KR20220029569A - Resin composition, electronic component, and manufacturing method of resin film - Google Patents

Abstract

It is a resin composition containing a polymer (A) and the crosslinking agent (B) containing the compound represented by following formula (1). Here, the polymer (A) contains the cyclic olefin polymer (A-1) having a protonic polar group, and the occupancy ratio of the monomer unit having a protonic polar group is 51 mol% or more, and has a protonic polar group At least one of those containing polyamideimide resin (A-2) is satisfied. In Formula (1), some R represents any one of an alkyl group and an alkoxy group, some R< ¹ > represents any one of a hydrogen atom, an alkyl group, and an alkoxy group, m-q are 0-4 represents the integer of each.

Description

Resin composition, electronic component, and manufacturing method of resin film

The present invention relates to a resin composition, an electronic component, and a method for producing a resin film. In particular, the present invention relates to a resin composition that can be suitably used for formation of an insulating film used for electronic parts, an electronic part provided with a resin film made of the resin composition, and a manufacturing method for manufacturing such a resin film.

Various resin films are formed as a planarization film, a protective film, an insulating film, etc. in electronic components, such as a liquid crystal display device, an organic electroluminescent display device, an integrated circuit element, and a solid-state image sensor.

For example, in Patent Document 1, as a photosensitive resin composition used to form a permanent film, it contains a polymer having a cyclic olefin structural unit, and PED (Post Exposure Delay) measured under specific conditions is 10% or less, The photosensitive resin composition whose swelling ratio measured by specific conditions (B) is 20 % or less is proposed. When the photosensitive resin composition concerning patent document 1 is used for manufacture of the electronic device provided with a permanent film, manufacture stability can be improved. Moreover, the photosensitive resin composition which concerns on patent document 1 can optionally contain crosslinking agents, such as an epoxy compound.

Further, in Patent Document 2, as a photosensitive resin composition used to form a sacrificial film, it contains a predetermined alkali-soluble resin and a photosensitizer, and heat-treats the photosensitive resin composition at 115° C. for 3 minutes to form a resin film. When it does, the photosensitive resin composition from which the static contact angle of water with respect to a resin film becomes 76 degrees or more and 95 degrees or less is proposed. Moreover, the photosensitive resin composition which concerns on patent document 2 can optionally contain crosslinking agents, such as an epoxy compound.

International Publication No. 2015/141525 Japanese Patent Laid-Open No. 2017-111447

In recent years, in order to improve the performance of an ITO (Indium Tin Oxide) electrode, which is one kind of transparent electrode applied for various purposes, improvement is in progress. Here, in order to improve the performance of the ITO electrode, it is preferable that there is no or few wrinkles in the ITO film provided in the ITO electrode. When the ITO film is wrinkled, the light transmittance of the laminate is deteriorated, and there is a possibility that the performance of the ITO electrode may be deteriorated. Therefore, it is preferable that the resin film formed adjacent to or adjacent to the ITO film can exhibit the performance of suppressing the occurrence of wrinkles on the surface of the ITO film when the ITO film is formed on the surface. Hereinafter, in this specification, the performance "to suppress that a wrinkle arises on the surface of an ITO film|membrane" is called "ITO wrinkle suppression performance."

In addition, in forming a resin film using a resin composition, in general, several chemical|medical solutions are used. If the resin film has suitable resistance to such a chemical, that is, chemical resistance, it becomes possible to form a resin film as designed. Therefore, it is calculated|required that the resin film is excellent in chemical-resistance.

Moreover, in recent years, in the process of forming an ITO film at the time of forming an ITO electrode, in order to obtain the ITO film which can show the outstanding performance, forming an ITO film into a film and heating under high-temperature conditions are examined. Accordingly, it is required for the resin film to have little film loss under high-temperature conditions, that is, to be excellent in heat resistance.

Thus, in recent years, it is calculated|required by the resin film that it is excellent in all of "ITO wrinkle suppression performance", "chemical-resistance", and "heat resistance". However, the resin film formed using the said conventional resin composition had room for improvement in that these attributes were improved in a good balance.

Then, this invention aims at providing the resin composition which can form the resin film excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance.

Moreover, this invention aims at providing the high-performance electronic component provided with the resin film formed using the resin composition of this invention.

Moreover, an object of this invention is to provide the manufacturing method of the resin film which can manufacture efficiently the resin film of this invention using the resin composition of this invention.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined for the purpose of solving the said subject. And, the present inventors, according to the resin composition containing a polymer (A) having a protonic polar group and a predetermined crosslinking agent (B) satisfying a predetermined composition, a resin excellent in ITO wrinkle suppression performance, chemical resistance, and heat resistance It found that it became possible to form a film|membrane, and completed this invention.

That is, this invention aims at solving the said subject advantageously, The resin composition of this invention contains the polymer (A) which has a protonic polar group, and the compound represented by following formula (1) A crosslinking agent A resin composition containing (B), wherein the polymer (A) having a protonic polar group contains the cyclic olefin polymer (A-1) having a protonic polar group, and occupancy of a monomer unit having a protonic polar group It is characterized by satisfying at least one of a ratio of 51 mol% or more and a polyamideimide resin (A-2) having a protonic polar group.

[Formula 1]

[In formula (1), a plurality of Rs each independently represent any one of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and a plurality of R ¹ are each independently a hydrogen atom; represents either an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m, n, p, and q represent an integer of 0 to 4, respectively.]

As described above, when a predetermined polymer having a protonic polar group (A) and a crosslinking agent (B) satisfying the above predetermined structure are contained in the resin composition, a resin film excellent in ITO wrinkle suppression performance, chemical resistance, and heat resistance is formed it becomes possible to

Here, it is preferable that the resin composition of this invention further contains a phenol type antioxidant (C). When the resin composition further contains a phenolic antioxidant (C), the light transmittance of the resin film obtained can be improved.

Moreover, in the resin composition of this invention, it is preferable that content of the said phenolic antioxidant (C) with respect to 100 mass parts of polymers (A) which has the said protonic polar group is 0.3 mass part or more and 15 mass parts or less. When the content of the antioxidant (C) with respect to the polymer (A) is within the above range, the light transmittance of the obtained resin film can be further improved, and the ITO wrinkle suppression performance can be further improved, and the antioxidant ( It can suppress that C) becomes easy to bleed out.

Moreover, in the resin composition of this invention, it is preferable that the said polymer (A) which has a protonic polar group is a cyclic olefin polymer which has a carboxyl group. By containing the cyclic olefin polymer which has a carboxyl group in a resin composition, the ITO wrinkle suppression performance of the resin film obtained can be improved further.

