JP2006307153A - Resin composition for screen printing and method for forming resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for screen printing having good in-plane film thickness uniformity and continuous printability, which is excellent in planarizing properties, transparency, adhesion and sealability and can form a resin film having low steam-permeability and being low dielectric, and being suitably applied to such uses for electric parts as a sealing film, an insulating film and a planarizing film. <P>SOLUTION: The resin composition for screen printing comprises an abliphatic olefin polymer having a structural unit represented by formula (1) or (2) and a structural unit represented by formula (3) or (4) and having ≥3,000 and <10,000 weight average molecular weight, and an aliphatic hydrocarbon compound (wherein R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom or a 1-10C hydrocarbon group; R<SP>3</SP>and R<SP>4</SP>are each a hydrogen atom, a 1-10C hydrocarbon group or a polar group, and either of R<SP>3</SP>and R<SP>4</SP>is a polar group; n is 0-2; R<SP>5</SP>-R<SP>8</SP>are each a hydrogen atom or a 1-10C hydrocarbon group; and m is 0-2). The method for forming the resin film has a process of applying the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition for screen printing and a method for forming a resin film. More specifically, the present invention relates to a resin composition for screen printing and a method for forming a resin film that can form a resin film suitable as a sealing film, an insulating film, a planarizing film, and the like for electronic components.

Various display elements such as organic electroluminescence elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, color filters, black matrices, and other electronic components include sealing films, element surfaces, Various functional films such as a flattening film for flattening the wiring and an insulating film for maintaining electrical insulation are provided. Such a functional film is formed using an inorganic material or an organic material alone or in combination. And especially when using for a display element, a solid-state image sensor, and a color filter, it is calculated | required that a functional film is excellent in transparency.
Furthermore, in addition to transparency, functional films such as a sealing film, an insulating film, and a planarization film are required to have physical properties. For example, low water vapor permeability is required for sealing films, low dielectric properties, that is, high electrical insulation is required for insulating films, and excellent flatness that does not follow steps is required for flattening films. It is done. These various films may be simultaneously mounted on one electronic component. In such a case, the materials of the respective films are closer from the viewpoint of improving the adhesion between the films. It is hoped that.
It is known that an alicyclic olefin polymer can provide a molded product excellent in low dielectric property, low water absorption, solvent resistance, transparency and the like. For example, as a sealant that can prevent deterioration of an organic EL light emitter even when used for a long period of time, it is an alicyclic olefin polymer having no polar group, and has a weight average molecular weight of 10,000 or more. An electroluminescent device sealing agent made of a high molecular weight polymer has been proposed (Patent Document 1). In addition, as a radiation-sensitive resin composition capable of forming a resin film having not only excellent dielectric constant, heat-resistant dimensional stability and flatness, but also good transparency and heat-resistant discoloration, two carboxyl groups are used. A radiation-sensitive resin composition containing an alkali-soluble alicyclic olefin resin having a repeating unit, an acid generator, a crosslinking agent, and a solvent has been proposed (Patent Document 2).
Incidentally, screen printing is widely used for forming a resin film. In screen printing, ink is placed on a screen that is not necessary for printing, and the ink is transferred to a substrate by rubbing with a squeegee. Screen printing has a relatively simple device, does not waste ink, and can print on a wide variety of materials such as paper, fiber, plastic, metal, and ceramics. Regardless of size, plane, or curved surface, it can be applied to almost any shape, and a resin film having a thick ink film, clear, excellent weather resistance, chemical resistance and the like can be obtained. However, in screen printing, there is a clearance between the screen plate and the substrate, ink is entangled in the plate mesh, the squeegee push force, the ink being pushed onto the substrate by ink rolling, and the plate tension. The coating amount is determined by the ink contact between the printing plate and the substrate by tearing the ink. Therefore, it is not easy to stably and continuously form a resin film having a uniform film thickness, and attempts have been made to develop a resin composition for screen printing having good in-plane film thickness uniformity and printing continuity. .
For example, a methylol group or an alkoxyl group is used as an insulating coating film forming resin composition that is excellent in coating film suitability in an ink state such as a screen printing method and has little deterioration over time in coating suitability, printed film dimensional accuracy, uniformity, etc. A resin composition containing a melamine resin having a methylol group or an alkoxyl group and a resin having crosslinking reactivity has been proposed (Patent Document 3). Moreover, as a thermosetting resin composition excellent in bending resistance, folding resistance, flexibility, plating resistance, heat resistance, PCT resistance, electrical insulation, adhesion, etc., two or more carboxyls in one molecule A thermosetting resin composition containing a polycarboxylic acid resin having a group, a resin having two or more epoxy groups in one molecule, and an organic solvent has been proposed (Patent Document 4).
JP 2003-59645 A JP 2004-212450 A JP-A-11-140147 JP-A-11-158252

The present inventor can form a resin film satisfying various characteristics required for the resin film for electronic parts as described above, and has a good in-plane film thickness uniformity and printing continuity. As a result of intensive investigations on the prior art to obtain a resin composition for printing, the resin film obtained by the sealing agent of Patent Document 1 is inferior in flatness and insufficient in adhesion to the substrate. Patent The resin film obtained from the resin composition of Document 2 is not sufficiently low in water vapor permeability required for the sealing film, and when the resin composition of Patent Documents 1 to 4 is used for screen printing, the surface It became clear that the inner film thickness uniformity and printing continuity were insufficient.
INDUSTRIAL APPLICABILITY The present invention is a resin film that is excellent as a sealing film, an insulating film, a flattening film, etc. for electronic parts, having excellent flatness, transparency, adhesion and sealing properties, and having low water vapor permeability and low dielectric properties It is an object of the present invention to provide a resin composition for screen printing having good in-plane film thickness uniformity and printing continuity, and a method for forming a resin film.

（ただし、式中、Ｒ¹とＲ²はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基であり、Ｒ³とＲ⁴はそれぞれ独立して水素原子、炭素数１〜１０の炭化水素基又は極性基であって、Ｒ³とＲ⁴のうちいずれか一方のみは極性基であり、ｎは０〜２の整数である。）

