JP4997766B2 - Resin composition, method for producing the same, and resin film - Google Patents

Description

  The present invention relates to a resin composition capable of forming a resin film having excellent transparency and in-plane film thickness uniformity, a method for producing the same, and a resin film.

  Various electronic display devices such as organic electroluminescence (hereinafter abbreviated as “EL”) devices and liquid crystal display devices, integrated circuit devices, solid-state imaging devices, color filters, black matrices, etc. Protective film for preventing deterioration and damage, sealing film for protecting contents, flattening film for flattening element surface and wiring, electrical insulating film for maintaining electrical insulation, arranged in layers Various functional resin films such as an interlayer insulating film for insulating between wirings are provided.

  These resin films may require not only low dielectric properties but also transparency as the resin film material is diversified.

  As a material for forming a resin film having transparency, for example, there is a resin composition containing an alicyclic olefin addition copolymer having a reactive silyl group having a specific structure. It is known that when an oxide is added, a cross-linked structure is formed to give a transparent resin film excellent in dimensional stability and the like (Japanese Patent Laid-Open No. 2003-160620).

  JP-A-11-327125 reports that the addition of inorganic fine particles such as colloidal silica to the photosensitive resin composition improves the oxygen plasma resistance, heat resistance, dry etching resistance, etc. of the resulting resin film. Yes. Japanese Patent Application Laid-Open No. 2003-156838 describes that a resin film excellent in coating film uniformity and storage stability can be obtained by adding a certain glycol solvent to an alicyclic olefin resin. ing. The alicyclic olefin resin disclosed herein can form a transparent electrical insulating film.

  Under these conventional techniques, the present inventor selected an alicyclic olefin resin as a resin component and added a silica sol proposed in JP-A-11-327125 in order to obtain a resin film having excellent transparency. An attempt was made to prepare a resin composition. However, when this resin composition is used, a resin film excellent in transparency can be obtained, but a resin film having a uniform film thickness in the plane (resin film having in-plane film thickness uniformity) cannot be obtained. It turns out that there is.

  Based on this knowledge, the present inventor has intensively studied to obtain a resin composition that can form a transparent and in-plane film thickness uniform resin film. As a result, when an alicyclic olefin resin having a certain kind of polar group is used as the resin component, even if inorganic fine particles such as silica sol are present, the resin has excellent transparency and in-plane film thickness uniformity. It was found that a resin composition capable of forming a film was obtained, and the present invention was completed.

Thus, according to the first aspect of the present invention, the following resin compositions (1) to (7) are provided.
(1) It contains an alicyclic olefin resin, inorganic fine particles, and a solvent having in the molecule one or more selected from the group consisting of a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group and an imide group. Resin composition.
(2) The filtration rate when filtered through a membrane filter having a diameter of 47 mm, a pore diameter of 1 μm and a porosity of 83% under a pressure of 23 ° C. and 0.5 kgf / cm ² is 20 g / min or more. The resin composition of (1).

(3) The solvent contains 500 parts by weight or more of a solvent in which the solubility of the alicyclic olefin resin at 23 ° C. is 20% by weight or more with respect to 100 parts by weight of the alicyclic olefin resin. The resin composition of (1).
(4) The resin composition according to (3), wherein the solvent is at least one selected from the group consisting of a glycol diether compound, a glycol monoether compound, and an amide compound.
(5) The alicyclic olefin resin has the formula (I)

[Wherein, R ^{1 to} R ⁴ are each independently a hydrogen atom or a formula: —X _n —R (X is a divalent group, n is 0 or 1, and R is a substituent. An optionally substituted alkyl group having 1 to 7 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, an aromatic group, a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group, Or an imide group), one or more of R ^{1 to} R ⁴ are represented by the formula: —X _n —R ^a (wherein X and n are as defined above, R ^a Is a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group, or an imide group. m is an integer of 0-2. ] The resin composition of (1) which is resin which has a repeating unit represented by these.
(6) The resin composition according to (1), wherein the inorganic fine particles have a primary particle diameter of 1 to 200 nm.
(7) The resin composition according to (1), wherein the inorganic fine particles are metal oxides.

According to 2nd of this invention, the manufacturing method of the resin composition of following (8)-(10) is provided.
(8) The resin composition according to (1), comprising a step of mixing a resin solution containing the alicyclic olefin resin and a solvent and an inorganic fine particle dispersion containing the inorganic fine particles and a dispersion medium. Manufacturing method.
(9) The method for producing a resin composition according to (8), wherein the solvent is at least one selected from the group consisting of a glycol diether compound, a glycol monoether compound, and an amide compound.
(10) The method for producing a resin composition according to (8) or (9), wherein the dispersion medium is at least one selected from the group consisting of glycol ether acetate compounds, glycol diether compounds, glycol monoether compounds, and amide compounds. .

According to the third aspect of the present invention, the following resin film (11) is provided.
(11) A resin film having a thickness of 0.1 to 200 μm formed using the resin composition according to any one of (1) to (7).

Hereinafter, the present invention will be described in detail.
1) Resin composition The resin composition of the present invention comprises an alicyclic olefin resin, inorganic fine particles, having in its molecule one or more selected from the group consisting of a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group and an imide group. And containing a solvent.

(1) Alicyclic olefin resin The alicyclic olefin resin used in the present invention is a polymerizable monomer having an alicyclic structure and a carbon-carbon double bond (hereinafter referred to as "alicyclic olefin monomer"). ) Is a polymer having a structural unit derived therefrom.
The alicyclic structure possessed by the alicyclic olefin monomer may be monocyclic or polycyclic (condensed polycyclic, bridged ring, combined polycyclic, etc.). From the viewpoints of the mechanical strength and heat resistance of the resin film, polycyclic is preferable.

  The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15. When the number of carbon atoms is within such a range, various characteristics such as heat resistance and pattern property of the resin film are highly balanced, which is preferable.

  In the alicyclic olefin resin, the proportion of the structural unit derived from the alicyclic olefin monomer is appropriately selected according to the purpose of use, but is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably. Is 70 to 100% by weight. When the proportion of the structural unit derived from the alicyclic olefin monomer is excessively small, the heat resistance of the resin film is inferior, which is not preferable.