Further, in the resin composition of the present invention, the polymer (A) having a protonic polar group is the cyclic olefin polymer (A-1) having a protonic polar group, and the cyclic olefin polymer having a protonic polar group ( It is preferable that A-1) is a ring-opened polymer. When the polymer (A) which has a protonic polar group is a ring-opening polymer, the processability of the resin film obtained can be improved.

Moreover, in the resin composition of this invention, it is preferable that content of the said crosslinking agent (B) with respect to 100 mass parts of polymer (A) which has the said protonic polar group is 5 mass parts or more and 160 mass parts or less. ITO wrinkle suppression performance of the resin film obtained as content of a crosslinking agent (B) is in the said predetermined range, chemical-resistance, and light transmittance can be improved.

Moreover, it is preferable that the resin composition of this invention contains at least one further among the compound which has two or more alkoxymethyl groups, and the compound which has two or more methylol groups. When the resin composition further contains at least one of a compound having two or more alkoxymethyl groups and a compound having two or more methylol groups, the chemical resistance of the resulting resin film can be further improved.

Moreover, the resin composition of this invention may contain the radiation sensitive compound (D) further. When the resin composition contains the radiation-sensitive compound (D), the resin film having a desired pattern can be favorably formed by patterning the resin film. Here, it is preferable that the said radiation sensitive compound (D) is a quinonediazide compound.

Moreover, this invention aims at solving the said subject advantageously, The electronic component of this invention is equipped with the resin film which consists of any one of the resin compositions mentioned above, It is characterized by the above-mentioned. Since the resin film formed using the resin composition mentioned above is excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance, since the electronic component provided with the said resin film can fully exhibit the desired function, it is high performance.

Moreover, this invention aims to solve the said subject advantageously, and the manufacturing method of the resin film of this invention includes the process of heating the coating film formed using the resin composition at 100 degreeC or more, It characterized by the above-mentioned do. By heating the coating film formed using any one of the resin compositions mentioned above at 100 degreeC or more efficiently, the resin film excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance can be manufactured.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the resin film excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance can be provided.

Moreover, according to this invention, the high-performance electronic component provided with the resin film formed using the resin composition of this invention can be provided.

Moreover, according to this invention, the manufacturing method of the resin film which can manufacture efficiently the resin film of this invention using the resin composition of this invention can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. The resin composition of this invention can be used for formation of a resin film. And, such a resin film may be suitably provided for an electronic component having an ITO electrode. And the electronic component of this invention is equipped with the resin film obtained using the resin composition of this invention. Moreover, such a resin film can be efficiently manufactured according to the manufacturing method of the resin film of this invention using the resin composition of this invention.

(resin composition)

The resin composition of the present invention is characterized in that it contains a polymer (A) having a protonic polar group that satisfies predetermined conditions described later, and a crosslinking agent (B) containing a compound represented by the following formula (1).

[Formula 2]

[In formula (1), a plurality of Rs each independently represent any one of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and a plurality of R ¹ are each independently a hydrogen atom; represents either an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m, n, p, and q represent an integer of 0 to 4, respectively.]

In addition, the resin composition of the present invention optionally further contains at least one of a phenolic antioxidant (C), a compound having two or more alkoxymethyl groups, and a compound having two or more methylol groups, and other additives. can do.

On the other hand, since the resin composition of the present invention contains a polymer (A) having a protonic polar group that satisfies a predetermined condition, and a crosslinking agent (B) that satisfies the predetermined structure, ITO wrinkle suppression performance, chemical resistance , and excellent heat resistance. This is because, in the resin film, the presence of a crosslinked structure in which a protonic polar group contained in the polymer (A) is crosslinked with a crosslinking agent (B), which satisfies a predetermined condition, increases the glass transition temperature of the resin film; It is presumed that this is because it contributes to enhancing the elastic modulus of the resin film in a high-temperature environment, increasing the tensile strength of the resin film in a high-temperature environment, and suppressing the tendency of the resin film to swell excessively when immersed in a chemical.

<Polymer (A) having a protonic polar group>

The polymer (A) having a protonic polar group contains the cyclic olefin polymer (A-1) having a protonic polar group, and the occupancy ratio of the monomer unit having a protonic polar group is 51 mol% or more, and protons It is characterized in that at least one of those containing polyamideimide resin (A-2) having a polar group is satisfied.

The polymer (A) which has a protonic polar group is a polymer formed by couple|bonding a protonic polar group with respect to the structure used as frame|skeleton. Here, the "protonic polar group" refers to a group containing an atom in which hydrogen is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. The atom to which hydrogen is directly bonded is preferably an atom belonging to the second or third period of Group 15 or 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, particularly preferably It is an oxygen atom.

Specific examples of the protonic polar group include polar groups having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a polar group having a nitrogen atom, such as a primary amino group, a secondary amino group, a primary amide group, and a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; and the like. Among these, it is preferable to have an oxygen atom, More preferably, it is a carboxyl group.

In this invention, there is no limitation in particular in the number of the protonic polar groups couple|bonded with the polymer (A) which has a protonic polar group, Furthermore, different types of protonic polar groups may be contained.

The skeleton of the polymer (A) having a protonic polar group is either (1) a polymer having a cyclic structure (alicyclic or aromatic ring) derived from a cyclic olefin monomer in the main chain, and (2) polyamideimide. On the other hand, even if it is a polymer having an amide bond and an imide bond in the repeating unit and can be referred to as a so-called "polyamide-imide resin," the polymer having a cyclic structure derived from a cyclic olefin monomer in the main chain is the above (1) It corresponds to "a polymer having a cyclic structure (alicyclic or aromatic ring) derived from a cyclic olefin monomer in its main chain" described in

In addition, from the viewpoint of further enhancing the ITO wrinkle suppression performance of the obtained resin film, as the polymer (A) having a protonic polar group, the skeleton is (1) in the main chain, a cyclic structure derived from a cyclic olefin monomer (alicyclic or aromatic It is preferable that at least a polymer having a ring) is used, in other words, the polymer (A) having a protonic polar group contains at least a cyclic olefin polymer. Hereinafter, as the polymer (A) having a protonic polar group, the cyclic olefin polymer is referred to as "cyclic olefin polymer (A-1)", and the polyamideimide resin having a protonic polar group is referred to as "polyamideimide resin (A)" -2)” is sometimes called. In addition, as a polymer (A) which has a protonic polar group, 1 type of polymer may be used independently and may be used combining multiple types of polymers. More specifically, as the polymer (A) having a protonic polar group, one or more types of cyclic olefin polymers (A-1) or one or more types of polyamideimide resins (A-2) are used, respectively. Alternatively, one or more types of cyclic olefin polymers (A-1) and one or more types of polyamideimide resins (A-2) may be used in combination. Among them, as described above, the polymer (A) having a protonic polar group preferably contains at least a cyclic olefin polymer (A-1), and the polymer (A) having a protonic polar group is a cyclic olefin polymer ( It is more preferable that it is A-1).