（ただし、式中、Ｒ⁵〜Ｒ⁸はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基であり、ｍは０〜２の整数である。）、
（２）脂肪族炭化水素化合物が、沸点１５０℃以上の脂環式炭化水素である(１)に記載のスクリーン印刷用樹脂組成物、
（３）脂環式オレフィン重合体における構造単位(ａ)と構造単位(ｂ)との合計に対する構造単位(ａ)の割合が、０.００５〜４０モル％である(１)又は(２)に記載のスクリーン印刷用樹脂組成物、
（４）脂環式オレフィン重合体における構造単位(ａ)と構造単位(ｂ)との合計に対する一般式(２)で表される構造単位と一般式(４)で表される構造単位との合計の割合が、９０モル％以上である(１)〜(３)のいずれか１項に記載のスクリーン印刷用樹脂組成物、
（５）固形分濃度が１〜７０重量％である(１)〜(４)のいずれか１項に記載のスクリーン印刷用樹脂組成物、
（６）２５℃における粘度が５〜１,０００,０００ｍＰａ・ｓである(１)〜(５)のいずれか１項に記載のスクリーン印刷用樹脂組成物、及び、
（７）(１)〜(６)のいずれか１項に記載のスクリーン印刷用塗料組成物を、スクリーン印刷法により基板に塗布する工程を有することを特徴とする樹脂膜の形成方法、
を提供するものである。 As a result of intensive studies to solve the above problems, the present inventor has obtained an alicyclic olefin polymer having a weight average molecular weight of 3,000 to 10,000 and a specific structural unit, and By using an alicyclic hydrocarbon having a boiling point of 150 ° C. or higher as a solvent, it is a transparent material having low water vapor permeability, high flatness, low dielectric properties, etc. necessary for sealing films, insulating films, flattening films, etc. It has been found that a resin film can be stably and continuously formed by screen printing with a uniform film thickness, and the present invention has been completed based on this finding.
That is, the present invention
(1) having a structural unit (a) represented by general formula (1) or general formula (2) and a structural unit (b) represented by general formula (3) or general formula (4); A resin composition for screen printing, comprising an alicyclic olefin polymer having a weight average molecular weight of 3,000 or more and less than 10,000, and an aliphatic hydrocarbon compound,

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom, having 1 to 10 carbon atoms. (It is a hydrocarbon group or a polar group, and only one of R ³ and R ⁴ is a polar group, and n is an integer of 0 to 2.)

(Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 0 to 2).
(2) The resin composition for screen printing according to (1), wherein the aliphatic hydrocarbon compound is an alicyclic hydrocarbon having a boiling point of 150 ° C. or higher,
(3) The ratio of the structural unit (a) to the total of the structural unit (a) and the structural unit (b) in the alicyclic olefin polymer is 0.005 to 40 mol% (1) or (2) A resin composition for screen printing according to claim 1,
(4) The structural unit represented by the general formula (2) and the structural unit represented by the general formula (4) with respect to the sum of the structural unit (a) and the structural unit (b) in the alicyclic olefin polymer. The resin composition for screen printing according to any one of (1) to (3), wherein the total ratio is 90 mol% or more,
(5) Resin composition for screen printing of any one of (1)-(4) whose solid content concentration is 1 to 70 weight%,
(6) The resin composition for screen printing according to any one of (1) to (5), which has a viscosity at 25 ° C. of 5 to 1,000,000 mPa · s, and
(7) A method for forming a resin film comprising a step of applying the coating composition for screen printing according to any one of (1) to (6) to a substrate by a screen printing method,
Is to provide.

  The resin composition for screen printing of the present invention has good printing continuity, and the resin film obtained from the composition has good in-plane film thickness uniformity, high transparency and adhesion, and low It is a water vapor permeable resin film with excellent flatness, high insulation, and excellent sealing properties. For example, sealing in the manufacture of electronic components such as integrated circuit elements, display elements, and solid-state imaging elements. It can be suitably used for forming a film, an insulating film, a planarizing film, and the like.

ただし、一般式(１)及び一般式(２)において、Ｒ¹とＲ²はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基であり、Ｒ³とＲ⁴はそれぞれ独立して水素原子、炭素数１〜１０の炭化水素基又は極性基であって、Ｒ³とＲ⁴のうちいずれか一方のみは極性基であり、ｎは０〜２の整数である。また、一般式(３)及び一般式(４)において、Ｒ⁵〜Ｒ⁸はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基であり、ｍは０〜２の整数である。
一般式(１)〜(４)における炭素数１〜１０の炭化水素基としては、例えば、アルキル基、シクロアルキル基、アリール基などを挙げることができる。アルキル基としては、例えば、メチル基、エチル基、ｉｓｏ−プロピル基、ｔｅｒｔ−ブチル基、ヘキシル基、ヘプチル基などを挙げることができる。シクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、２−メチルシクロヘキシル基、シクロオクチル基などを挙げることができる。アリール基としては、例えば、フェニル基、２−メチルフェニル基、ベンジル基などを挙げることができる。これらの中で、炭素数１〜１０の炭化水素基が炭素数が１〜６のアルキル基であることが好ましく、炭素数１〜４のアルキル基であることがより好ましく、エチル基であることがさらに好ましい。 The resin composition for screen printing of the present invention comprises a structural unit (a) represented by general formula (1) or general formula (2) and a structural unit represented by general formula (3) or general formula (4). and an alicyclic olefin polymer having a weight average molecular weight of 3,000 or more and less than 10,000, and an alicyclic hydrocarbon having a boiling point of 150 ° C. or higher.

However, the general formula (1) and general formula (2), R ¹ and R ² are each independently a hydrocarbon group having 1 to 10 hydrogen atoms or carbon atoms, R ³ and R ⁴ are each independently hydrogen atom, a hydrocarbon group or a polar group having 1 to 10 carbon atoms, either one of R ³ and R ⁴ only is a polar group, n is an integer of 0-2. Moreover, in General formula (3) and General formula (4), R < ⁵ > -R < ⁸ > is respectively independently a hydrogen atom or a C1-C10 hydrocarbon group, and m is an integer of 0-2.
As a C1-C10 hydrocarbon group in General formula (1)-(4), an alkyl group, a cycloalkyl group, an aryl group etc. can be mentioned, for example. Examples of the alkyl group include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, a hexyl group, and a heptyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a cyclooctyl group, and the like. Examples of the aryl group include a phenyl group, a 2-methylphenyl group, and a benzyl group. Among these, the hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and an ethyl group. Is more preferable.

Examples of the polar group in the general formula (1) and the general formula (2) include a polar group having an oxygen atom such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group; a primary amino group and a secondary group Polar groups having nitrogen atoms such as amino groups, primary amide groups, secondary amide groups (N-alkylamide groups); protic polar groups such as polar groups having sulfur atoms such as thiol groups; ester groups ( An alkoxycarbonyl group and an aryloxycarbonyl group), an epoxy group, a halogen atom, a nitrile group, an alkoxyl group, an acryloyl group, and a carbonyloxycarbonyl group composed of R ³ and R ⁴ (an acid anhydride of a dicarboxylic acid). Product residues), N-substituted imide groups, carbonyl groups, tertiary amino groups, sulfone groups and other aprotic polar groups; and the like.
Among these, in terms of obtaining a polymer having high adhesion to other materials and high heat resistance, a protic polar group is preferable, a polar group having an oxygen atom and a polar group having a nitrogen atom are more preferable, A polar group having an oxygen atom is more preferred, and a carboxyl group is particularly preferred.
In the structural unit (a) of the alicyclic olefin polymer in the present invention, there is one polar group, but the presence of such a polar group is caused by the fact that the resin film formed by the composition of the present invention is applied to the substrate. It is thought that it contributes to exhibiting high adhesion and low water vapor permeability in a balanced manner.