  The alicyclic olefin resin used in the present invention is one or more selected from the group consisting of a carboxyl group (hydroxycarbonyl group), a dicarboxylic anhydride group (carbonyloxycarbonyl group), a hydroxyl group, and an imide group in the molecule. (Hereinafter, these may be collectively referred to as “specific polar groups”).

  The specific polar group may be directly bonded to the carbon atom constituting the alicyclic structure that is the main chain of the resin, or may be bonded to the carbon atom constituting the alicyclic structure as a group including the specific polar group. Also good. In the latter case, the specific polar group is bonded to the carbon atom constituting the alicyclic structure via a divalent organic group such as an alkylene group.

  Examples of the group containing a specific polar group include a group containing a carboxyl group, a group containing a dicarboxylic anhydride group, a group containing a hydroxyl group, and a group containing an imide group.

Examples of the group containing a carboxyl group include a hydroxycarbonylalkyl group and a hydroxycarbonylphenyl group.
The group containing a dicarboxylic anhydride group is represented by an alkyleneoxycarbonyloxyalkyl group, [— (CH ₂ ) _p —CO—O—CO— (CH ₂ ) _p — (p represents an arbitrary natural number)]. And the like.

Examples of the group containing a hydroxyl group include a group containing a phenolic hydroxyl group such as a hydroxyphenyl group and a hydroxyphenylalkyl group; a group containing an alcoholic hydroxyl group such as a hydroxyalkyl group, a hydroxyalkoxy group and a hydroxyalkoxycarbonyl group. It is done.
Examples of the group containing an imide group include an N-phenyldicarboximide group.

  Among these, preferred specific examples of the specific polar group or the group containing the specific polar group include a carboxyl group, a hydroxycarbonylmethyl group, a carbonyloxycarbonyl group, a hydroxyl group, a hydroxymethoxy group, and a 2-hydroxyethoxy group.

  The alicyclic olefin resin used in the present invention may have only one type of specific polar group, or may have two or more types combined. From the viewpoint of highly balancing various properties of the resin composition of the present invention and the resin film obtained from the composition, the alicyclic olefin resin preferably has a combination of two or more, and has a carboxyl group and It is particularly preferable to have an imide group.

  As the alicyclic olefin resin used in the present invention, a resin having a repeating unit represented by the formula (I) is preferable because it provides a resin film having excellent transparency.

In the formula (I), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a group represented by the formula: —X _n —R. However, at least ^one of R ^{1 to} R ⁴ is a group represented by the formula: —X _n —R ^a (R ^a represents the specific polar group). Moreover, when any two of R ^{1 to} R ⁴ are groups represented by the formula: —X _n —R ^a , they are bonded to different carbons (for example, R ¹ and R ³ ). preferable.

Formula: in _-X n -R, X represents a divalent group.
Specific examples of X include alkylene groups such as methylene group, ethylene group and propylene group; arylene groups such as o-phenylene group, m-phenylene group, p-phenylene group and naphthalene group; group represented by —O— A group represented by -R ^b -CO-R ^b- (R ^b represents an alkylene group or an arylene group); and the like. Here, specific examples of the alkylene group and arylene group for R ^b include the same alkylene groups and arylene groups as those described above for X.
Among these, an alkylene group or an arylene group is preferable from the viewpoint of stability.
n is 0 or 1.
M is an integer of 0 to 2, and is preferably 0 or 1.

  R represents an optionally substituted alkyl group having 1 to 7 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, an aromatic group, or the specific polar group. To express.

Examples of the alkyl group having 1 to 7 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, n-pentyl group, 1- Methylbutyl group, 2-methylbutyl group, isopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 2-ethylbutyl group, 3-methylpentyl group, isohexyl group, n-heptyl group, 1-methyl Examples include hexyl group, 2-methylhexyl group, 3-methylhexyl group, 2-ethyl-3-methylbutyl group, isoheptyl group and the like.
Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

  Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydroxyl group; acyl group such as acetyl group and benzoyl group; alkoxyl group such as methoxy group, ethoxy group and isopropoxy group; phenoxy group, 4- Aryloxy groups such as methylphenoxy group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and t-butoxycarbonyl group; alkylcarbonyloxy groups such as acetoxy group; arylcarbonyloxy groups such as benzoyloxy group; nitro group; A cyano group; and the like.

  As an aromatic group, a phenyl group which may have a substituent such as a phenyl group, 2-chlorophenyl group, 4-methylphenyl group; 1-naphthyl group, 2-naphthyl group, 6-methyl-1-naphthyl A naphthyl group which may have a substituent such as a group; a pyridyl group which may have a substituent such as a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group;

  The method for obtaining the alicyclic olefin resin used in the present invention is not particularly limited, and examples thereof include the following methods (i) to (iv).

(I) A resin obtained by polymerizing an alicyclic olefin monomer having no specific polar group in the presence of a radical polymerization initiator is modified by a known method using a compound containing the specific polar group. The method of introducing a specific polar group.

  Examples of the compound containing a specific polar group include acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethylacrylic acid, 2-hydroxyethylmethacrylic acid, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2 2.1] unsaturated carboxylic acid compounds such as hept-5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, And imide derivatives thereof; unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride; and the like.

(Ii) A polymer obtained by polymerizing an alicyclic olefin monomer having a polar group other than a specific polar group such as an alkoxycarbonyl group and having no specific polar group in the presence of a radical polymerization initiator. A method of inducing a polar group other than the specific polar group contained in the obtained polymer into a specific polar group by hydrolysis or reduction by a known method.

The polar group other than the specific polar group is a group that can be derived into the specific polar group by a chemical reaction such as hydrolysis or reduction. ^{Specifically, -OR c; -OCOR c; -COOR} c; N- substituted amide group; and the like. Here, R ^c is a linear, branched or alicyclic saturated hydrocarbon group or unsaturated hydrocarbon group. The saturated hydrocarbon group or unsaturated hydrocarbon group may be substituted with a group containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom (excluding a hydroxyl group and a hydroxycarbonyl group).

  In the method of (i), (ii), when the alicyclic olefin monomer having no specific polar group is radically polymerized, addition copolymerization with the alicyclic olefin monomer or as necessary Other monomers capable of ring-opening copolymerization (hereinafter referred to as “other monomers”) may be added. Moreover, you may hydrogenate the unsaturated bond part of resin obtained as needed according to a conventional method.