<<Cyclic Olefin Polymer (A-1)>>

Examples of the cyclic olefin polymer (A-1) include a polymer of one or two or more cyclic olefin monomers, or a copolymer of one or two or more cyclic olefin monomers and a monomer copolymerizable therewith. In this case, it is preferable to use the cyclic olefin monomer (a) which has a protonic polar group at least as a monomer for forming a cyclic olefin polymer (A-1).

The cyclic olefin monomer (a) having a protonic polar group (hereinafter also simply referred to as “cyclic olefin monomer (a)”) is not particularly limited, and the cyclic olefin monomer (a) having a protonic polar group (a) ) (hereinafter referred to as "monomer (a)" as appropriate.) As a specific example, 2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-hydroxycarbo Nylbicyclo[2.2.1]hepto-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2,3-dihydroxycarbonylbicyclo[2.2 .1]hepto-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 3-methyl-2-hydroxycarbonylbicyclo[2.2 .1]hepto-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyltricyclo[5.2.1.0 ^2,6 ] Deca-3,8-diene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo[6.2 .1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4 -Carboxymethyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, N-(hydroxycarbonylmethyl)bicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylpentyl) )bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(dihydroxycarbonylethyl)bicyclo[2.2.1]hepto-5-ene-2,3-di Carboxyimide, N-(dihydroxycarbonylpropyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylphenethyl)bicyclo[2.2.1 ]hepto-5-ene-2,3-dicarboxyimide, N-(2-(4-hydroxyphenyl)-1-(hydroxycarbonyl)ethyl)bicyclo[2.2.1]hepto-5-ene -2,3-dicarboxyimide, N- carboxyl group-containing cyclic olefins such as (hydroxycarbonylphenyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide; 2-(4-hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(4-hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene, 4- (4-hydroxyphenyl)tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-methyl-4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^{3, 6.0 2,7} ]dodeca-9-ene, 2-hydroxybicyclo[2.2.1]hepto-5-ene, 2-hydroxymethylbicyclo[2.2.1]hepto-5-ene, 2 -Hydroxyethylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hepto-5-ene, 2,3-dihydroxymethylbicyclo[ 2.2.1]hepto-5-ene, 2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(hydroxyethoxycarbonyl)bicyclo[ 2.2.1]hepto-5-ene, 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)bicyclo[2.2.1]hepto-5-ene, 2 -(2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl)bicyclo[2.2.1]hepto-5-ene, 3-hydroxytricyclo[5.2.1.0 ^{2, 6} ]deca-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0 ^2,6 ]deca-4,8-diene, 4-hydroxytetracyclo[6.2.1.1 ^{3,6.0 2, 7} ]dodeca-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4- Methyl-4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, N-(hydroxyethyl)bicyclo[2.2.1]hepto- and hydroxyl group-containing cyclic olefins such as 5-ene-2,3-dicarboxyimide and N-(hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide. there is. Among them, from the viewpoint of further enhancing the ITO wrinkle suppression performance of the resulting resin film, a carboxyl group-containing cyclic olefin is preferable, and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca- 9-ene is particularly preferred. In addition, as a cyclic olefin monomer (a), 1 type or multiple types of monomers can be used.

The content rate of the unit derived from the cyclic olefin monomer (a) in the cyclic olefin polymer (A-1) is 100 mol% of all repeating units constituting the cyclic olefin polymer (A-1), , 51 mol% or more is preferable, 55 mol% or more is more preferable, 99 mol% or less is preferable, 90 mol% or less is more preferable, 80 mol% or less is still more preferable, and 75 mol% or less is more more preferably In addition, the content rate of the unit derived from the said cyclic olefin monomer (a) may be 100 mol%. By making the content rate of the unit derived from a cyclic olefin monomer (a) into the said range, the ITO wrinkle suppression performance of the resin film obtained, chemical-resistance, and heat resistance can be improved still more with good balance.

In addition, the cyclic olefin polymer (A-1) used by this invention may be a copolymer obtained by copolymerizing the cyclic olefin monomer (a) which has a protonic polar group, and this and the monomer (b) copolymerizable. As such a copolymerizable monomer, a cyclic olefin monomer having a polar group other than a protonic polar group (b1), a cyclic olefin monomer having no polar group (b2), and a monomer other than a cyclic olefin (b3) (hereinafter, appropriately “ Monomer (b1)", "monomer (b2)", and "monomer (b3).") are mentioned. Here, the monomers (b1) to (b3) can be used in a range that does not affect the properties. And, it is preferable that the cyclic olefin polymer (A-1) is comprised from a monomer (a) and a monomer (b1). Further, among the monomers (b1) listed below, N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3- which is a cyclic olefin having an N-substituted imide group. Preference is given to using dicarboxyimides.

Specific examples of the polar group other than the protonic polar group of the cyclic olefin monomer (b1) having a polar group other than the protonic polar group include an ester group (the alkoxycarbonyl group and the aryloxycarbonyl group are generically referred to.), N-substituted imine and an epoxy group, a halogen atom, a cyano group, a carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid), an alkoxy group, a carbonyl group, a tertiary amino group, a sulfone group, and an acryloyl group. Among them, as the polar group other than the protonic polar group, an ester group, an N-substituted imide group, and a cyano group are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable. .

In addition, the following cyclic olefins are mentioned as a specific example of a monomer (b1).

Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo[2.2.1]hepto-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5 -Methyl-5-methoxycarbonylbicyclo[2.2.1]hepto-2-ene, 9-acetoxytetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9- Methoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-ethoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca- 4-ene, 9-n-propoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-isopropoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, 9-n-butoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl-9-meth Toxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl-9-isopropoxy carbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl -9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene etc. are mentioned.

Examples of the cyclic olefin having an N-substituted imide group include N-phenylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-ethylhexyl)- 1-Isopropyl-4-methylbicyclo[2.2.2]octo-5-ene-2,3-dicarboxyimide, N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene -2,3-dicarboxyimide, N-[(2-ethylbutoxy)ethoxypropyl]-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(endo- and bicyclo[2.2.1]hepto-5-ene-2,3-diyldicarbonyl)dimethyl aspartate.

Examples of the cyclic olefin having a cyano group include 9-cyanotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 5-cyanobicyclo[2.2.1]hepto-2-ene, and the like.

Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methyl-9-chlorotetracyclo[6.2 .1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene and the like.

The cyclic olefin monomer (b1) which has polar groups other than these protonic polar groups may be used individually, respectively, and may be used in combination of 2 or more type.