In the present invention, the proportion of the structural unit (a) in the total of the structural unit (a) and the structural unit (b) is preferably 0.005 to 40 mol%, and 0.01 to 30 mol%. It is more preferable that it is 0.02 to 20 mol%. When the proportion of the structural unit (a) is 0.005 to 40 mol%, a resin film having high adhesion and heat resistance and low water vapor permeability can be easily obtained. Further, the total ratio of the structural unit (a) and the structural unit (b) is preferably 65 mol% or more in the total structural units of the alicyclic olefin polymer. Such an alicyclic olefin polymer is suitable as an alicyclic olefin polymer for constituting a resin film.
The ratio of the total of the structural unit represented by the general formula (2) and the structural unit represented by the general formula (4) to the total of the structural unit (a) and the structural unit (b), that is, the main chain unsaturated bond From the viewpoint of obtaining high heat resistance, the hydrogenation rate is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 98 mol% or more. High heat resistance has an advantage that its characteristics are prevented or suppressed from being deteriorated by heating during molding or use as a product.

ただし、一般式(５)において、Ｒ¹とＲ²はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基であり、Ｒ³とＲ⁴はそれぞれ独立して水素原子、炭素数１〜１０の炭化水素基又は極性基であって、Ｒ³とＲ⁴のうちいずれか一方のみは極性基であり、ｎは０〜２の整数である。また、一般式(６)において、Ｒ⁵〜Ｒ⁸はそれぞれ独立して水素原子又は炭素数１〜１０の炭化水素基であり、ｍは０〜２の整数である。一般式(５)及び一般式(６)における炭素数１〜１０の炭化水素基としては、一般式(１)〜(４)について述べたものと同じ基を挙げることができる。一般式(５)における極性基としては、一般式(１)〜(２)について述べたものと同じ基を挙げることができる。 The alicyclic olefin polymer used in the resin composition for screen printing of the present invention is an alicyclic olefin having a polar group represented by the general formula (5) and a nonpolar olefin represented by the general formula (6). An alicyclic olefin can be obtained by ring-opening polymerization in the presence of a metathesis catalyst. Furthermore, after the polymerization reaction, a hydrogenation reaction can be performed as necessary. Moreover, after obtaining an alicyclic olefin polymer having a polar group that generates a carboxyl group by hydrolysis of a nitrile group, ester group, amide group, acid anhydride group, etc., this is hydrolyzed and converted to a carboxyl group You can also

However, in the general formula (5), R ¹ and R ² are each independently a hydrocarbon group having 1 to 10 hydrogen atoms or carbon atoms, R ³ and R ⁴ are each independently hydrogen, carbon 1 10 to 10 hydrocarbon groups or polar groups, and only one of R ³ and R ⁴ is a polar group, and n is an integer of 0 to 2. Moreover, in General formula (6), R < ⁵ > -R < ⁸ > is respectively independently a hydrogen atom or a C1-C10 hydrocarbon group, and m is an integer of 0-2. As a C1-C10 hydrocarbon group in General formula (5) and General formula (6), the same group as what was described about General formula (1)-(4) can be mentioned. Examples of the polar group in the general formula (5) include the same groups as those described for the general formulas (1) to (2).

In the present invention, the ring-opening polymerization can be carried out in the presence of a metathesis catalyst. Examples of the metathesis catalyst include platinum group compounds such as ruthenium, rhodium, palladium, iridium, osmium, and platinum; tungsten, molybdenum, or rhenium, and periodic groups 1, 2, 4, 12, 13, or 14. A compound comprising an element having the element-carbon bond or the element-hydrogen bond; a catalyst comprising a halide or acetylacetonide such as titanium, vanadium, zirconium, tungsten, molybdenum, and an organoaluminum compound; Ruthenium compounds having an organic compound such as (cyclopentadienyl) ruthenium, bis (tricyclohexylphosphine) benzylideneruthenium dichloride, [(p-cymene) (CH ₃ CN) ₃ Ru] (BF ₄ ) ₂ as a ligand, etc. Can be mentioned. Among these, metathesis catalysts containing molybdenum, ruthenium, osmium, etc. are relatively stable to oxygen and moisture in the air and are not easily deactivated, so they can be produced even in the atmosphere. Among these, a metathesis catalyst containing ruthenium is particularly preferable because of its high polymerization activity.
In the present invention, the hydrogenation reaction of the alicyclic olefin polymer can be performed in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include homogeneous catalysts in which organic acid salts such as titanium, cobalt, nickel, or acetylacetone salts are combined with organic metal compounds such as lithium, magnesium, aluminum, tin; palladium, platinum, ruthenium, rhodium, etc. A solid catalyst having a noble metal supported on a support; a noble metal complex catalyst such as rhodium, rhenium, ruthenium; a homogeneous hydrogenation catalyst mainly composed of a group 8-10 transition metal compound of the periodic table; a group 8-10 transition metal Examples thereof include a supported catalyst supported on a carrier.

The structural unit (a) is a structural unit represented by the general formula (1) or (2), and is obtained by ring-opening polymerization of an alicyclic olefin having a polar group represented by the general formula (5). Obtainable. Examples of the alicyclic olefin having a polar polar group include 5-carboxybicyclo [2.2.1] hept-2-ene, 5-methyl-5-carboxybicyclo [2.2.1] hept. 2-ene, 5-carboxymethyl-5-carboxy bicyclo [2.2.1] hept-2-ene, 8-carboxy-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca 3-ene, 8-methyl-8-carboxylate cycloaliphatic olefins having tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-carboxyl group, such as ene; 5- ( 4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 8- (4- hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-8- (4- Hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3 and the like alicyclic olefin having a hydroxyl group such as ene. In these, the alicyclic olefin which has a carboxyl group can be used conveniently.

Examples of the alicyclic olefin having an aprotic polar group include 5-acetoxybicyclo [2.2.1] hept-2-ene and 5-methoxycarbonylbicyclo [2.2.1] hept-2. - ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 8-acetoxy tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca -3 - ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-ethoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene, 8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8-isopropoxycarbonyl tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10]} dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8-methyl-8 n- butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0 .1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10]} dodeca-3-ene How an alicyclic olefin with an ester group; 8-cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-8-cyano-tetracyclo [4. 4.0.1, ² , ^5.1,10 ] alicyclic olefins having a nitrile group such as dodec-3-ene and 5-cyanobicyclo [2.2.1] hept-2-ene; be able to. These alicyclic olefins having an ester group or a nitrile group as an aprotic polar group can generate a protic polar group by hydrolysis.
Alicyclic olefin having a polar group, 8-carboxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene and 8-methyl-8-carboxy tetracyclo [4. 4.0.1, ² , ^5.1,10 ] dodec-3-ene can be particularly preferably used.