(Iii) A method of copolymerizing an alicyclic olefin monomer having no specific polar group and an alicyclic olefin monomer having a specific polar group.
In this method, when copolymerizing, other monomers may be added if necessary, and if necessary, the unsaturated bond portion of the obtained resin is hydrogenated according to a conventional method. Also good.

  Further, in the method of (iii), an alicyclic olefin monomer having no specific polar group and an alicyclic olefin monomer having a specific polar group are opened in the presence of an organic ruthenium polymerization catalyst. After metathesis copolymerization, if necessary, hydrogenate the unsaturated bond portion according to a conventional method, and if necessary, induce a polar group other than the specific polar group to the specific polar group by hydrolysis or the like, The target alicyclic olefin resin can be obtained. According to this method, an alicyclic olefin resin having a specific polar group with a narrow molecular weight distribution can be obtained efficiently.

  The organic ruthenium polymerization catalyst used here is a catalyst containing ruthenium that promotes ring-opening polymerization. Among these, a polymerization catalyst mainly composed of an organoruthenium compound coordinated with a neutral electron donating ligand is preferable. A neutral electron donating ligand is a ligand that has a neutral charge when pulled away from the central metal (ie, ruthenium).

  A more preferable organic ruthenium compound is a compound in which an anionic ligand is coordinated together with a neutral electron-donating ligand. Anionic ligands are ligands that have a negative charge when pulled away from ruthenium.

  The organic ruthenium compound may further contain a counter anion. The counter anion refers to an anion that forms an ion pair with a ruthenium cation, and is not particularly limited as long as it is an anion that can form such a pair.

  Specific examples of the organic ruthenium compound include bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropenylidene ruthenium dichloride, bis (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, bis ( Tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, bis (1,3-diisopropylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazoline-2-ylidene) benzylidene ruthenium dichloride, (1,3- Dimesitylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl Dazorijin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, and the like.

  Further, in order to enhance the polymerization activity of the polymerization catalyst described above, nitrogen-containing compounds such as pyridines; phosphines; 1,3-diisopropylimidazoline-2-ylidene, 1,3-dimesitylimidazolidin-2-ylidene described above, etc. A neutral electron donating compound such as a heterocyclic carbene compound may be added at a ratio of 1 to 100 times by weight with respect to the ruthenium metal in the polymerization catalyst.

Further, when the polymerization catalyst described above is used, in order to increase the polymerization activity, for example, a diazo compound such as N ₂ CHCOOEt; an acetylene compound such as phenylacetylene; a silyl compound such as Et ₂ SiH and Ph ₂ MeSiH; It can also be used at a ratio of 1 to 100 times by weight with respect to the ruthenium metal. Here, Et represents an ethyl group, Ph represents a phenyl group, and Me represents a methyl group.

(Iv) In the above methods (i) to (iii), an aromatic polymerizable monomer is used instead of a part or all of the alicyclic olefin monomer, and the resin obtained The target alicyclic olefin resin can also be obtained by a method of hydrogenating an aromatic carbon-carbon double bond.

  Specific examples of the polymerizable monomer used to obtain the alicyclic olefin resin in the above methods (i) to (iv) are shown in the following (a) to (d). In addition, the compound illustrated as an alicyclic olefin monomer which has a specific polar group is a monomer which gives the repeating unit represented by the said Formula (I).

(A) An alicyclic olefin monomer having a carboxyl group as a specific polar group 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-hydroxycarbonylmethylbicyclo [2.2.1] hept 2-ene, 5,6-di (hydroxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5,6-di (hydroxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxycarbonyl-5-hydroxycarbonylmethylbicyclo [2.2.1] hept-2-ene Bicycloheptene derivatives such as 5-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-hydroxycarbonylmethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5,6-di (hydroxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-methyl-5-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-methyl-5,6-di (hydroxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-hydroxycarbonyl-5-hydroxycarbonylmethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene; 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxycarbonylmethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (hydroxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8,9-di (hydroxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxycarbonyl-8-hydroxycarbonylmethyltetracyclo [4.4.0.1 ^2,5 . ^{Tetracyclododecene} derivatives such as 1 ^7,10 ] dodec-3-ene;

11-hydroxycarbonylhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-hydroxy carbonyl-methyl hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11,12-di (hydroxy-carbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-methyl-11-hydroxy carbonyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-methyl-11,12-di (hydroxy-carbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-hydroxy carbonyl-11-hydroxycarbonyl-methyl hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . Etc.; 0 ^9,14] hex cycloheptanone decene derivatives such heptadeca-4-ene.

(B) Cycloaliphatic olefin monomer having a dicarboxylic anhydride group as a specific polar group Bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-methylbicyclo [2 2.1] Bicycloheptene derivatives such as hept-2-ene-5,6-dicarboxylic acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8,9-dicarboxylic anhydride, 8-methyltetracyclo [4.4.0.1 ^2,5 . Tetracyclododecene derivatives such as 1 ^7,10 ] dodec- ³ -ene-8,9-dicarboxylic anhydride, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene-11,12-dicarboxylic acid anhydride, 11-methyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene-11,12-hexafluoro cycloheptanone decene derivatives such as dicarboxylic anhydrides; like.

(C) Cycloaliphatic olefin monomer having hydroxyl group as specific polar group 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2 -Ene, 5,6-dihydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2-hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-methyl- 5- (2-hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (3-hydroxypropoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-methyl- 5- (3-hydroxypropoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (4-hydroxybutoxycarbonyl) bicyclo [2.2.1] hept-2 -Bicycloheptene derivatives such as ene;

8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-bis (hydroxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-hydroxyethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-hydroxyethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (3-hydroxypropoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (3-hydroxypropoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (4-hydroxybutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . ^{Tetracyclododecene} derivatives such as 1 ^7,10 ] dodec-3-ene;

11-hydroxyhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-hydroxy methylhexahydrophthalic cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11,12-bis (hydroxymethyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11- (2-hydroxyethoxy carbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-methyl-11-(2-hydroxyethoxy carbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11- (3-hydroxy-propoxycarbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11-methyl-11-(3-hydroxypropoxy carbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene, 11- (4-hydroxy-butoxycarbonyl) hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . Etc.; 0 ^9,14] hex cycloheptanone decene derivatives such heptadeca-4-ene.

