Glycidyl type (including methyl glycidyl type) epoxy resins such as glycidyl group substituted active hydrogen bonded to nitrogen atom such as glycidyl ester of carboxylic acid, aniline, isocyanuric acid, etc., and olefin bond in molecule are epoxidized The resulting vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohex Of alicyclic epoxy resin such as ru-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, glycidyl ether of paraxylylene-modified phenol resin, glycidyl ether of metaxylylene / paraxylylene-modified phenol resin, terpene-modified phenol resin Examples include glycidyl ether, glycidyl ether of dicyclopentadiene modified phenolic resin, glycidyl ether of cyclopentadiene modified phenolic resin, glycidyl ether of polycyclic aromatic ring modified phenolic resin, glycidyl ether of naphthalene ring-containing phenolic resin, biphenyl type epoxy resin, etc. These can be used singly or in combination of two or more.

(E) Component The epoxy resin curing agent (E) of the present invention is not particularly limited as long as it works as an epoxy resin curing agent, and examples thereof include phenolic compounds, acid anhydrides, and amine compounds. Of these, phenol compounds are preferred. Examples of the phenolic compound include phenols such as phenol, cresol, xylenol, hydroquinone, resorcin, catechol, bisphenol A, bisphenol F, or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and formaldehyde, acetaldehyde, propionaldehyde. , A resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde under an acidic catalyst; a phenol resin having a xylylene skeleton synthesized from phenols and dimethoxyparaxylene; a phenol having a dicyclopentadiene skeleton Resin; Phenolic resin having cyclopentadiene skeleton; Melamine modified phenolic resin; Terpene modified phenolic resin; Polycyclic aromatic modified phenolic resin; Examples thereof include naphthol resins having a xylylene skeleton, and these can be used alone or in combination of two or more.

  The amount of the curing agent used is a curing effective amount, and a suitable blending amount varies depending on the specific type, but generally 1 to 100 parts by mass, preferably 5 to 50 parts per 100 parts by mass of the epoxy resin. The range is part by mass. This is because if the amount of the curing agent used is less than 1 part by mass, it will be difficult to cure the composition of the present invention satisfactorily. This is because the resin is diluted to require a long time for curing, and further, the physical properties of the cured product are deteriorated.

  The present invention may further contain an epoxy resin curing catalyst. In this case, the epoxy resin curing catalyst used in the present invention is not particularly limited, and examples of the phosphorus catalyst include triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate, and compounds as shown below. .

（式中、Ｒ⁴〜Ｒ¹¹は、水素原子、フッ素、臭素、ヨウ素等のハロゲン原子、炭素数が１〜８のアルキル基、アルケニル基、アルキニル基、炭素数が１〜８のアルコキシ基、トリフルオロメチル基、フェニル基等が挙げられ、全ての置換基が同一でも異なっていてもよい。）

(Wherein R ^{4 to} R ¹¹ are a hydrogen atom, a halogen atom such as fluorine, bromine or iodine, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group having 1 to 8 carbon atoms, (A trifluoromethyl group, a phenyl group, etc. are mentioned, and all the substituents may be the same or different.)

  Further, as the amine catalyst, imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like are blended. Among these, one kind alone or two kinds or more can be used.

  The compounding ratio of the polyimide-polysiloxane copolymer having a functional group reactive to the epoxy group of the present invention, the epoxy resin, and the epoxy resin curing agent is important. In the present invention, the curing reaction is carried out by utilizing the reaction between the functional group reactive to the epoxy group and the epoxy group, but if the epoxy group is too small, the adhesive force with the adherend is not sufficient, and if it is too much, Since the elastic modulus is increased by the excess epoxy resin, it is not suitable for producing a flexible polyimide resin composition. Therefore, the mixture of the epoxy resin and the epoxy resin curing agent is 1 to 900 parts by mass, preferably 5 to 400 parts by mass with respect to 100 parts by mass of the block copolymer (A).

  Moreover, the compounding quantity of the said epoxy resin curing catalyst is 40 mass parts or less (0-40 mass parts) normally with respect to a total of 100 mass parts of an epoxy resin and an epoxy resin hardening | curing agent, Preferably 0.01-40 masses Part, more preferably about 0.1 to 20 parts by mass. If the amount of the epoxy resin curing catalyst is too small, it may take a long time for curing, or sufficient curability may not be obtained, and if it is too large, the storage stability of the composition may be poor.