The structural unit (b) is a structural unit represented by the general formula (3) or the general formula (4), and is obtained by ring-opening polymerization of a nonpolar alicyclic olefin represented by the general formula (6). be able to.
Examples of the nonpolar alicyclic olefin represented by the general formula (6) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylbicyclo [2.2. 1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2.2.1] hept-2-ene, 5-methylidenebicyclo [2. 2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name) : dicyclopentadiene), tetracyclo [8.4.0.1 ^11,14 .0 ^3,7] pentadeca -3,5,7,11,12- pentaene, tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dec-3-ene (trivial name: tetracyclododecene), 8-methyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8 -Ethyltetra Cyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca -3 - ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10]} dodeca-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, pentacyclo [6.5.1.1 ^{3, 6.} 0 ^2,7 .0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, tetracyclo [9.2.1.0 ^2,10 .0 ^3,8] tetradeca -3,5,7,12 Tetraene (also known as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fur Oren), pentacyclo [7.4.0.1 ^3,6 .1 ^10,13 .0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7 .0 ^{2, 10.0 3,8]} such as pentadeca-5,12-diene can be mentioned.

The alicyclic olefin polymer used in the resin composition for screen printing of the present invention includes structural units other than the structural unit (a) and the structural unit (b) (hereinafter referred to as “other structural units”), For example, other structural units derived from a monomer that can be ring-opening polymerized by a metathesis catalyst may be contained. Examples of the monomer for introducing such other structural unit include cycloolefins such as cyclobutene, cyclopentene, 3-phenylcyclopentene, cycloheptene, and cyclooctene.
The weight average molecular weight (Mw) of the alicyclic olefin polymer used in the present invention is from 3,000 to less than 10,000, more preferably from 4,000 to less than 9,500, and even more preferably 5,000. It is less than 9,000. The weight average molecular weight of the alicyclic olefin polymer can be determined as a polystyrene-converted weight average molecular weight by gel permeation chromatography using tetrahydrofuran at 40 ° C. as a solvent. When the weight average molecular weight of the alicyclic olefin polymer is from 3,000 to less than 10,000, a resin film excellent in transparency, in-plane film thickness uniformity, and adhesion can be obtained.
The glass transition temperature of the alicyclic olefin polymer is preferably 20 to 250 ° C, more preferably 50 to 200 ° C, and further preferably 70 to 170 ° C. The glass transition temperature of the alicyclic olefin polymer can be measured using a differential scanning calorimeter (DSC).
In the present invention, in the ring-opening polymerization of an alicyclic olefin, vinyl compounds such as allyl chloride, allyl alcohol and acrylamide; diene compounds such as 1,5-hexadiene and 1,6-heptadiene; α-such as 1-hexene When a molecular weight adjusting agent such as an olefin compound is added in an amount of 0.1 to 10 mol% based on the total amount of the monomer, the molecular weight of the ring-opening polymer can be easily adjusted. When the amount of the molecular weight modifier used is small, a polymer having a relatively high weight average molecular weight is obtained, and conversely, when the amount is large, a polymer having a relatively low weight average molecular weight is obtained.

The resin composition for screen printing of the present invention contains an aliphatic hydrocarbon compound in addition to the alicyclic olefin polymer. In the present invention, the aliphatic hydrocarbon compound is preferably an alicyclic hydrocarbon having a boiling point of 150 ° C. or more, more preferably an alicyclic hydrocarbon having a boiling point of 150 to 250 ° C., and a boiling point of 160 to 250 ° C. It is more preferable that it is 230 degreeC alicyclic hydrocarbon, and it is especially preferable that it is alicyclic hydrocarbon whose boiling point is 170-200 degreeC. If the boiling point of the alicyclic hydrocarbon is too high, the volatility at the time of forming the resin film is inferior. For this reason, if sufficient volatilization is performed, the resin film may be oxidatively deteriorated. Examples of alicyclic hydrocarbons having a boiling point of 150 ° C. or higher include cyclooctane (boiling point 151 ° C.), cyclononane (boiling point 171 ° C.), cyclodecane (boiling point 201 ° C.), cycloundecane (boiling point 91 ° C. (1.6 kPa)), etc. Such as cyclononene (boiling point 168 ° C.), cyclooctadiene, 1,4,7-cyclodecatriene, 1,5,9-cyclodecatriene (boiling point 231 ° C.), cyclooctyne (boiling point 157 ° C.), etc. Saturated alicyclic monocyclic hydrocarbons; saturated alicyclic polycyclic hydrocarbons such as decahydronaphthalene (common name: decalin, boiling point 190 ° C, cis-trans mixture), and unsaturated such as dicyclopentadiene (boiling point 170 ° C) Alicyclic polycyclic hydrocarbons: limonene (boiling point 176 ° C.), m-menthane (boiling point 167 ° C.), p-menthane (boiling point 171 ° C.), 3-p-mente (Boiling point 169 ° C.), α-ferrandolene (boiling point 67 ° C. (2.1 kPa)), β-ferrandylene (boiling point 180 ° C.), α-pinene (boiling point 156 ° C.), β-pinene (boiling point 165 ° C.), etc. And sesquiterpenes such as α-selinene (boiling point 143 ° C. (2.7 kPa)) and β-serinene (boiling point 134 ° C. (17.8 kPa)). These alicyclic hydrocarbons can be used individually by 1 type, or can also be used in combination of 2 or more type. Among these, decahydronaphthalene and p-menthane can be preferably used.
In the screen printing resin composition of the present invention, the blending amount of the alicyclic hydrocarbon having a boiling point of 150 ° C. or higher is 20 to 10,000 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. Preferably, the amount is 50 to 5,000 parts by weight, and more preferably 100 to 1,000 parts by weight.
In the present invention, the mixing method of the alicyclic olefin polymer and the alicyclic hydrocarbon having a boiling point of 150 ° C. or higher is not particularly limited. For example, a stirrer and a magnetic stirrer, a high-speed homogenizer, a dispersion, a planetary stirrer, It can mix using a shaft stirrer, a ball mill, a three-roll. The alicyclic olefin polymer and the alicyclic hydrocarbon having a boiling point of 150 ° C. or higher are mixed in an arbitrary order, and then filtered using a filter having a pore size of about 0.5 μm, for use. preferable.