(D) N-phenyl-substituted imide compounds such as alicyclic olefin monomer N-phenyl- (5-norbornene-2,3-dicarboximide) having an imide group as a specific polar group;

Among these, the following monomers are particularly preferable.
Bicycloheptene derivatives such as 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxycarbonyl) bicyclo [2.2.1] hept-2-ene, and 8-hydroxycarbonyl Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (hydroxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . ^{Tetracyclododecene} derivatives such as 1 ^7,10 ] dodec-3-ene;
Bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] hexacycloheptadecene derivatives such as dodec-3-ene-8,9-dicarboxylic anhydride;

5- (2-hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (3-hydroxypropoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 8- (3 -Hydroxypropoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5- (4-hydroxybutoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxybutoxycarbonyl) tetracyclo [4.4.0 .1 ^2,5 . 1 ^7,10 ] hexacycloheptadecene derivatives such as dodec-3-ene;
N-phenyl-substituted imide compounds such as N-phenyl- (5-norbornene-2,3-dicarboximide);

Examples of the alicyclic olefin monomer having no specific polar group include the following (e) and (f).
(E) Cycloaliphatic olefin monomer having no polar group Bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept- 2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2. 1] hept-2-ene, 5-vinyl-bicyclo [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 ^2,8 ] tetradeca-3,5,7,12,11-tetraene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

(F) Alicyclic olefin monomer having a polar group other than a specific polar group Formate, acetate, propionate, butyrate, etc. of bicycloheptene derivative, tetracyclododecene derivative, hexacycloheptadecene derivative of (c) above, Groups that can be modified to a hydroxyl group, such as valates and benzoates: -OCOR ^c- bonded alicyclic olefin monomers; bicycloheptene derivatives, tetracyclododecene derivatives, hexacycloheptadecene derivatives, etc. of (c) above A group that can be modified to a carboxyl group, such as methyl ester, ethyl ester, isopropyl ester, n-butyl ester, t-butyl ester, phenyl ester, benzyl ester, and the like: an alicyclic olefin monomer to which —COOR ^c is bonded; etc. Here, R ^c represents the same meaning as described above.

Specific examples of the alicyclic olefin monomer having a polar group other than the specific polar group include 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5- And methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene.
These alicyclic olefin monomers can be used alone or in combination of two or more.

Other monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. ethylene or α-olefin having 2 to 20 carbon atoms; 1,4-hexadiene, 4-methyl Non-conjugated dienes such as -1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; and the like. These monomers can be used alone or in combination of two or more.
Some α-olefins function as molecular weight regulators described later when used for ring-opening copolymerization of alicyclic olefin monomers.

  In the ring-opening polymerization of the alicyclic olefin monomer, the molecular weight of the ring-opening polymer can be easily adjusted by adding about 0.1 to 10 mol% of the molecular weight modifier with respect to the total amount of the monomer. When the amount of the molecular weight modifier used is small, a polymer having a relatively large weight average molecular weight (Mw) is obtained, and conversely, when the amount is large, a polymer having a relatively small weight average molecular weight (Mw) is obtained.

A vinyl compound, a diene compound, etc. can be used as a molecular weight modifier.
Examples of vinyl compounds include α-olefin compounds such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene compounds such as styrene and vinyltoluene; ether compounds such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide; Examples of the diene compound include non-conjugated diene compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene. Conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene; Among these, α-olefin compounds such as 1-hexene are particularly preferable.

  Examples of the alicyclic olefin resin obtained include, for example, a ring-opening polymer of an alicyclic olefin monomer and a hydrogenated product thereof, an addition polymer of an alicyclic olefin monomer, an alicyclic olefin monomer, and Addition polymers with vinyl compounds, monocyclic cycloalkene polymers, alicyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers and hydrogenated products thereof, aromatic ring hydrogenated products of aromatic olefin polymers, etc. Is mentioned. In the present invention, these alicyclic olefin resins may be used alone or in combination of two or more.

  Among these, a ring-opening polymer of an alicyclic olefin monomer and a hydrogenated product thereof, an addition polymer of an alicyclic olefin monomer, an addition polymer of an alicyclic olefin monomer and a vinyl compound, An aromatic ring hydrogenated product of an aromatic olefin polymer is preferred, and a hydrogenated product of a ring-opened polymer of an alicyclic olefin monomer is particularly preferred.

(2) Inorganic fine particles Examples of the inorganic fine particles used in the present invention include simple metals, inorganic oxides, inorganic carbonates, inorganic sulfates, and inorganic phosphates. From the viewpoints of heat resistance and oxidation resistance, inorganic oxides are used. Are preferred, and metal oxides are particularly preferred.

  Examples of the metal oxide include silicon oxides such as colloidal silica, aerosil, and glass; aluminum oxides such as alumina; zirconium oxides such as zirconia; titanium oxides such as titania. Among these, colloidal silica, alumina, zirconia, and titania are preferable, and the use of colloidal silica is particularly preferable from the viewpoint of productivity.

The primary particle diameter of the inorganic fine particles used in the present invention is usually 1 to 200 nm, and preferably 1 to 150 nm, more preferably 5 to 100 nm, from the viewpoint of transparency and pattern formability. Further, when the primary particle diameter of the inorganic fine particles is within this range, a resin composition having a filtration rate in the range described later can be easily obtained.
Here, the primary particle diameter is measured by the BET method (specific surface area measurement method) based on the true density when it is assumed to be a true sphere.

  The amount of inorganic fine particles used can be arbitrarily selected according to the application of the resin film to be formed. For example, in the case of obtaining a transparent resin film for a display element, usually 5 to 1000 parts by weight, preferably 5 to 800 parts by weight, based on 100 parts by weight of the alicyclic olefin resin having the specific polar group described above. The amount is preferably 10 to 500 parts by weight.

(3) Solvent The solvent used in the present invention is not particularly limited as long as it contains an organic solvent (good solvent) in which the alicyclic olefin resin can be dissolved.
As the good solvent, those having a solubility of the alicyclic olefin resin at 23 ° C. of 20% by weight or more are preferable.