  The resin composition of the present invention is desirably well stirred for 5 minutes or more in order not to separate the components after blending the above components. The polyimide resin composition thus obtained is soluble in an aprotic polar solvent such as cyclohexanone or NMP, and can be used as it is as a varnish.

  In addition to the components (A) to (E), the composition of the present invention includes, for example, an antioxidant, a heat stabilizer, a conductive filler, a pigment, and a dye within a range that does not impair the effects of the present invention. Etc. can be added depending on the purpose.

  The composition of the present invention can be prepared by mixing the above-described components (A) to (E) and optionally other components by a conventional method. Specifically, for example, a laika machine equipped with a stirring device and a heating device, a three-roll, a ball mill, a planetary mixer, and the like can be used. Moreover, you may use these mixing apparatuses in combination of 2 or more types suitably.

  A method for applying the composition to the surface of a substrate such as a silicon wafer by screen printing will be described. First, the surface of the substrate is covered with a mask having openings of a required pattern, and the composition is put into the squeegee portion. Next, the composition is filled in the openings of the masking member by moving the squeegee and moving the mask while pressing the composition (filling step). Next, the mask is removed. Thus, a pattern of the composition can be formed on the surface of the substrate.

  The composition pattern thus formed is then cured. For curing, for example, curing is performed stepwise at a low temperature of room temperature (20 ° C. ± 5 ° C.) to 200 ° C., and if necessary, high temperature curing (post-cure) of 200 to 350 ° C. is performed.

  A pattern formed by screen printing using the resin composition of the present invention has high resolution, and a uniform film thickness can be obtained without causing mesh residue, blurring, deterioration of foam removal properties, and the like. Also, because it is excellent in continuous formability, it is a passivation film on the surface of a semiconductor element at the wafer level, a protective film, a junction protective film at a junction of a diode, a transistor, a VLSI α-ray shielding film, an interlayer insulating film, an ion implantation mask, etc. Besides, for screen printing suitable for forming conformal coating of printed circuit boards, liquid crystal surface element alignment films, glass fiber protective films, solar cell surface protective films or conductive films containing conductive fillers, etc. The resin composition can be used over a wide range.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the physical property measurement method and the screen printing method are as follows.

[Glass-transition temperature]
Measuring device: TM-7000 (manufactured by ULVAC-RIKO)
Measurement mode: Tensile mode Test piece shape: 15 mm x 5 mm x 50 μm
Measurement temperature: room temperature to 300 ° C. (temperature increase 5 ° C./min)
[Young's modulus]
Measuring device: Solid viscoelasticity measuring device (manufactured by Yoshimizu)
Test piece shape: 20 mm × 5 mm × 50 μm
Measurement temperature: room temperature to 300 ° C. (temperature increase 5 ° C./min)
[GPC]
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: THF Flow rate: 0.6 ml / min
Sample concentration: 1.0% by mass
Molecular weight conversion: Standard polystyrene [screen printing]
Screen printing machine: MODEL MC212 (manufactured by CW PRICE CO. INC.)
Screen mask: 325 mesh, Milk thickness: 15 μm, Mesh thickness: 35 μm
Deterioration of the pattern shape after 100 times of continuous molding was confirmed by setting the mask, filling the composition with a squeegee, and removing the mask as one molding process. Then, it was cured in an oven at 100 ° C. × 0.5 hours + 250 ° C. × 4 hours, and the resulting pattern was observed for mesh eyes, foaming and pattern edge bleeding.