In addition to the alicyclic olefin polymer and the alicyclic hydrocarbon having a boiling point of 150 ° C. or higher, the resin composition for screen printing of the present invention, if necessary, includes a crosslinking agent, a radiation sensitive compound, an antioxidant, and other additives. An agent can be included.
The crosslinking agent can be selected according to the kind of polar group of the alicyclic olefin polymer, and two or more functional groups capable of reacting with the polar group of the alicyclic olefin polymer in the molecule, preferably 3 The compound which has more than can be used suitably. When the alicyclic olefin polymer has a protic polar group, examples of preferred functional groups include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an oxetanyl group, and an isocyanate group. Among these, an amino group, an epoxy group, an oxetanyl group, and an isocyanate group are preferable, and an epoxy group and an oxetanyl group are particularly preferable.
As the crosslinking agent having an epoxy group, an epoxy compound having two or more epoxy groups is preferable, an epoxy compound having three or more epoxy groups is more preferable, and because of good compatibility with the alicyclic olefin polymer, A polyfunctional epoxy compound having an alicyclic structure and having 3 or more epoxy groups is more preferable. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, and epoxy acrylate heavy compound. Examples include coalescence.

As the cross-linking agent having an oxetanyl group, an oxetanyl compound having two or more oxetanyl groups is preferable, and from the viewpoint of good compatibility with an alicyclic olefin polymer, it has an alicyclic structure and has two oxetanyl groups. The polyfunctional oxetanyl compound having the above is more preferable. Examples of oxetanyl compounds include hydroxyl groups such as bisoxetanes, trisoxetanes, novolac oxetanes, calixarene oxetanes, cardo oxetanes, polyhydroxystyrene oxetanes, and silicone resins such as silsesquioxane. And an ether compound with a resin having a hydrogen atom.
The molecular weight of the crosslinking agent is preferably from 100 to 100,000, more preferably from 500 to 50,000, more preferably from 1,000 to 10,000, from the viewpoint of stability during heating and gelation efficiency. More preferably. The amount of the crosslinking agent can be selected according to the purpose of use, and is preferably 1 to 1,000 parts by weight, and preferably 5 to 500 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. It is more preferable that the amount is 10 to 100 parts by weight. When the blending amount of the crosslinking agent is 1 to 1,000 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer, the heat resistance of the formed resin film can be highly improved.

  A radiation sensitive compound can be used when patterning a resin film using actinic radiation. A radiation-sensitive compound is a compound that can absorb actinic radiation such as ultraviolet rays and electron beams and cause a chemical reaction. In the present invention, when an alicyclic olefin polymer having a protic polar group is used, it is preferably a compound capable of controlling its alkali solubility. Examples of radiation sensitive compounds include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds that are widely used as photoacid generators in radiation sensitive resin compositions for photolithography. . Of these, azide compounds are preferable, and quinonediazide compounds are particularly preferable. The compounding amount of the radiation sensitive compound is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, and 10 to 40 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. More preferably it is. When the amount of the radiation sensitive compound is 1 to 100 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer, when the resin film formed on the substrate is patterned, the radiation irradiated part and the radiation unirradiated The difference in solubility with the part becomes large, patterning by development is easy, and radiation sensitivity is also high.

  Examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-tert. -Butyl-4'-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3'-tert-butyl-5'-methyl- 2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), alkyl Bisphenol and the like can be mentioned. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate. Among these, from the viewpoint of maintaining transparency during heating, a phenol-based antioxidant is preferable, and pentaerythritol tetrakis (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate) [Irganox] (Registered trademark) 1010] is particularly preferable.

Examples of other additives include sensitizers, surfactants, latent acid generators, adhesion assistants, antistatic agents, antifoaming agents, pigments, and dyes. Examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4- Examples thereof include benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.
Surfactants are used for the purpose of preventing striations and improving coatability. For example, nonionic surfactants; fluorosurfactants; silicone surfactants; (meth) acrylic Examples include acid copolymer surfactants.
The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin film obtained from the resin composition for screen printing of the present invention, for example, a cationic polymerization catalyst that generates an acid by heating, Examples include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. Of these, sulfonium salts and benzothiazolium salts can be suitably used.
Examples of the adhesion assistant include a functional silane coupling agent, and specific examples thereof include, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyl Examples include trimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Among these, γ-glycidoxypropyltrimethoxysilane can be preferably used.

The resin composition for screen printing of the present invention preferably has a solid content concentration of 1 to 70% by weight, more preferably 5 to 50% by weight, and even more preferably 10 to 40% by weight. When the concentration of the solid content comprising the alicyclic olefin polymer and other components added as necessary is 1 to 70% by weight, the operability is good and the thickness of the resin film can be easily controlled. In-plane film thickness uniformity and printing continuity of the resin film are improved.
The resin composition for screen printing of the present invention has a viscosity at 25 ° C. of preferably 5 to 1,000,000 mPa · s, more preferably 10 to 10,000 mPa · s, and more preferably 20 to 1,000 mPa · s. -More preferably, it is s. When the viscosity at 25 ° C. is 5 to 1,000,000 mPa · s, the operability is good, the thickness of the resin film can be easily controlled, and the in-plane film thickness uniformity and printing continuity of the resin film are improved. improves.
A resin film can be formed by applying the resin composition for screen printing of the present invention to a substrate, drying, and crosslinking the resin as necessary. The substrate is not particularly limited as long as it is a molded body that does not dissolve in a resin solution. For example, a substrate constituting an electronic component such as a printed wiring board, a silicon substrate, a glass substrate, or a plastic substrate; a support substrate such as a resin film or a metal film And the like. The substrate may be one on which an electronic circuit such as a thin transistor or a light emitter is mounted. When using a substrate that constitutes an electronic component as the substrate, the resin film obtained by applying a resin solution to the substrate and drying is cross-linked with the resin in the film if necessary, and the functionality in the component is maintained as it is. Become a film. When a support substrate is used as the substrate, a resin film obtained by applying a resin solution on the support substrate and drying is laminated on a substrate constituting an arbitrary electronic component by a film lamination method or the like. By cross-linking the resin in the laminated resin film, an electronic component on which a functional film is formed can be obtained.

The conditions for drying the applied resin solution are preferably 30 to 150 ° C., more preferably 60 to 120 ° C., preferably 0.5 to 90 minutes, more preferably 1 to 60 minutes, and even more preferably 1. The method of leaving for -30 minutes can be mentioned. There is no restriction | limiting in particular in the method of drying, For example, heat drying, reduced pressure drying, air drying etc. can be mentioned.
The resin in the resin film can be cross-linked by a method according to the type of the cross-linking agent, for example, by heating or light irradiation. The heating can be performed using, for example, a hot plate or an oven. The heating temperature is preferably 100 to 250 ° C., and the heating time can be appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when a hot plate is used, it is preferably 5 to 60 minutes, and when an oven is used, it is preferably 10 to 90 minutes. Heating can be performed in an inert gas atmosphere as necessary. Light irradiation can be performed by irradiating light rays such as ultraviolet rays using an exposure machine or the like. The irradiation time can be arbitrarily set in consideration of the intensity of light to be irradiated and the thickness of the film.