Specific examples of the cyclic olefin monomer (b2) having no polar group include bicyclo[2.2.1]hepto-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo[2.2.1 ]hepto-2-ene, 5-butyl-bicyclo[2.2.1]hepto-2-ene, 5-ethylidene-bicyclo[2.2.1]hepto-2-ene, 5-methylidene-bicyclo[ 2.2.1]hepto-2-ene, 5-vinyl-bicyclo[2.2.1]hepto-2-ene, tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common name: dicyclopenta diene), tetracyclo[10.2.1.0 ^2,11 0 ^4,9 ]pentadeca-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4 -ene (also called "tetracyclododecene"), 9-methyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-ethyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methylidene-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, 9-vinyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-propenyl -tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^4,8 ]pentadeca-5,12- diene, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, tetracyclo[9.2.1.0 ^2,10 0.0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^4,8 ]pentadeca-12-ene, and the like.

The cyclic olefin monomer (b2) which does not have these polar groups may be used individually, respectively, and may be used in combination of 2 or more type.

Specific examples of the monomer (b3) other than the cyclic olefin include a chain olefin. Examples of the chain olefin 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- ?-olefins having 2 to 20 carbon atoms, such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene.

Monomers (b3) other than these cyclic olefins can be used individually or in combination of 2 or more types, respectively.

The cyclic olefin polymer (A-1) is obtained by homopolymerizing the cyclic olefin monomer (a) or by polymerization with one or more monomers selected from monomers (b1) to (b3) as desired. The polymerization method is not particularly limited, and any polymerization method can be employed. Especially, it is preferable to employ|adopt the ring-opening polymerization method. As the polymer (A) having a protonic polar group, if the cyclic olefin polymer (A-1) is a ring-opened polymer, the workability of the resulting resin film can be improved. More specifically, it is preferable that the cyclic olefin polymer (A-1) is a ring-opened polymer including a structure according to the following formula (RO-COP).

[Formula 3]

[In the formula (RO-COP), R ¹ and R ² represent hydrogen or a group or structure corresponding to each of the monomers (a), (b1) and (b2) described above. On the other hand, R ¹ and R ² may form a ring structure together.]

Moreover, you may further hydrogenate the polymer obtained by superposition|polymerization. In this specification, the hydrogenated polymer shall also be contained in the cyclic olefin polymer (A-1) which has a protonic polar group. On the other hand, when the cyclic olefin polymer (A-1) is a hydrogenated polymer, it is preferable that 95.0% or more of the carbon-carbon double bonds contained in the main chain and other than the main chain are hydrogenated, and 97.0% or more. It is more preferable that it is a polymer formed by hydrogenation, and it is still more preferable that it is a polymer formed by hydrogenation of 99.0% or more.

Cyclic olefin polymer (A-1) can also be obtained by the method of introduce|transducing a protonic polar group into a cyclic olefin polymer which does not have a protonic polar group using a well-known modifier, and performing hydrogenation if desired. Here, you may perform hydrogenation with respect to the polymer before introduction of a protonic polar group.

Further, the cyclic olefin polymer (A-1) may be obtained by a method of further introducing a protonic polar group into the cyclic olefin polymer having a protonic polar group.

On the other hand, when the cyclic olefin polymer (A-1) is a polymer obtained by hydrogenating a ring-opened polymer having a structure according to the formula (RO-COP), the cyclic olefin polymer (A-1) is It is preferred to include a structure according to the formula.

[Formula 4]

[In the formula, R ¹ and R ² represent hydrogen or a group or structure corresponding to each of the above monomers (a), (b1) and (b2), or a hydride thereof. On the other hand, R ¹ and R ² may form a ring structure together.]

[Ratio of Occupational Ratio of Monomer Units Having Protonic Polar Group in Polymer (A-1)]

When the occupancy ratio of the monomer unit having a protonic polar group in the polymer (A-1) is 51 mol% or more, the reaction between the crosslinking agent (B) and the protonic polar group occurs at a sufficient frequency, and at a sufficient frequency Since a crosslinked structure is formed, the ITO wrinkle suppression performance of the resin film obtained, chemical-resistance, and heat resistance can be improved with good balance. Moreover, it is preferable that the occupation ratio of the monomeric unit which has a protonic polar group in polymer (A-1) is 55 mol% or more, It is preferable that it is 100 mol% or less, It is more preferable that it is 80 mol% or less, 75 It is more preferable that it is mol% or less. If the occupancy ratio of the monomer unit having a protonic polar group in the polymer (A-1) is 55 mol% or more, the ITO wrinkle suppression performance, chemical resistance, and heat resistance of the resulting resin film can be improved in a more balanced way. Moreover, the tensile strength and tensile elongation performance of the resin film obtained as the occupation ratio of the monomeric unit which has a protonic polar group in a polymer (A-1) being below the said upper limit can be raised with good balance.

<<Polyamideimide resin (A-2)>>

"Polyamideimide resin (A-2)" as the polymer (A) having a protonic polar group is a polymer having an amide bond and an imide bond in a repeating unit (ie, polyamideimide resin), and a protonic polar group It is a polymer with On the other hand, polyamideimide resin (A-2) can be obtained also by the method of introduce|transducing a protonic polar group into polyamideimide which does not have a protonic polar group using a well-known modifier. In addition, the polyamideimide resin (A-2) may be obtained by a method of further introducing a protonic polar group into a polyamideimide having a protonic polar group. Therefore, among the various polyamideimides listed below, those having a protonic polar group can be used as they are or by further modification by introducing a protonic polar group. For those without a protonic polar group, a known modifier is used. It can be used after being modified to introduce a protonic polar group.

As polyamideimide resin (A-2), the polyamideimide which has a branched structure, and the polyamideimide which has a linear structure are mentioned. Among them, as the polyamideimide, a polyamideimide having a branched structure is preferable. When the polyamideimide resin (A-2) is a polyamideimide having a branched structure, the chemical resistance of the resin composition can be improved.

The polyamideimide having a branched structure includes, for example, a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), and further, the following structural formulas (α), (β), and a compound having any one or more of the terminal structures represented by (γ), a compound represented by the following formula (4), a polyamideimide resin having a branched structure (manufactured by DIC Corporation, Unidic EMG-793), branched and polyamideimide resin (manufactured by DIC Corporation, Unidic EMG-1015) having a type structure.

[Formula 5]

[However, in Formula (2), R ₁ represents an organic group having a cyclic aliphatic structure having 6 to 13 carbon atoms.]

[Formula 6]

[However, in Formula (3), R ₁ represents an organic group having a cyclic aliphatic structure having 6 to 13 carbon atoms, and R ₂ represents a linear hydrocarbon structure having a number average molecular weight of 700 to 4500.]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[However, in formula (4), n is an integer of 2 or more and 200 or less.]