  The amount of good solvent used is usually 500 parts by weight or more with respect to 100 parts by weight of the alicyclic olefin resin, and from the viewpoint of obtaining desired transparency, 500 to 10,000 parts by weight is preferable, and 500 to 5 1,000 parts by weight is more preferable, and 900 to 2,000 parts by weight is particularly preferable.

  As good solvents, glycol diether compounds such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, propylene glycol methyl ethyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol mono- glycol monoether compounds such as n-butyl ether; amide compounds such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide; alicyclic ether compounds such as tetrahydrofuran; alicyclic ketone compounds such as cyclohexanone; It is done. Among these, a glycol diether compound, a glycol monoether compound, and an amide compound are preferable because of easy filtration of the resin composition.

In the resin composition of the present invention, a mixed solvent of a good solvent and a solvent other than the good solvent (poor solvent) can be used as the solvent.
Examples of the poor solvent include glycol monoether acetate compounds such as propylene glycol monomethyl ether acetate.
The use amount of the poor solvent is usually 200% by weight or less, preferably 100% by weight or less based on the good solvent because it is easy to obtain a resin film having excellent in-plane film thickness uniformity.

(4) Other components In addition to the components described above, various additives can be added to the resin composition of the present invention depending on the purpose.
Additives include photosensitizers such as quinonediazide compounds; cross-linking agents having two or more reactive groups such as amino groups, carboxyl groups, hydroxyl groups, epoxy groups, isocyanate groups, vinyl groups (preferred specific examples include methylol compounds and epoxies). Curing agents such as solid sulfonic acid compounds, amine compounds such as imidazole compounds, etc .; surfactants such as fluorine-based compounds and silicon-based compounds; antioxidants such as hindered phenol compounds An adhesion assistant such as a silane coupling agent, a sensitizer such as a phenol compound, an antistatic agent, an antifoaming agent, a dispersant, and the like.

2) Manufacturing method of resin composition Although there is no special restriction | limiting in the method of manufacturing the resin composition of this invention, From the reasons that it is excellent in operativity and the composition excellent in filterability is obtained, the said fat After preparing an alicyclic olefin resin solution (hereinafter simply referred to as “resin solution”) and an inorganic fine particle dispersion by respectively mixing a cyclic olefin resin and inorganic fine particles with an arbitrary liquid medium, It is preferable to have a step of mixing a resin solution containing an alicyclic olefin resin and a solvent and an inorganic fine particle dispersion containing the inorganic fine particles and a dispersion medium. These liquid media can be all or part of the solvent constituting the resin composition of the present invention.

As the liquid medium (solvent) used for dissolving the alicyclic olefin resin, the above-mentioned good solvents are preferable, and glycol diether compounds, glycol monoether compounds, and amide compounds are particularly preferable.
As the liquid medium (dispersion medium) used for dispersing the inorganic fine particles, the above-described solvents are preferable, and glycol monoether acetate compounds, glycol diether compounds, glycol monoether compounds, and amide compounds are particularly preferable.

  Among metal oxides, many silicon oxides are commercially available in a state of being dispersed in water or an organic dispersion medium. In the present invention, as long as it is dispersed in an organic dispersion medium, it can be used as it is for the production of a resin composition, or it can be used by exchanging the dispersion medium with another dispersion medium (dispersion medium exchange) as necessary. it can. A dispersion medium that is water can also be used after exchanging the dispersion medium.

  There is no particular limitation on the method of mixing the resin solution and the inorganic fine particle dispersion, and both the inorganic fine particle dispersion and the inorganic fine particle dispersion are added to the container at the same time. However, from the viewpoint of preventing the aggregation of fine particles, a method of adding a resin solution to the inorganic fine particle dispersion is preferable.

Although there is no particular limitation on the temperature at the time of mixing, it is generally set to a temperature at which the evaporation can be suppressed in consideration of the boiling point of the solvent in the resin composition. Therefore, the mixing temperature at normal pressure is usually 10 to 50 ° C., preferably 10 to 40 ° C., more preferably 15 to 35 ° C.
Mixing may use a container with a stirrer or a container installed on a shaker.

  The resin composition of the present invention is capable of forming a resin film having excellent in-plane film thickness uniformity, but a resin having a higher filtration rate forms a resin film having better in-plane film thickness uniformity. It is preferable because it is possible.

Here, the filtration rate is an average rate when filtration is performed using a membrane filter having a diameter of 47 mm, a pore size of 1 μm, and a porosity of 83% under normal pressure (23 ° C.) and 0.5 kgf / cm ² (gauge pressure). This rate is usually 20 g / min or more, preferably 30 g / min or more, more preferably 40 g / min or more. The resin composition having such a filtration rate gives a resin film having particularly excellent in-plane film thickness uniformity. Here, the porosity is the ratio of the pore volume to the total volume of the membrane filter including the pores.

  A resin composition having a filtration rate in the above-described range can be easily obtained by the above-described method for producing a resin composition of the present invention. Moreover, the method of adjusting the amount of solvent can also be employ | adopted as a method of adjusting the filtration rate using the same component.

3) Resin film By using the resin composition of the present invention, a resin film having a thickness of 0.1 to 200 μm can be easily formed. The resulting resin film is a thin film having excellent transparency and in-plane film thickness uniformity.

  The resin film of the present invention can be formed on a substrate having an arbitrary shape. The resin film of the present invention can be used together with the substrate, but if necessary, the resin film can be peeled off from the substrate and used alone.

  The type and material of the substrate used for forming the resin film of the present invention are not particularly limited. The substrate used may be a single layer substrate or a substrate composed of a plurality of layers. Specific examples of the substrate to be used include a substrate having wiring such as a printed wiring board and a display substrate; a flat substrate such as a glass substrate; a resin or a metal that is appropriately separated from the resin film after forming the resin film Support films and support plates; and the like.

  There is no special restriction | limiting in the method of forming a resin film on a board | substrate, For example, the method etc. which apply | coat a resin composition on a board | substrate and heat and dry the coating film of the obtained resin composition are mentioned.

  Examples of a method for applying the resin composition of the present invention on a substrate include methods such as spraying, roll coating, and spin coating.