The film lamination method is, for example, a method in which a resin solution is applied to a supporting substrate, a solvent is removed by heat drying to obtain a B stage film, and then this B stage film is laminated on the substrate. The heating and drying conditions vary depending on the type and blending ratio of each component, but are preferably 30 to 150 ° C, more preferably 60 to 120 ° C, preferably 0.5 to 90 minutes, more preferably 1 to 60 minutes. More preferably, it can be performed for 1 to 30 minutes. The lamination can be performed using a pressure bonding machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator. The resin film formed on the substrate may be patterned.
The thickness of the resin film thus obtained can be appropriately set according to the purpose of use of the resin film, but is usually preferably 0.1 to 1,000 μm, preferably 0.3 to 500 μm. More preferably, it is more preferably 0.5 to 100 μm. When the thickness is 0.1 to 1,000 μm, a resin film having a water vapor transmission rate of 1,500 g / m ² · 24 h or less can be obtained.
The resin film obtained from the resin composition for screen printing of the present invention includes a sealing film, an insulating film, a planarizing film, etc. in the manufacture of electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices. It can be used for forming. In particular, in a display element such as an organic EL element and a display device including the same, it is suitably used for forming a sealing film, an insulating film, a planarizing film, etc. provided in a state of covering elements and wirings provided on a substrate. be able to.
The resin composition for screen printing of the present invention has good printing continuity, and the resulting resin film has good uniformity in film thickness, high transparency and adhesion, and low water vapor permeability. In addition, it is excellent in flatness, high insulative properties, and can suppress the corrosion and deterioration of the sealed contents in contact with the resin film by water, and can constitute an electronic component that can be driven stably for a long period of time. .

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The hydrogenation rate, weight average molecular weight, viscosity, in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties and printing continuity are the methods shown below. Measured according to
(1) Hydrogenation rate Hydrogenation rate, that is, the sum of the structural unit represented by the general formula (2) and the structural unit represented by the general formula (4) with respect to the sum of the structural unit (a) and the structural unit (b) Was measured by ¹ H-NMR using a nuclear magnetic resonance apparatus [JEOL Ltd., JNM-ECA500].
(2) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) of the polymer was measured by polystyrene conversion using tetrahydrofuran as a solvent using a high-speed gel permeation chromatograph [Tosoh Corporation, HLC-8220GPC].
(3) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer.
(4) In-plane film thickness uniformity Resin for screen printing using a stainless steel screen [Tokyo Process Service Co., Ltd., ST500] on a 150 mm × 150 mm × 1.4 mm glass substrate [Corning, Corning 1737 Glass]. The composition was applied using a micro squeegee [Microtech Co., Ltd.] at a squeegee speed of 50 mm / sec. Using a screen printer [Microtech Co., Ltd., MT-320TVC]. Then, it heated for 30 minutes at 80 degreeC using the hotplate, and formed the resin film with a film thickness of 3 micrometers. About the obtained resin film, the film thickness of 121 points | pieces in the surface was measured using the optical film thickness meter [Nanometrics Japan Co., Ltd., Nanometrics Nanospec M6500]. The measurement point was an intersection when a glass substrate of 150 mm × 150 mm was divided into 12 parts vertically and horizontally. Based on the measured film thickness, the in-plane film thickness uniformity was calculated by the following equation.
In-plane film thickness uniformity (%) = {(film thickness maximum value−film thickness minimum value) / (average film thickness)} × 100
The smaller this value, the more uniform the film thickness of the resin film in the substrate surface. Generally, when the uniformity of the in-plane film thickness is high, the application property of the resin composition is also good. When this value was less than 10%, it was evaluated as x when the value was 10% or more.
(5) Flatness A resin film having a film thickness of 3 μm was formed on a silicon oxide film substrate having a level difference of 2 μm by the same method as the in-plane film thickness uniformity. The silicon oxide film step portion of the obtained substrate was measured using a contact-type film thickness measuring instrument [KLA Tencor Co., Ltd., P-10], and when the step was less than 0.2 μm, ○, 0.2 μm It evaluated as x at the above time.
(6) Light transmittance A resin film having a film thickness of 2 μm was formed on a glass substrate [Corning, Corning 1737 glass] by the same method as the in-plane film thickness uniformity. About this resin film, the light transmittance was measured at a wavelength of 550 nm using a spectrophotometer [JASCO Corporation, V-560]. The measured value was converted into a light transmittance of 2.0 μm and evaluated based on the Lambert-Beer equation. The higher the light transmittance, the better the transparency.
(7) Water vapor transmission rate On a polyimide film [Toray DuPont, Kapton 100H] having a thickness of 25 μm, a resin film having a thickness of 3 μm was formed in the same manner as the in-plane film thickness uniformity. About this composite film, the water-vapor-permeation rate was measured on 40 degreeC and 90% RH conditions using the water-vapor-permeation measuring apparatus [MOCON company, PERMATRAN-W] according to JISK7192 7.B method. Similarly, the water vapor permeability of the resin film was calculated based on the following equation by measuring the water vapor permeability of the polyimide film itself.
Water vapor permeability of resin film = (1 / composite membrane permeability-1 / polyimide film permeability) ^-1
The lower the water vapor transmission rate, the higher the performance of protecting the internal electronic material.
(8) Insulation A resin film having a thickness of 3 μm was formed on a P-type silicon wafer (resistance value of 1Ω or less) by the same method as that for evaluating the in-plane film thickness uniformity. Current-voltage characteristics were evaluated using a mercury prober [CVmap92A, manufactured by Four Dimension Inc.]. That is, the value of the current flowing in the resin film when a voltage amount of 1 MV / cm was applied was measured. Current value when less than 3 × 10 ^-10 A / cm ² is ○, was × when 3 × 10 ^-10 A / cm ² or more.
(9) Adhesiveness A resin film having a film thickness of 2 μm was formed on a glass substrate [Corning, Corning 1737 glass] by the same method as in-plane film thickness uniformity. About this resin film, according to JISK5600-5-6, 100 places were observed and the part which did not peel was counted. The more parts that did not peel off, the higher the adhesion.
(10) Sealing properties (emission luminance evaluation of organic electroluminescence elements)
Using a sealed organic electroluminescence device manufactured by the method described later, a test was performed in which the sample was allowed to stand for 10,000 hours in an environment of 40 ° C. and 90% RH. A direct current voltage was applied to each of the elements before and after the standing test using the chromium electrode layer as an anode and the transparent electrode layer as a cathode.
After the neglect test, as in the case before the neglect test, when a dark spot was not seen on the light emitting surface, ○, a dark spot was generated after the neglect test, but when blue light emission was confirmed from the cathode side from 5V in the bright place △ when the visibility is good (that is, when the number of generated dark spots is small), a dark spot is generated after the standing test, and when blue light emission is confirmed from the cathode side from 5 V in a bright place When the property was bad (that is, when the number of generated dark spots was large), it was evaluated as x.
(11) Printing continuity A resin film having a film thickness of 2 μm was continuously formed three times on a glass substrate [Corning, Corning 1737 glass] by the same method as the in-plane film thickness uniformity. The obtained resin film was measured for film thickness by the same method as the in-plane film thickness uniformity, and the standard deviation of the average value of the film thickness after 1 to 3 printings was evaluated as printing continuity. As this value is smaller, it means that the film thickness of the resin film is uniform even when continuously printed, and it can be said that the printing continuity is excellent. When this value was less than 0.5 μm, it was evaluated as ○, and when it was 0.5 μm or more, it was evaluated as ×.