The polyamideimide resin having a protonic polar group having a structure represented by the formula (4) comprises, for example, isophorone diisocyanate isocyanurate represented by the following formula (5) and trimellitic anhydride It can be obtained by reacting.

[Formula 11]

In such a reaction, a polyfunctional polyol containing two or more hydroxyl groups may be added as a chain transfer agent to introduce a moiety having a urethane structure into a partial structure of the formula (4). By introducing a moiety having a urethane structure into a partial structure of the formula (4), the physical properties of the polyamideimide having a branched structure can be controlled. As a site|part which has a urethane structure, the site|part represented by following formula (6) is mentioned, for example.

[Formula 12]

[However, in the formula (6), R ₁ represents an organic group having a cyclic aliphatic structure having 6 to 13 carbon atoms, and R ₂ represents a linear hydrocarbon structure having a number average molecular weight of 700 to 4500.]

Moreover, as polyamideimide which has a linear structure, the compound etc. which are represented by following formula (7) are mentioned, for example.

[Formula 13]

[However, in the formula (7), n is an integer of 2 or more and 400 or less.]

The compound represented by the said Formula (7) is obtained by making trimellitic anhydride and isophorone diisocyanate react.

<Crosslinking agent (B)>

A crosslinking agent (B) is a compound which acts so that the ITO wrinkle suppression performance of a resin film, chemical-resistance, and heat resistance may be improved by forming a crosslinked structure in a resin film. A crosslinking agent (B) contains the compound represented by following formula (1), It is characterized by the above-mentioned. When the crosslinking agent (B) contains the compound represented by the following formula (1), it becomes possible to impart high heat resistance to the resin film as compared with an epoxy resin conventionally used as a crosslinking agent. Moreover, in addition to the compound represented by following formula (1), a crosslinking agent (B) may contain the dimer of the compound represented by following formula (1), and another multimer.

[Formula 14]

[In formula (1), a plurality of Rs each independently represent any one of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and a plurality of R ¹ are each independently a hydrogen atom; represents either an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m, n, p, and q represent an integer of 0 to 4, respectively.]

Here, the alkyl group having 1 to 6 carbon atoms that may be included in R and R ¹ is not particularly limited, but for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, such as straight chain, branched chain, or an alkyl group having a cyclic structure. Among these, as a C1-C6 alkyl group, a methyl group and an ethyl group are preferable and a methyl group is more preferable.

In addition, the alkoxy group having 1 to 6 carbon atoms that may be included in R and R ¹ is not particularly limited, but for example, a straight chain such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, and an alkoxy group having a branched chain or cyclic structure. Among these, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, and a propoxy group are preferable and a methoxy group is more preferable.

Here, it is preferable that m, n, p, and q are all "0", in other words, the compound represented by Formula (1) from a viewpoint of improving the heat resistance of the resin film obtained further does not have a substituent. In this case, all hydrogen atoms are couple|bonded with the position where "R" can couple|bond in said Formula (1).

Moreover, it is preferable that all R< ¹ > are hydrogen atoms.

Moreover, it is preferable that the compound which satisfy|fills Formula (1) is a compound which does not have a substituent, and is a compound which satisfy|fills the following structure (1-alpha) which consists of three glycidyl ether groups couple|bonded at predetermined positions. On the other hand, when the crosslinking agent (B) contains a compound satisfying the following structure (1-α), the crosslinking agent (B) is a dimer of a compound satisfying the following structure (1-α), the following structure The compound satisfying (1-β) may be included. Such a crosslinking agent (B) is marketed as "Techmore VG3101L" by the PRINTEC company.

[Formula 15]

<<Content of crosslinking agent (B)>>

And the content of the crosslinking agent (B) with respect to 100 parts by mass of the polymer (A) having a protonic polar group in the resin composition is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and 25 parts by mass It is more preferable that it is more than a part, It is preferable that it is 160 mass parts or less, It is more preferable that it is 140 mass parts or less, It is still more preferable that it is 55 mass parts or less. ITO wrinkle suppression performance of the resin film obtained as content of the crosslinking agent (B) with respect to the polymer (A) which has a protonic polar group is more than the said lower limit, chemical-resistance, and light transmittance can be improved. Moreover, the ITO wrinkle suppression performance and chemical-resistance of the resin film obtained as content of the crosslinking agent (B) with respect to the polymer (A) which has a protonic polar group is below the said upper limit can be improved further. On the other hand, when the crosslinking agent (B) contains both the dimer of the compound represented by Formula (1) and the compound represented by Formula (1), it is preferable that these total content satisfy|fill the said family register range Do.

<Phenolic antioxidant (C)>

As a phenolic antioxidant (C), a conventionally well-known thing can be used. For example, as the phenolic antioxidant (C), 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di acrylate-based compounds such as -t-amyl-6-[1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl]phenylacrylate; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxy Phenyl) propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m-cresol), 4 ,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis[2-[3-(3) -t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1, 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ], triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], alkyl-substituted phenolic compounds such as tocopherol; 6-(4-Hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3,5 -Dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis -Octylthio-1,3,5-triazine, 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine Triazine group-containing phenolic compounds, such as; etc. can be used. Among them, an alkyl-substituted phenol-based compound is preferable, and it is more preferable to use pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. On the other hand, the compound as a phenolic antioxidant (C) does not have two or more alkoxymethyl groups, and does not have two or more methylol groups.

<<Content of phenolic antioxidant (C)>>

And, in the resin composition, the content of the phenolic antioxidant (C) with respect to 100 parts by mass of the polymer (A) having a protonic polar group is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, , 15 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 8 parts by mass or less is still more preferable. The light transmittance of the resin film obtained as content of the phenolic antioxidant (C) with respect to the polymer (A) which has a protonic polar group is more than the said lower limit can be improved. In addition, when the content of the phenolic antioxidant (C) with respect to the polymer (A) having a protonic polar group is below the upper limit, the ITO wrinkle suppression performance of the obtained resin film can be further improved, and the antioxidant ( It can suppress that C) becomes easy to bleed out.

<A compound having two or more alkoxymethyl groups and a compound having two or more methylol groups>

The compound which has two or more alkoxymethyl groups, and the compound which has two or more methylol groups are components which can act so that the ITO wrinkle suppression performance of the resin film obtained may be improved further. Moreover, the chemical-resistance of a resin film can be improved by mix|blending the compound which has two or more alkoxymethyl groups, and the compound which has two or more methylol groups with a resin composition. It is preferable that a resin composition contains the compound which has two or more alkoxymethyl groups at least from a viewpoint of exhibiting such an effect still more favorably.

<<Compound having two or more alkoxymethyl groups>>

Examples of the compound having two or more alkoxymethyl groups include a phenol compound in which two or more alkoxymethyl groups are directly bonded to an aromatic ring, a melamine compound in which an amino group is substituted with two or more alkoxymethyl groups, and two or more alkoxymethyl groups. and a urea compound substituted with .