[Synthesis Example 1]
To a 1 L separable flask equipped with a Dean-Stark apparatus connected with a reflux condenser, a thermometer, and a stirrer was added 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 45 as an acid dianhydride component. .11 parts by mass and 445 parts by mass of cyclohexanone were added and stirred at 50 ° C. to disperse the acid dianhydride. After adding 103.20 parts by mass of diaminosiloxane KF-8010 [both ends γ-aminopropyldimethylsiloxy group-blocked dimethylpolysiloxane (weight average molecular weight 860), manufactured by Shin-Etsu Chemical Co., Ltd.] as a diamine component, And stirred for 12 hours to synthesize polyamic acid oligomer solution-1. Further, 40 ml of toluene was added as a dehydrating solvent, followed by heat dehydration at about 160 ° C. for 8 hours to distill off about 4.3 ml of water. Thus, an acid anhydride-terminated polyimide oligomer solution-1 was synthesized.
When the infrared absorption spectrum of the resin obtained by distilling off the solvent of this resin solution and drying under reduced pressure was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and 1770 cm ^−1. And the absorption based on an imide group was confirmed at 1720 cm ⁻¹ . Furthermore, when the weight average molecular weight (polystyrene conversion) by GPC was measured, it was about 10800.

５９．３６質量部及びシクロヘキサノン３１１質量部を仕込み、５０℃で撹拌溶解させた。これに酸二無水物成分として２，２−ビス（３，４−ベンゼンジカルボン酸アンヒドリド）パーフルオロプロパン４４．４２質量部を少量ずつ添加した後、室温で１２時間撹拌反応させて、ポリアミック酸オリゴマー溶液−２を合成した。更に脱水溶剤としてトルエン４０ｍｌを添加した後、約１６０℃で８時間加熱脱水を行い、約３．６ｍｌの水分を留去した。これにより、アミノ基末端のポリイミドオリゴマー溶液−２を合成した。 Subsequently, an aromatic diamine having the phenolic hydroxyl group shown below as a diamine component: diamine-1 in a reaction apparatus similar to the above.

59.36 parts by mass and 311 parts by mass of cyclohexanone were charged and stirred and dissolved at 50 ° C. To this, 44.42 parts by mass of 2,2-bis (3,4-benzenedicarboxylic acid anhydride) perfluoropropane as an acid dianhydride component was added little by little, followed by stirring reaction at room temperature for 12 hours to obtain a polyamic acid oligomer. Solution-2 was synthesized. Further, 40 ml of toluene was added as a dehydrating solvent, followed by heat dehydration at about 160 ° C. for 8 hours to distill off about 3.6 ml of water. Thereby, polyimide oligomer solution-2 having amino group terminals was synthesized.

When an infrared absorption spectrum of the isolated resin was measured in the same manner as described above, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups at 1770 cm ⁻¹ and 1720 cm ^−1. The absorption based on the phenolic hydroxyl group was confirmed at 3500 cm ⁻¹ . Furthermore, when the weight average molecular weight (polystyrene conversion) by GPC was measured, it was about 7500.

  The prepared polyimide oligomer solution-2 was charged into a 1 L separable flask equipped with a Dean-Stark apparatus connected with a reflux condenser, a thermometer, and a stirrer, and stirred at 50 ° C. After the polyimide oligomer solution-1 was added dropwise thereto, the mixture was stirred at 50 ° C. for 6 hours. Thereafter, 20 ml of toluene was added, followed by heat dehydration at about 160 ° C. for 8 hours to distill off about 0.7 ml of water. Thereby, a cyclohexanone solution (polyimide siloxane solution-1) of a partially blocked polyimide-polysiloxane copolymer containing a uniform brown transparent phenolic hydroxyl group was synthesized. The obtained solution can be isolated as a resin by distilling off the solvent and then drying under reduced pressure.

A test specimen for measurement was prepared by the following procedure.
First, a support such as an organic separator and a metal foil is prepared, and the obtained polyimide-polysiloxane copolymer cyclohexanone solution is cast on the support so that the film thickness after drying is about 50 μm. It was applied by the method. After drying this at 80 ° C. for 30 minutes, the obtained adhesive film was peeled off from a support such as an organic separator or metal foil, fixed to a stainless steel frame, heat-treated at 200 ° C. for 2 hours, and dried and cured. . In this way, a target resin film for measurement having a smooth surface was obtained. The glass transition temperature of the obtained resin film by a thermomechanical test was 190 ° C., and the Young's modulus at 25 ° C. was 450 MPa.