  There is no special restriction on the temperature for heating and drying the coating film of the resin composition, and it is usually 150 to 300 ° C, preferably 200 to 250 ° C. Moreover, there is no special restriction | limiting in the time to heat and dry, for example, when using a hotplate, it is 5 to 60 minutes normally, and when using an oven, it is 30 to 90 minutes normally. When it is necessary to obtain a highly transparent resin film, it is preferable to heat in a nitrogen atmosphere.

A curing component such as a crosslinking agent may be added to the resin composition of the present invention. When the curing component is added, the resin film can be cured on the substrate by heating.
There is no particular limitation on the heating method for curing, and for example, a method of heating and drying a coating film of the resin composition of the present invention containing a curing component, followed by further heating can be mentioned. Heating for curing can be performed by a heating device such as a hot plate or an oven.

The resin film may cover the entire substrate or may partially cover the substrate surface, such as in a pattern.
Examples of a method for forming a patterned resin film on a substrate include a photolithography method using the resin body composition of the present invention to which a photosensitive agent is added.

  A specific method for forming a patterned resin film by photolithography was obtained by applying and drying (prebaking) a resin composition containing a photosensitive agent on a substrate in the same manner as described above. The resin film is irradiated with actinic radiation as necessary through a mask pattern to form a latent image pattern in the resin film, and the resin film having the latent image pattern is brought into contact with an alkali developer. A method of forming a patterned resin film on the substrate by revealing the pattern by the above method can be mentioned. Furthermore, if the patterned resin film is heated (post-baked), the patterned resin film can be cured.

The type of actinic radiation is not particularly limited, and examples thereof include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, and proton beam lines, and visible light and ultraviolet light are preferable.
The radiation dose to be irradiated can be arbitrarily set depending on the purpose of use of the transparent resin film, the thickness of the film, and the like. The pattern may be formed by irradiating actinic radiation through a mask or may be formed by direct drawing with an electron beam or the like.

The resin film of the present invention is excellent in transparency. The transparency of the resin film can be evaluated by measuring the transmittance of the resin film with a spectrophotometer.
The resin film of the present invention is excellent in in-plane film thickness uniformity. The in-plane film thickness uniformity is evaluated by measuring the in-plane film thickness under the conditions described in the examples, and evaluating the in-plane film thickness and the difference between the maximum value and the minimum value of the film thickness. It can be evaluated that the smaller this difference is, the better the in-plane film thickness uniformity is.

  The resin film of the present invention in the form of a film or pattern is excellent not only in in-plane film thickness uniformity but also in electrical characteristics such as dielectric characteristics. Accordingly, it can be used as electronic parts such as display elements, integrated circuit elements, solid-state imaging elements, and resin films for electronic parts such as display color filters, protective films, planarization films, and electrical insulating films.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by the following examples. Parts and% are based on mass unless otherwise specified.

<Evaluation method>
(1) Primary particle diameter of inorganic fine particles The average particle diameter of the inorganic fine particles is determined according to the method of JIS Z8830 using a specific surface area / pore distribution measuring device (product name “Tristar 300”, manufactured by Shimadzu Corporation). It measured by BET method (specific surface area measuring method) which calculates a surface area from the adsorption amount of nitrogen gas.

(2) Measurement of molecular weight of resin and hydrogenation rate The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were determined by measurement by gel permeation chromatography (GPC) using cyclohexane as an eluent.
The hydrogenation rate was determined by measuring the ¹ H-NMR spectrum and calculating the ratio (mol%) of the hydrogenated carbon-carbon double bond to the carbon-carbon double bond before hydrogenation.

(3) Filtration speed 100 g of a mixed solution of resin and inorganic fine particles under a pressure of 23 ° C. and 0.5 kgf / cm ² , using a filtration device (product name “LS-47V”, manufactured by Advantech), diameter 47 mm, pore diameter Filtration through a 1 μm hydrophilic polytetrafluoroethylene membrane filter (product name “H100A07A”, manufactured by Advantech, porosity 83%, mass 1.3 mg / cm ² , thickness 35 μm, water flow rate 73 ml / min · cm ² ) The average filtration rate (g / min) was determined from the filtration amount and the filtration time.
Here, the water flow rate is obtained by filtering distilled water at 25 ° C. filtered through a membrane filter having a pore diameter of 0.1 μm under a reduced pressure of −0.069 MPa, and expressing the flow rate in ml / minute per 1 cm ² .

(4) Transmittance The resin composition was rotated at a rotation speed of 16.7 rotations / second on a glass substrate (product name “1737 AMLCD”, manufactured by Corning) cut to a thickness of 0.7 mm × length 100 mm × width 100 mm. The applied coating film was dried on a hot plate at 100 ° C. for 2 minutes to obtain a resin film having a thickness of 1 to 3 μm. Next, this resin film was heated at 230 ° C. for 1 hour in a clean oven under a nitrogen atmosphere.

  The transmittance of the resin film thus formed was measured with a spectrophotometer. The transmittance was calculated by converting the film thickness to 2 μm and calculating the total light transmittance so that each could be compared. The greater this value, the better the transparency.

(5) Uniform in-plane film thickness A chromium-deposited glass substrate was prepared by depositing chromium in a thickness of 2000 mm on a glass substrate (manufactured by Corning) having a thickness of 0.7 mm × length of 650 mm × width of 550 mm. The chrome-deposited glass substrate was spin-coated at a rotation speed of 16.7 rev / sec. The obtained coating film was dried on a hot plate at 100 ° C. for 2 minutes in a nitrogen atmosphere to obtain a thickness of 1. A 5 μm resin film was obtained.

  The film thickness at 121 points in the surface of the obtained resin film was measured with an optical film thickness meter (product name “Nanometrics Nanospec M6500”, manufactured by Nanometrics Japan). The measurement point was an intersection when a glass substrate of 650 mm × 550 mm was divided into 12 parts in length and width. Based on the film thickness at this measurement point, the value calculated by the following formula was defined as the in-plane film thickness uniformity. The smaller this value, the better the in-plane film thickness uniformity of the resin film.