As a phenol compound formed by direct bonding of two or more alkoxymethyl groups to an aromatic ring, for example, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, etc. dimethoxymethyl substituted phenolic compounds; 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl (for example, trade name "TMOM-BP", manufactured by Honshu Chemical Industry Co., Ltd.), 1,1-bis[3 tetramethoxymethyl-substituted biphenyl compounds such as ,5-di(methoxymethyl)-4-hydroxyphenyl]-1-phenylethane; Hexame such as 4,4',4''-(ethylidine)tris[2,6-bis(methoxymethyl)phenol] (for example, trade name "HMOM-TPHAP-GB", manufactured by Honshu Chemical Industry Co., Ltd.) A thoxymethyl-substituted triphenyl compound; is mentioned.

Examples of the melamine compound in which an amino group is substituted with two or more alkoxymethyl groups include N,N'-dimethoxymethylmelamine, N,N',N''-trimethoxymethylmelamine, N,N,N ',N''-Tetramethoxymethylmelamine, N,N,N',N',N''-Pentamethoxymethylmelamine, N,N,N',N',N'',N''- Hexamethoxymethylmelamine (For example, a brand name "Nikalac MW-390LM", a brand name "Nikalac MW-100LM", both are manufactured by Sanwa Chemical), or these polymers, etc. are mentioned.

Examples of the urea compound substituted with two or more alkoxymethyl groups include a trade name "Nikalac MX270", a trade name "Nikalac MX280", and a trade name "Nikalac MX290" (all manufactured by Sanwa Chemical).

<<Compound having two or more methylol groups>>

As a compound which has two or more methylol groups, the phenol compound formed by two or more methylol groups directly couple|bonding with an aromatic ring is mentioned, for example.

And, as a phenol compound formed by direct bonding of two or more methylol groups to an aromatic ring, 2,4-dihydroxymethyl-6-methylphenol, 2,6-bis(hydroxymethyl)-p-cresol, 4 -tert-butyl-2,6-bis(hydroxymethyl)phenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane (trade name "DM-BIPC-F", manufactured by Asahi Organic Co., Ltd.) , bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane (trade name "DM-BIOC-F", manufactured by Asahi Organic Co., Ltd.), 2,2-bis(4-hydroxy-3,5- Dihydroxymethylphenyl) propane (trade name "TM-BIP-A", manufactured by Asahi Organic Co., Ltd.) etc. are mentioned.

Among the compounds having two or more alkoxymethyl groups and compounds having two or more methylol groups, N,N,N',N',N which is one kind of compound having two or more alkoxymethyl groups from the viewpoint of high reactivity '',N''-hexamethoxymethylmelamine is preferred.

<<Content of a compound having two or more alkoxymethyl groups and a compound having two or more methylol groups>>

When the resin composition contains both or either one of the compound having two or more alkoxymethyl groups and the compound having two or more methylol groups, their total content is 100 mass of the polymer (A) having a protonic polar group It is preferable to set it as 1 mass part or more and 100 mass parts or less per part. When the total content of the compound having two or more alkoxymethyl groups and the compound having two or more methylol groups is within the above range, the ITO wrinkle suppression performance of the resin film can be further improved. In particular, when the total content of the compound having two or more alkoxymethyl groups and the compound having two or more methylol groups is below the above upper limit, film reduction in the curing step under high temperature conditions of 100° C. or more can be suppressed, and the heat resistance of the resin film can be further increased.

<Other additives>

The resin composition of this invention may contain other additives other than the above arbitrarily. As such other additives, a polyfunctional epoxy compound having a structure different from that of the above-mentioned crosslinking agent (B), a silane coupling agent, a surfactant, an antioxidant different from the above-mentioned phenolic antioxidant (C), and a radiation-sensitive compound (D) and the like.

<<Polyfunctional epoxy compound having a structure different from that of the crosslinking agent (B)>>

Specific examples of the polyfunctional epoxy compound having a structure different from that of the crosslinking agent (B) include, for example, an epoxy compound having dicyclopentadiene as a skeleton (trade name "HP-7200", manufactured by DIC Corporation), 2,2-bis 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of (hydroxymethyl)-1-butanol (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name "EHPE3150"; Daicel Corporation), epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”) , manufactured by Daicel), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (aliphatic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel), 3 ,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (trade name "Celoxide 2021", "Celoxide 2021P", manufactured by Daicel), ε-caprolactone-modified 3',4' -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (trade name "Celoxide 2081", manufactured by Daicel Corporation), 1,2:8,9-diepoxylimonene (trade name "Celoxide 3000", Daicel Corporation) Epoxy compound which has an alicyclic structure, such as manufacture); And, bisphenol A epoxy compound (trade names "jER825", "jER827", "jER828EL", "jERYL980", manufactured by Mitsubishi Chemical Corporation, brand names "EPICLON840", "EPICLON850", manufactured by DIC), bisphenol F-type epoxy compound (brand name) "jER806", "jER807", "jERYL983U", manufactured by Mitsubishi Chemical, trade names "EPICLON830", "EPICLON835", manufactured by DIC), hydrogenated bisphenol A epoxy compound (brand names "jERYX8000", "jERYX8034" manufactured by Mitsubishi Chemical, trade name) "ST-3000" manufactured by Nippon-Tsumikin Co., Ltd., trade name "Rika Resin HBE-100" manufactured by Nippon Rica, trade name "Epollite 4000" manufactured by Kyoei Chemical Co., Ltd.), long-chain bisphenol A type epoxy resin (trade name "EXA-4816") , "EXA-4850-150", "EXA-4850-1000" manufactured by DIC Corporation), EO-modified bisphenol A type epoxy compound (trade names "adekaresin EP-4000L", "adekaresin EP-4010L", ADEKA Corporation Manufactured), a polyfunctional epoxy having a naphthalene skeleton such as a phenol novolak-type polyfunctional epoxy compound (trade name "jER152", manufactured by Mitsubishi Chemical Corporation), 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene, etc. Compound (trade name "HP-4032D", manufactured by DIC), dicyclopentadiene dimethanol diglycidyl ether (trade name "adekaresin EP-4000L", "adekaresin EP-4088L", manufactured by ADEKA), glycidyl Cydylamine type epoxy resin (trade name "jER630", manufactured by Mitsubishi Chemical Corporation, brand name "TETRAD-C", "TETRAD-X", manufactured by Mitsubishi Gas Chemical Company), chain-type alkyl polyfunctional epoxy compound (trade name "SR-TMP", Sakamoto Pharmaceutical Co., Ltd.), polyfunctional epoxy polybutadiene (trade name "Epolide PB3600", manufactured by Daicel), (trade name "Epolide PB4700", manufactured by Daicel), glycidyl polyether compound of glycerin (trade name "SR-") GLG”, manufactured by Sakamoto Pharmaceutical Co., Ltd.), diglycerin polyglycerol Cydyl ether compound (trade name "SR-DGE", manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyglycerol polyglycidyl ether compound (trade name "SR-4GL", manufactured by Sakamoto Chemical Industries, Ltd.), having a structure represented by the following formula (X) Epoxy compounds which do not have alicyclic structures, such as an epoxy compound ("WHR-991S" by Nippon Kayaku Co., Ltd.); and the like. In addition, these can be used individually by 1 type or in combination of multiple types. Especially, the epoxy compound which has an alicyclic structure, ie, an alicyclic epoxy compound, is preferable. By mix|blending an alicyclic epoxy compound with a resin composition, transparency of the resin film obtained can be improved.