[Synthesis Example 2]
To a 1 L separable flask equipped with a Dean-Stark apparatus connected with a reflux condenser, a thermometer, and a stirrer was added 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 45 as an acid dianhydride component. .11 parts by mass and 2,2-bis (3,4-benzenedicarboxylic acid anhydride) perfluoropropane 44.42 parts by mass and cyclohexanone 636 parts by mass were stirred at 50 ° C. to disperse the acid dianhydride. . After adding 103.20 parts by mass of diaminosiloxane KF-8010 [both ends γ-aminopropyldimethylsiloxy group-blocked dimethylpolysiloxane (weight average molecular weight 860), manufactured by Shin-Etsu Chemical Co., Ltd.] as a diamine component, And stirred for 12 hours to synthesize polyamic acid solution-1 with an excess of acid anhydride.

５９．３６質量部及びシクロヘキサノン１２０質量部を仕込み、５０℃で撹拌溶解させた。これに予め調製したポリアミック酸溶液−１を滴下し、室温で１２時間撹拌反応させてポリアミック酸溶液−２を合成した。更に脱水溶剤としてトルエン６０ｍｌを添加した後、約１６０℃で８時間加熱脱水を行い、約８．６ｍｌの水分を留去した。これにより、繰返し単位がランダムに配列した部分ブロック化構造を持たないポリイミドシロキサン溶液−２を合成した。得られた溶液は溶媒を留去後、減圧乾燥することで樹脂として単離することができる。 An aromatic diamine having a phenolic hydroxyl group shown below as a diamine component: diamine-1 in a 1 L separable flask equipped with a Dean-Stark apparatus, a thermometer, and a stirrer connected with a separately prepared reflux condenser

59.36 parts by mass and 120 parts by mass of cyclohexanone were charged and dissolved by stirring at 50 ° C. Polyamic acid solution-1 prepared in advance was added dropwise thereto, and the mixture was reacted with stirring at room temperature for 12 hours to synthesize polyamic acid solution-2. Further, 60 ml of toluene was added as a dehydrating solvent, followed by heat dehydration at about 160 ° C. for 8 hours to distill off about 8.6 ml of water. As a result, a polyimidesiloxane solution-2 having no partially blocked structure in which repeating units were arranged at random was synthesized. The obtained solution can be isolated as a resin by distilling off the solvent and then drying under reduced pressure.

When the infrared absorption spectrum of the resin isolated by distilling off the solvent of the obtained solution and drying under reduced pressure was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and 1770 cm. Absorption based on an imide group was confirmed at ⁻¹ and 1720 cm ⁻¹ , and absorption based on a phenolic hydroxyl group was confirmed at 3500 cm ⁻¹ . Furthermore, when the weight average molecular weight (polystyrene conversion) by GPC was measured, it was about 100,000.

A test specimen for measurement was produced in the same procedure as in Synthesis Example 1.
The glass transition temperature of the obtained resin film by a thermomechanical test was 130 ° C., and the Young's modulus at 25 ° C. was 1100 MPa.

[Example 1]
50 parts by mass of the partially blocked polyimide-polysiloxane copolymer obtained in Synthesis Example 1, 100 parts by mass of N-methyl-2-pyrrolidone, 25 parts by mass of 1,3-dimethyl-2-imidazolidinone, orthocresol Novolac epoxy resin: EOCN1020 (Nippon Kayaku Co., Ltd., 220 g / Eq) 35.64 parts by mass, phenol novolac: TD2131 (Dainippon Ink Co., Ltd., 110 g / Eq) 12.43 parts by mass, tertiary phosphorus system Catalyst: 0.5 parts by mass of triphenylphosphine TPP (made by Hokuko Chemical Co., Ltd.), 20 parts by mass of spherical silica fine particles Admafine SC2500-SE [manufactured by Admatechs Co., Ltd., average particle size 0.5 μm], and fumed silica R972 [manufactured by Nippon Aerosil Co., Ltd.] 2 parts by mass are mixed uniformly to obtain a paste-like resin composition. It was.