<Synthesis Example 1>
8-hydroxycarbonyltetracyclododecene 60 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 40 parts, 1-hexene 1.3 parts, (1,3-dimethylimidazolidine-2- Iridene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (0.05 parts) and tetrahydrofuran (400 parts) were charged into a nitrogen-substituted glass pressure-resistant reactor and reacted at 70 ° C. for 2 hours with stirring to obtain a resin solution (a) ( Solid content concentration: about 20%) was obtained.
This resin solution (a) was transferred into an autoclave equipped with a stirrer, and reacted at a hydrogen pressure of 4 MPa and a temperature of 150 ° C. for 5 hours to contain a hydrogenated resin (hydrogenation rate 99%) (resin solution (b) (solid Partial concentration: about 20%).

  Next, 100 parts of the resin solution (b) and 1 part of activated carbon powder were placed in a heat-resistant autoclave and reacted at a hydrogen pressure of 4 MPa and a temperature of 150 ° C. for 3 hours. After completion of the reaction, the reaction solution was filtered through a fluororesin filter having a pore size of 0.2 μm to separate activated carbon to obtain a resin solution (c). At this time, filtration could be performed without any delay.

  Next, the resin solution (c) was poured into ethyl alcohol, and the produced crumb was dried to obtain a resin (1). Resin (1) had a polyisoprene equivalent Mw of 5,500 and Mn of 3,200. The hydrogenation rate was 99%.

<Synthesis Example 2>
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 100 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts, and cyclohexane 400 parts. Then, it was charged into a nitrogen-substituted glass pressure-resistant reactor and subjected to a polymerization reaction and a hydrogenation reaction in the same manner as in Synthesis Example 1 to obtain a resin (A). Resin (A) had Mw of 5,300 and Mn of 3,200. The hydrogenation rate was 99%.

  Next, 100 parts of the resin (A) obtained above, 100 parts of N-methylpyrrolidone, 500 parts of propylene glycol, and 84.5 parts of 85% potassium hydroxide were charged into the reactor, and the whole volume was kept at 190 ° C. for 4.5 hours. Stir with heating. The obtained reaction solution was poured into a large amount of a mixed solution of water, tetrahydrofuran and hydrochloric acid to coagulate the hydrolyzate. The coagulated polymer was washed with water and dried to obtain a hydrolyzed resin (2). The hydrolysis rate of the resin (2) was 95%.

<Synthesis Example 3>
5- (2-hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-2-ene 100 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidin-2-ylidene (tricyclohexylphosphine) benzylidene 0.05 parts of ruthenium dichloride and 400 parts of tetrahydrofuran were charged into a nitrogen-substituted glass pressure-resistant reactor, and a polymerization reaction and a hydrogenation reaction were performed in the same manner as in Synthesis Example 1 to obtain a resin (3). Resin (3) had Mw of 5,500 and Mn of 3,300. The hydrogenation rate was 99%.

<Synthesis Example 4>
8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene 100 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts, and cyclohexane 400 parts Then, it was charged into a nitrogen-substituted glass pressure-resistant reactor and subjected to a polymerization reaction and a hydrogenation reaction in the same manner as in Synthesis Example 1 to obtain a resin (B). Resin (B) had Mw of 5,500 and Mn of 3,200. The hydrogenation rate was 99%.

<Example 1>
30 parts of the resin (1) obtained in Synthesis Example 1 was mixed with 120 parts of propylene glycol ethyl methyl ether (EDM) and dissolved, and then filtered through a fluororesin membrane filter having a pore size of 1.0 μm. A 20% resin solution (1) was prepared.
50 parts of EDM in 100 parts of organosilica sol (product name “PMA-ST”, manufactured by Nissan Chemical Industries; dispersion medium = propylene glycol monomethyl ether acetate (PGMEA), solid content concentration = 30%), which is a surface-treated colloidal silica) Was added and stirred to prepare a silica sol dispersion (1) having a silica sol concentration of 20%. The primary particle diameter of the silica sol particles in this dispersion (1) was about 20 nm.
150 parts of the silica sol dispersion (1) and 150 parts of the resin solution (1) are mixed, and 0.1 parts of a silicon-based surfactant (product name “KP-341”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added thereto. After mixing and dissolving, the mixture was further stirred for 30 minutes to obtain a resin composition (1). For the resin composition (1), the filtration rate was measured, and the transparency and in-plane film thickness uniformity were evaluated.

<Example 2>
Silica sol is prepared by adding 20 parts of propylene glycol ethyl methyl ether (EDM) and 30 parts of propylene glycol monomethyl ether acetate (PGMEA) to 100 parts of organosilica sol (product name “PMA-ST”, manufactured by Nissan Chemical Co., Ltd.). Dispersion liquid (2) was prepared. The primary particle diameter of the silica sol particles in this dispersion (2) was about 20 nm.
150 parts of the silica sol dispersion (2) and 150 parts of the resin solution (1) are mixed, and 0.1 parts of a silicon-based surfactant (product name “KP-341”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added thereto. After mixing and dissolving, the mixture was further stirred for 30 minutes to obtain a resin composition (2). For the resin composition (2), filtration rate measurement, transparency, and in-plane film thickness uniformity were evaluated.

<Example 3>
30 parts of the resin (1) obtained in Synthesis Example 1 was mixed with 120 parts of N-methyl-2-pyrrolidone (NMP) and dissolved, and then filtered through a fluororesin membrane filter having a pore size of 1.0 μm. A resin solution (2) having a concentration of 20% was prepared.
Organosilica sol (product name “PMA-ST”, manufactured by Nissan Chemical Industries, Ltd .; dispersion medium = propylene glycol monomethyl ether acetate (PGMEA), solid content concentration = 30%) 100 parts of NMP is added and stirred, and the silica sol concentration A 20% silica sol dispersion (3) was prepared. The primary particle diameter of the silica sol particles in this dispersion (3) was about 20 nm.
A resin composition (3) was prepared in the same manner as in Example 1, except that the resin solution (1) was changed to the resin solution (2) and the silica sol dispersion (1) was changed to the silica sol dispersion (3). did. The resin composition (3) was measured for filtration rate, transparency, and in-plane film thickness uniformity.