[Formula 16]

It is preferable that content of the polyfunctional epoxy compound from which a structure differs from a crosslinking agent (B) in a resin composition is 100 mass parts or less per 100 mass parts of polymers (A) which have a protonic polar group. The chemical-resistance of a resin film can be improved efficiently that content of an epoxy-group containing compound is 100 mass parts or less. On the other hand, when the resin composition contains a polyfunctional epoxy compound having a structure different from that of the crosslinking agent (B) in addition to the predetermined crosslinking agent (B) described above, the polyfunctionality having a structure different from that of the crosslinking agent (B) and the crosslinking agent (B) The total content of the epoxy compound is << content of the cross-linking agent (B)>>, and the content of the cross-linking agent (B) with respect to 100 parts by mass of the polymer (A) having a protonic polar group in the resin composition It is preferable to satisfy the range.

<<Silane coupling agent, surfactant, and antioxidant >>

A silane coupling agent functions so that the adhesiveness between the resin film obtained using the resin composition of this invention, and the base material with which the said resin film was formed may be improved. In addition, it does not specifically limit as a silane coupling agent, A well-known thing can be used (for example, refer Unexamined-Japanese-Patent No. 2015-94910). More specifically, as a silane coupling agent, alkoxysilanes, such as glycidoxy propyl trimethoxysilane, can be used suitably.

In addition, content of a silane coupling agent is 0.01 mass part or more and 10 mass parts or less per 100 mass parts of polymers (A) which have a protonic polar group normally.

Surfactant is a component which can improve the coatability of the resin composition of this invention. The surfactant is not particularly limited, and known silicone-based surfactants, fluorine-based surfactants, polyoxyalkylene-based surfactants, methacrylic acid copolymer-based surfactants, and acrylic acid copolymer-based surfactants can be used (for example, , see International Publication No. 2017/163981). Especially, as surfactant, silicone type surfactants, such as an organosiloxane polymer, can be used suitably.

In addition, content of surfactant is 0.01 mass part or more and 1 mass part or less per 100 mass parts of polymers (A) which have a protonic polar group normally.

The antioxidant different from the above-mentioned phenolic antioxidant (C) is a component which can improve the stability of the resin composition of this invention. It does not specifically limit as antioxidant, Well-known antioxidant, such as a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant, and a lactone antioxidant, can be used (For example, International Publication No. 2017/163981) Reference).

In addition, a silane coupling agent, surfactant, and antioxidant other than the above-mentioned phenolic antioxidant (C) can be used individually by 1 type, respectively, or in combination of 2 or more type. In addition, the quantity of the antioxidant different from the silane coupling agent mix|blended with a resin composition, surfactant, and the above-mentioned phenolic antioxidant (C) can be adjusted arbitrarily.

<<Radiation-sensitive compound (D)>>

The radiation-sensitive compound (D) is a compound capable of causing a chemical reaction when irradiated with radiation. Here, it does not specifically limit as a radiation, For example, visible light; ultraviolet ray; X-ray; light rays of a single wavelength, such as g-rays, h-rays, and i-rays; laser beams such as KrF excimer laser beam and ArF excimer laser beam; Particle beams, such as an electron beam; and the like. It does not specifically limit as a radiation sensitive compound (D), An acetophenone compound, a triaryl sulfonium salt, and an azide compound can be used. Especially, azide compounds, such as a quinonediazide compound, can be used suitably. A radiation-sensitive compound (D) can be used individually by 1 type or in combination of 2 or more type. In addition, the quantity of the radiation-sensitive compound (D) mix|blended with the resin composition can be adjusted arbitrarily. When the resin composition contains the radiation-sensitive compound (D), the resin film having a desired pattern can be favorably formed by patterning the resin film.

<solvent>

It does not specifically limit as a solvent which the resin composition of this invention can contain arbitrarily, A well-known solvent can be used as a solvent of a resin composition. Examples of such solvents include linear ketones, alcohols, alcohol ethers, esters, cellosolve esters, propylene glycol, diethylene glycols such as diethylene glycol ethyl methyl ether, and saturated γ-lactones. , halogenated hydrocarbons, aromatic hydrocarbons, and polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide (see, for example, International Publication No. 2015/033901).

In addition, these solvents can be used individually by 1 type or in mixture of 2 or more types.

The amount of the solvent in the resin composition is not particularly limited, and with respect to 100 parts by mass of the polymer (A) having a protonic polar group, preferably 10 parts by mass or more, preferably 10000 parts by mass or less, more preferably 5000 It is a mass part or less, More preferably, it is 1000 mass parts or less.

<Method for producing a resin composition>

The resin composition of this invention can be prepared by mixing the above-mentioned component by a known method, and filtering arbitrarily. Here, for mixing, known mixers such as a stirrer, agitator, ball mill, sand mill, bead mill, pigment disperser, ceruleaner, ultrasonic disperser, homogenizer, planetary mixer, and fill mixer can be used. In addition, the general filtration method using filter media, such as a filter, can be employ|adopted for filtration of a mixture.

(Method for producing a resin film)

The resin film made of the resin composition of the present invention can be produced by the method for producing a resin film of the present invention, including a step (curing step) of heating a coating film formed using the resin composition of the present invention described above at 100 ° C. or higher. can The manufacturing method of the resin film of this invention may further include the process (coating film formation process) of forming a coating film using the resin composition of this invention on the board|substrate which forms a resin film. Moreover, as the resin composition of this invention, it is also possible to form a patterned resin film using the resin composition containing a radiation sensitive compound (D). In this case, when forming a coating film, operation of patterning a coating film may be performed, and a bleaching process may be further performed after a coating film formation process, before a hardening process.

<coating film formation process>

The arrangement of the coating film on the substrate on which the resin film is formed is not particularly limited, and can be performed according to known methods such as a coating method and a film lamination method.