Example 1
Providing structural units (a) 8- carboxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene (hereinafter referred to as TCDC.) 5.4 parts by weight (5 mol %), giving the structural units (b) 8- ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene (hereinafter referred to as ETD.) 94.6 parts by weight (95 mol%) 1,5-hexadiene 5.5 parts by weight, 1,3-dimesitylimidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts by weight and toluene 400 parts by weight, The mixture was charged in a nitrogen pressure-resistant glass pressure reactor and subjected to ring-opening polymerization reaction at 70 ° C. for 2 hours with stirring to obtain a polymer solution (solid-liquid concentration of about 20% by weight). The polymer had a weight average molecular weight of 6,000 and a number average molecular weight of 2,900. A part of this polymer solution was transferred to an autoclave equipped with a stirrer, and hydrogen was dissolved at 150 ° C. at a pressure of 4 MPa and reacted for 5 hours. A polymer hydrogenated solution containing a hydrogenated polymer (solid-liquid component) A concentration of about 20% by weight) was obtained. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 6,000. The results are shown in Table 1.
1 part by weight of powdered activated carbon was added to 100 parts by weight of the polymer hydrogenated solution, and the mixture was placed in an autoclave, and hydrogen was dissolved at 150 ° C. at a pressure of 4 MPa for 3 hours while stirring. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm, and activated carbon was separated to obtain a polymer solution. Filtration could be performed without delay. 233 parts by weight of decalin (cis-trans mixture, boiling point 190 ° C.) was added to this polymer solution, and the mixed solution was concentrated under reduced pressure using an evaporator to remove toluene, thereby obtaining a resin decalin solution. This decalin solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin solution (A).
The resin film A was formed using the resin solution (a), and the in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties and printing continuity were evaluated. . The results are shown in Table 2.

Example 2
Example 1 except that the amount of TCDC was 1.1 parts by weight (1 mol%), the amount of ETD was 98.9 parts by weight (99 mol%), and the amount of 1,5-hexadiene was 4 parts by weight. Resin solution (I) was prepared in the same manner. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 8,200. The results are shown in Table 1.
The resin film B was formed using the resin solution (a), and the in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties and printing continuity were evaluated. . The results are shown in Table 2.
Example 3
Except that the amount of TCDC was 21.3 parts by weight (20 mol%), the amount of ETD was 78.7 parts by weight (80 mol%), and the amount of 1,5-hexadiene was 3.5 parts by weight. A resin solution (c) was prepared in the same manner as in 1. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 8,900. The results are shown in Table 1.
The resin film C was formed using the resin solution (U), and the in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties and printing continuity were evaluated. . The results are shown in Table 2.
Example 4
A resin solution (D) was prepared in the same manner as in Example 1 except that 233 parts by weight of p-menthane (cis-trans mixture, boiling point 171 ° C.) was added instead of 233 parts by weight of decalin. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 6,000. The results are shown in Table 1.
The resin film D was formed using the resin solution (D), and the in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties and printing continuity were evaluated. . The results are shown in Table 2.

Comparative Example 1
Example 1 except that the amount of TCDC was 6.5 parts by weight (6 mol%), the amount of ETD was 93.5 parts by weight (94 mol%), and the amount of 1,5-hexadiene was 2 parts by weight. A resin solution (e) was prepared by the method described above. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 16,300. The results are shown in Table 1.
The resin film E was formed using the resin solution (e), and the in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties and printing continuity were measured. . The results are shown in Table 2.
Comparative Example 2
The resin solution (f) was prepared in the same manner as in Example 1 except that TCDC was not used and the amount of ETD was 100 parts by weight (100 mol%) and the amount of 1,5-hexadiene was 3.5 parts by weight. Prepared. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 8,800. The results are shown in Table 1.
A resin film F was formed using a resin solution (f), and in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties, and printing continuity were measured. . The results are shown in Table 2.
Comparative Example 3
50 parts by weight of a bisphenol A type epoxy resin [Japan Epoxy Resin Co., Ltd., Epicoat 828], 5 parts by weight of a photoacid generator [Asahi Denka Kogyo Co., Ltd., Adekaoptomer SP-170] and polytetramethylene glycol [Mitsubishi Chemical Co., Ltd., PTMG1000] 10 parts by weight using a homodisper type stirring mixer [Special Machine Chemical Co., Ltd., Homodisper L], uniformly stirring and mixing at a stirring speed of 3,000 rpm, and then having a pore size of 0.45 μm. A resin solution (ki) was prepared by filtration through a polytetrafluoroethylene filter. The weight average molecular weight of this polymer was 7,000. The results are shown in Table 1.
A resin film G was formed using a resin solution (ki), and in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties, and printing continuity were measured. . The results are shown in Table 2.

Comparative Example 4
A resin solution (C) was prepared in the same manner as in Example 1 except that 233 parts by weight of 1,2-dimethylcyclohexane (cis body, boiling point 130 ° C.) was added instead of 233 parts by weight of decalin. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 6,000. The results are shown in Table 1.
A resin film H was formed using a resin solution (K), and in-plane film thickness uniformity, flatness, light transmittance, water vapor transmittance, insulation, adhesion, sealing properties, and printing continuity were evaluated. . The results are shown in Table 2.
Comparative Example 5
A resin solution (ke) was prepared in the same manner as in Example 1 except that 233 parts by weight of furfuryl alcohol (boiling point 171 ° C.) was added instead of 233 parts by weight of decalin. The hydrogenation rate of this polymer hydrogenated product was 100%, and the weight average molecular weight was 6,000. The results are shown in Table 1.
An attempt was made to form the resin film I using the resin solution (ke), but the resin was deposited from the solution, and a uniform resin film could not be formed. It was not possible to evaluate transmittance, water vapor permeability, insulating properties, adhesion, sealing properties, and printing continuity.
In Examples 1-4, Comparative Examples 1-2, and Comparative Examples 4-5, the gas chromatograph [Shimadzu Corporation] showed that the polymerization conversion rate of the ring-opening polymerization reaction of the alicyclic olefin was 100%. It was confirmed by a manufacturing company, GC-17A] that no alicyclic olefin remained.