<Example 4>
30 parts of the resin (1) obtained in Synthesis Example 1 was mixed with 120 parts of propylene glycol monoethyl ether (PGEE) and dissolved, and then filtered through a fluororesin membrane filter having a pore size of 1.0 μm. A 20% resin solution (3) was prepared.
Organosilica sol (product name “PMA-ST”, manufactured by Nissan Chemical Industries; dispersion medium = propylene glycol monomethyl ether acetate (PGMEA), solid content concentration = 30%) A 20% silica sol dispersion (4) was prepared. The primary particle diameter of the silica sol particles in this dispersion (4) was about 20 nm.
A resin composition (4) was prepared in the same manner as in Example 1, except that the resin solution (1) was changed to the resin solution (3) and the silica sol dispersion (1) was changed to the silica sol dispersion (4). did. For the resin composition (4), filtration rate measurement, transparency, and in-plane film thickness uniformity were evaluated.

<Example 5>
30 parts of the resin (2) obtained in Synthesis Example 2 and 120 parts of propylene glycol ethyl methyl ether (EDM) as a solvent were mixed and dissolved, and then filtered through a membrane filter having a pore size of 1.0 μm. A 20% resin solution (4) was prepared. A resin composition (5) was prepared in the same manner as in Example 1, except that the resin solution (1) was changed to the resin solution (4). For the resin composition (5), filtration rate measurement, transparency, and in-plane film thickness uniformity were evaluated.

<Example 6>
30 parts of the resin (3) obtained in Synthesis Example 3 and 120 parts of propylene glycol ethyl methyl ether (EDM) as a solvent were mixed and dissolved, and then filtered through a membrane filter having a pore size of 1.0 μm. A 20% resin solution (5) was prepared. A resin composition (6) was prepared in the same manner as in Example 1, except that the resin solution (1) was changed to the resin solution (5). For the resin composition (6), filtration rate measurement, transparency, and in-plane film thickness uniformity were evaluated.

<Comparative Example 1>
30 parts of the resin (A) obtained in Synthesis Example 2 and 120 parts of cyclohexane (CH) as a solvent were mixed and dissolved, and then filtered through a membrane filter having a pore size of 1.0 μm to obtain a resin solution having a resin concentration of 20%. (6) was prepared.
Silica sol dispersion (5) was prepared by adding 50 parts of cyclohexane (CH) to 100 parts of organosilica sol (product name “PMA-ST”, manufactured by Nissan Chemical Co., Ltd.). The primary particle diameter of the silica sol particles in this dispersion (5) was about 20 nm.
150 parts of this silica sol dispersion (5) and 150 parts of the resin solution (6) were mixed to prepare a resin composition (7). The resin composition (7) was measured for filtration rate, transparency, and in-plane film thickness uniformity.

<Comparative example 2>
30 parts of the resin (B) obtained in Synthesis Example 4 and 120 parts of cyclohexane (CH) as a solvent were mixed and dissolved, and then filtered through a membrane filter having a pore size of 1.0 μm to obtain a resin solution having a resin concentration of 20%. (7) was prepared.
150 parts of the silica sol dispersion (5) obtained in Comparative Example 1 and 150 parts of the resin solution (7) were mixed to prepare a resin composition (8). The resin composition (8) was not a uniform solution because fine particles were precipitated.
The results of the above examples and comparative examples are summarized in Table 1 below.

第１表より、特定極性基を有する脂環式オレフィン樹脂を用いた実施例１〜６の樹脂組成物は、透明性、面内膜厚均一性に優れた樹脂膜を形成できることがわかる。特に、ろ過速度が速い樹脂組成物を用いると、面内膜厚均一性により優れた樹脂膜の得られることがわかる。

From Table 1, it can be seen that the resin compositions of Examples 1 to 6 using the alicyclic olefin resin having a specific polar group can form a resin film excellent in transparency and in-plane film thickness uniformity. In particular, it can be seen that when a resin composition having a high filtration rate is used, a resin film superior in in-plane film thickness uniformity can be obtained.

  The resin composition of the present invention contains an alicyclic olefin resin having a specific polar group, inorganic fine particles, and a solvent, is excellent in filterability, and has both excellent transparency and in-plane film thickness uniformity. It is useful as a film forming material.

The resin film of the present invention is excellent in electrical characteristics such as transparency, in-plane film thickness uniformity, and dielectric characteristics. Therefore, it can be used as a resin film for electronic parts such as electronic parts such as display elements, integrated circuit elements, solid-state imaging elements, and color filters for display, protective films, planarization films, and electrical insulating films.

Claims (8)

A hydrogenated product of a ring-opening polymer of an alicyclic olefin monomer having at least one selected from the group consisting of a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group and an imide group, inorganic fine particles, and , A solvent consisting of at least one selected from the group consisting of a glycol diether compound, a glycol monoether compound and an amide compound, with respect to 100 parts by weight of the hydrogenated product of the ring-opening polymer of the alicyclic olefin monomer, A resin composition comprising 500 parts by weight or more . The hydrogenated product of the ring-opening polymer of the alicyclic olefin monomer has the formula (I)

[Wherein, R ^{1 to} R ⁴ are each independently a hydrogen atom or a formula: —X _n —R (X is a divalent group, n is 0 or 1, and R is a substituent. An optionally substituted alkyl group having 1 to 7 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, an aromatic group, a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group, Or an imide group), wherein one or more of R ^{1 to} R ⁴ have the formula: —X _n —R ^a (wherein X and n represent the same meaning as described above, R ^a is a carboxyl group, a dicarboxylic anhydride group, a hydroxyl group or an imide group. m is an integer of 0-2. The resin composition according to claim 1, wherein the resin has a repeating unit represented by the formula:   The resin composition according to claim 1, wherein the inorganic fine particles have a primary particle diameter of 1 to 200 nm.   The resin composition according to claim 1, wherein the inorganic fine particle is a metal oxide. A step of mixing a resin solution containing a hydrogenated product of a ring-opening polymer of the alicyclic olefin monomer and a solvent, and an inorganic fine particle dispersion containing the inorganic fine particles and a dispersion medium. The manufacturing method of the resin composition of Claim 1 to do. The method for producing a resin composition according to claim 5 , wherein the solvent is at least one selected from the group consisting of a glycol diether compound, a glycol monoether compound, and an amide compound. The method for producing a resin composition according to claim 5 or 6 , wherein the dispersion medium is at least one selected from the group consisting of a glycol ether acetate compound, a glycol diether compound, a glycol monoether compound, and an amide compound. A resin film having a thickness of 0.1 to 200 μm, formed using the resin composition according to claim 1 .