A test specimen for measurement was prepared by the following procedure.
First, a support such as an organic separator or a metal foil is prepared, and the cyclohexanone solution of the pasty resin composition obtained above is cast on the support so that the film thickness after drying is about 50 μm. It was applied by the method. After drying this at 80 ° C. for 30 minutes, the obtained adhesive film was peeled off from a support such as an organic separator or metal foil, fixed to a stainless steel frame, heat-treated at 200 ° C. for 2 hours, and dried and cured. . In this way, a target resin film for measurement having a smooth surface was obtained. The glass transition temperature of the obtained resin film by a thermomechanical test was 190 ° C., and the Young's modulus at 25 ° C. was 1050 MPa.
When the screen printability was confirmed, no meshes, foaming and pattern edge bleeding were observed, and a good pattern could be obtained.

[Comparative Example 1]
50 parts by mass of a polyimidesiloxane resin having no partially blocked structure in which the repeating units obtained in Synthesis Example 2 are randomly arranged, 100 parts by mass of N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolide Non-25 parts by mass, ortho-cresol novolac type epoxy resin: EOCN1020 (manufactured by Nippon Kayaku Co., Ltd., 220 g / Eq) 35.64 parts by mass, phenol novolac: TD2131 (manufactured by Dainippon Ink Co., Ltd., 110 g / Eq) 12.43 Part by mass, tertiary phosphorus catalyst: 0.5 part by mass of triphenylphosphine TPP (made by Hokuko Chemical Co., Ltd.), spherical silica fine particle Admafine SC2500-SE [manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm] 20 Parts by mass and 2 parts by mass of fumed silica AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.) It was mixed to obtain a paste-like resin composition.

A test specimen for measurement was prepared in the same procedure as in Example 1.
The resin film produced in the same manner from the paste-like resin composition had a glass transition temperature of 150 ° C. and a Young's modulus of 3500 MPa at 25 ° C. by a thermomechanical test, and was a film having a high elastic modulus.
When the screen printability was confirmed, no meshes, foaming and pattern edge bleeding were observed, and a good pattern could be obtained.

Claims (5)

(A) a partial block polyimide-polysiloxane copolymer having a repeating unit represented by the following structural formulas (2) and (8) and capable of containing a repeating unit represented by the following structural formula (1);

(In the formula, X is one or more of tetravalent organic groups including an aromatic ring or an aliphatic ring, Y ₁ is a divalent organic group, and Y ₂ is ₂ represented by the following structural formula (3). Y ₃ is a divalent organic group represented by the following structural formula (9 ′) The molar ratio of Y _{2 to} the sum of the groups Y ₁ , Y ₂ , Y ₃ is Y ₂ / _{(Y 1 + Y 2 + Y} 3) = a .01 to .80, group Y _1, Y _2, the molar ratio of Y ₃ to the sum of Y _{3 is, Y 3 / (Y 1 +} Y 2 + Y 3) = 0.01 to 0.99, k is a natural number of 1 to 50, m is a natural number of 1 to 50, and j is a natural number of 1 to 50.)

Wherein R ¹ is a divalent organic group having 3 to 9 carbon atoms, R ² and R ³ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 It is an integer of ~ 150.)

(In the formula, R independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. K is a natural number of 1 to 5.)
(B) Spherical metal oxide fine particles whose surface is treated with a silane coupling agent and having an average particle diameter of 0.05 to 10 μm: 5 to 350 parts by mass with respect to 100 parts by mass of component (A),
(C) an organic solvent,
(D) an epoxy resin having at least two epoxy groups in one molecule;
(E) Curing agent for the above epoxy resin: It contains a curing effective amount of the component (D), and the total amount of the components (D) and (E) is 1 to 900 masses per 100 parts by mass of the component (A). A resin composition for screen printing, which is a part. The silane coupling agent according to claim 1, amino group, a glycidyl group, a mercapto group, a ureido group, hydroxy group, an alkoxy group, characterized in that at least one compound having an active group selected from mercapto groups serial mounting of screen printing a resin composition. Component (B) has an average particle diameter of claim 1 or 2 SL placing the screen printing resin composition characterized by containing 60 to 100 wt% of spherical silica of 0.05 to 10 [mu] m. The resin composition for screen printing according to any one of claims 1 to 3 , comprising an organic solvent having a boiling point of 200 ° C or higher as the component (C). (C) A component is 10-500 mass parts with respect to 100 mass parts of (A) component, The resin composition for screen printing of any one of Claims 1 thru | or 4 characterized by the above-mentioned.