From this result, when using a resin composition for screen printing obtained by using an alicyclic olefin polymer having a specific structural unit with a controlled weight average molecular weight and an alicyclic hydrocarbon having a boiling point of 150 ° C. or higher. High transparency, good in-plane film thickness uniformity, high adhesion, low water vapor permeability, excellent insulation, flatness, sealing, printing continuity, electronic It turns out that the resin film for electronic components suitable for manufacture of components is obtained.
Even if it has a specific structural unit, in Comparative Example 1 using an alicyclic olefin polymer whose weight average molecular weight is too high, the in-plane film thickness uniformity, flatness, sealing property, and printing continuity are Inferior. In Comparative Example 2 using an alicyclic olefin polymer having no specific structural unit, sealing properties and printing continuity are inferior. In the comparative example 3 which used the epoxy resin instead of the alicyclic olefin polymer, it is inferior to insulation and sealing performance. In Comparative Example 4 using cis-1,2-dimethylcyclohexane having a boiling point of 130 ° C. as a solvent, in-plane film thickness uniformity, planarization, sealing, and printing continuity are inferior. In Comparative Example 5 using furfuryl alcohol as a solvent, a uniform resin film cannot be formed.

(Formation of sealed organic electroluminescence device)
A reverse taper type resin partition layer having a film thickness of 3.5 μm is provided on a glass plate having a chromium electrode layer patterned on the surface, with a light shielding film having a thickness of 1.0 μm on a glass plate having a size of 25 mm × 75 mm × 1.1 mm. The organic electroluminescence element substrate thus obtained was fixed to a substrate holder of a vapor deposition apparatus [Nippon Vacuum Technology Co., Ltd.], and N, N′-bis (3-methylphenyl) -N, 200 mg of N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine (hereinafter abbreviated as “TPD”) was added, and 4,4′-bis (2 , 2′-diphenylvinyl) biphenyl (hereinafter abbreviated as DPVBi) 200 mg, and the vacuum chamber was depressurized to 1 × 10 ⁻⁴ Pa.
Next, the boat containing TPD was heated to 215 to 220 ° C., and TPD was evaporated at an evaporation rate of 0.1 to 0.3 nm / second to form a hole injection transport layer having a thickness of 60 nm. The substrate temperature at this time was room temperature. Without removing this from the vacuum chamber, the DPVBi-containing boat is heated to 240 ° C., and DPVBi is vapor-deposited on the hole injecting and transporting layer at a vapor deposition rate of 0.1 to 0.3 nm / second to emit light with a film thickness of 40 nm. A layer was formed. The substrate temperature at this time was also room temperature. This was taken out from the vacuum chamber, a stainless steel mask was placed on the light emitting layer, and fixed to the substrate holder again. Then, tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ³ ) was placed on the molybdenum boat. ) 200 mg was put, another 1 g of magnesium ribbon was put in a boat made of molybdenum, 500 mg of silver wire was put in a tungsten basket, and these boats were mounted in a vacuum chamber. Next, from the pressure of the vacuum vessel was reduced to 1 × 10 ^-4 Pa, the boat Alq ³ containing heated to 230 ° C., the light emitting layer on the at the Alq ³ vapor deposition rate 0.01～0.03Nm / sec Evaporation was performed to form an electron injection layer having a thickness of 20 nm. Further, silver is deposited on the electron injection layer at a deposition rate of 0.01 nm / second, and at the same time, magnesium is deposited on the electron injection layer at a deposition rate of 0.14 nm / second, and a mixed metal of magnesium and silver is used. An electron injection metal layer having a thickness of 10 nm was formed. Finally, this was transferred to another vacuum chamber, and an In—Zn—O-based amorphous transparent conductive layer having a thickness of 200 nm was formed on the electron-injecting metal layer by DC sputtering through the same mask. The DC sputtering conditions were a mixed gas of argon and oxygen (volume ratio 1000: 5) as a sputtering gas, a pressure of 0.3 Pa, and a DC output of 40 W. Thus, the light-emitting part of the organic electroluminescence element was formed by forming the transparent electrode layer (cathode) composed of the electron injection metal layer and the amorphous transparent conductive layer.
Resin solutions (A) to (K) are applied to the surface of the glass plate obtained above with the light emitting part of the organic electroluminescence element at a thickness of 3.5 μm in the same manner as the in-plane film thickness uniformity. This was applied and heated on a hot plate at 80 ° C. for 30 minutes to form a resin film having a thickness of 3 μm on the transparent electrode layer (cathode). In this manner, a sealed organic electroluminescence element was produced. Sealability was evaluated using this element.

  The resin composition for screen printing of the present invention has good printing continuity, and the resin film obtained from the composition has good in-plane film thickness uniformity, high transparency and adhesion, and low It is a water vapor permeable resin film with excellent flatness, high insulation, and excellent sealing properties. For example, sealing in the manufacture of electronic components such as integrated circuit elements, display elements, and solid-state imaging elements. It can be suitably used for forming a film, an insulating film, a planarizing film, and the like.

Claims (7)

It has a structural unit (a) represented by general formula (1) or general formula (2) and a structural unit (b) represented by general formula (3) or general formula (4), and has a weight average molecular weight. A resin composition for screen printing, comprising: an alicyclic olefin polymer having a molecular weight of 3,000 or more and less than 10,000; and an aliphatic hydrocarbon compound.

(In the formula, R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom, having 1 to 10 carbon atoms. (It is a hydrocarbon group or a polar group, and only one of R ³ and R ⁴ is a polar group, and n is an integer of 0 to 2.)

(However, in formula, R < ⁵ > -R < ⁸ > is a hydrogen atom or a C1-C10 hydrocarbon group each independently, and m is an integer of 0-2.)   The resin composition for screen printing according to claim 1, wherein the aliphatic hydrocarbon compound is an alicyclic hydrocarbon having a boiling point of 150 ° C. or higher.   The ratio of the structural unit (a) to the total of the structural unit (a) and the structural unit (b) in the alicyclic olefin polymer is 0.005 to 40 mol%. Resin composition for screen printing.   Ratio of the total of the structural unit represented by the general formula (2) and the structural unit represented by the general formula (4) to the total of the structural unit (a) and the structural unit (b) in the alicyclic olefin polymer. The resin composition for screen printing according to any one of claims 1 to 3, wherein is 90 mol% or more.   Solid content concentration is 1 to 70 weight%, The resin composition for screen printing of any one of Claims 1-4.   The resin composition for screen printing according to any one of claims 1 to 5, which has a viscosity at 25 ° C of 5 to 1,000,000 mPa · s.   A method for forming a resin film, comprising a step of applying the coating composition for screen printing according to any one of claims 1 to 6 to a substrate by a screen printing method.