Formation of the coating film by the coating method can be performed by heat-drying (pre-baking), after apply|coating a resin composition on a board|substrate. On the other hand, as a method of applying the resin composition, for example, various methods such as a spray coating method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a bar coating method, a screen printing method, and an inkjet method. can be hired Heat drying conditions vary depending on the type and blending ratio of components contained in the resin composition, but the heating temperature is usually 30 to 150° C., preferably 60 to 120° C., and the heating time is usually 0.5 to 90 minutes, Preferably it is for 1 to 60 minutes, More preferably, it is for 1 to 30 minutes.

In addition, in formation of the coating film by the film lamination method, after apply|coating a resin composition on base materials for B-stage film formation, such as a resin film or a metal film, and heat-drying (pre-baking) to obtain a B-stage film, then, this It can carry out by laminating|stacking a B-stage film on a board|substrate. In addition, application|coating of the resin composition on the base material for B-stage film formation, and heat-drying of a resin composition can be carried out similarly to the application|coating and heat-drying of the resin composition in the above-mentioned application|coating method, and can be performed. In addition, lamination|stacking can be performed using crimping machines, such as a pressure laminator, a press, a vacuum laminator, a vacuum press, and a roll laminator.

The patterning of the coating film, which is an arbitrary operation, uses a known patterning method such as, for example, a method of irradiating the coating film before patterning with radiation to form a latent image pattern, and then contacting the coating film having the latent image pattern with a developer to make the pattern visible. can be done by

Here, the radiation is not particularly limited as long as it can improve the solubility of the radiation-irradiated portion in the developer by causing the radiation-sensitive compound (D) to undergo a chemical reaction, and any radiation can be used. Specifically, for example, visible light; ultraviolet ray; X-ray; light rays of a single wavelength, such as g-rays, h-rays, and i-rays; laser beams such as KrF excimer laser beam and ArF excimer laser beam; Particle beams, such as an electron beam; etc. can be used. In addition, these radiations can be used individually by 1 type or in mixture of 2 or more types.

In addition, as a developing solution, well-known alkali developing solutions, such as an aqueous solution of an alkaline compound, can be used.

In addition, it does not specifically limit as a method and conditions for making a coating film contact a developing solution, A well-known method and conditions are employable.

Moreover, in order to deactivate the radiation-sensitive compound (D) contained in the resin composition as needed, you may perform a bleaching process. In a bleaching process, arbitrary radiation can also be irradiated with respect to the coating-film whole surface. The method illustrated for formation of the said latent image pattern can be used for irradiation of a radiation. In addition, you may heat a resin film simultaneously with irradiation of a radiation or after irradiation. In a bleaching process, transparency of the resin film obtained can be improved further by deactivating a radiation-sensitive compound (D).

<curing process>

In a hardening process, a coating film is hardened by heating (post-baking) at the temperature of 100 degreeC or more.

Heating of a coating film is not specifically limited, For example, it can perform using a hotplate, oven, etc. In addition, you may perform a heating in an inert gas atmosphere as needed. Examples of the inert gas include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is especially preferable.

Here, the temperature at the time of heating a coating film in a hardening process needs to be 100 degreeC or more, It is preferable that it is 150 degreeC or more, It is more preferable that it is 200 degreeC or more, It is still more preferable that it is 250 degreeC or more. When the resin composition of this invention is used, even when the temperature at the time of heating a coating film is high at 100 degreeC or more, it can form into a film favorably. Moreover, although the upper limit of the temperature at the time of heating a coating film in a hardening process is not specifically limited, It is preferable that it is 400 degrees C or less.

On the other hand, the time for heating the coating film in the curing step can be appropriately selected depending on the area or thickness of the coating film, equipment used for heating, and the like, but may be, for example, 10 to 120 minutes.

And it is preferable that the transmittance|permeability of the light of wavelength 400nm of the resin film which passed through such a hardening process is 95 % or more. In addition, "transmittance" can be measured according to the method described in an Example.

(Electronic parts)

The electronic component of this invention is equipped with the resin film which consists of the resin composition of this invention mentioned above. And since the electronic component of this invention is equipped with the resin film excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance formed from the resin composition of this invention, it is high performance.

<Types of Electronic Components>

The kind of electronic component of this invention is not specifically limited. For example, since the resin film which consists of the resin composition of this invention is excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance, the electronic component of this invention is on the surface of the resin film which consists of the resin composition of this invention. It may be an electronic component provided with an ITO electrode, in which the ITO film|membrane is arrange|positioned. Further, for example, the resin film of the present invention may be an interlayer insulating film of a redistribution layer provided in a semiconductor device.

Example

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In addition, in the following description, "%" and "part" which show quantity are a mass basis, unless there is particular notice. Also, the pressure is a gauge pressure.

In Examples and Comparative Examples, the ITO wrinkle suppression performance, chemical resistance, heat resistance (heat loss), and light transmittance of the resin film were evaluated using the following methods, respectively.

<ITO wrinkle suppression performance>

The resin compositions obtained in Examples and Comparative Examples were coated on a glass substrate (Corning 1737, manufactured by Corning) by spin coating, and then dried (pre-baked) by heating at 120° C. for 2 minutes using a hot plate to form a coating film. . Next, a resin film with a film thickness of 2 µm was formed by heating up from 30°C to 250°C at 10°C/min in a nitrogen atmosphere using an oven and then performing post-baking heated at 250°C for 60 minutes. On this resin film, an ITO transparent electrode was formed to a film thickness of 40 nm by a sputtering apparatus (the Shibaura Illetek company make, "i-Miller CFS-4EP-LL", stage temperature 30 degreeC). The glass substrate of the obtained laminated body with an ITO transparent electrode was cut|disconnected to 1.5 cm square, and the test piece was produced. After setting the glass substrate side of the produced test piece on the hotplate heated at 200 degreeC for 5 minutes, it cooled to room temperature. Next, the ITO transparent electrode side surface of the test piece was observed with an optical microscope (100 times), and the ratio of the area of the wrinkle portion to the total area (1.5 cm × 1.5 cm) of the surface of the resin film was calculated, according to the following standards evaluated. On the other hand, the area of the wrinkle part was extracted by binarizing the image obtained with the optical microscope.

A: There is no generation|occurrence|production of wrinkles on the surface of a resin film.

B: Although wrinkles were generated on the surface of the resin film, the area of the wrinkled portion was less than 1/4 of the total area of the surface of the resin film.

C: Although wrinkles are generated on the surface of the resin film, the area of the wrinkle portion is at least 1/4 of the total area of the surface of the resin film.

<Chemical resistance>

The resin compositions obtained in Examples and Comparative Examples were coated on a glass substrate (Corning 1737, manufactured by Corning) by spin coating, and then dried (pre-baked) by heating at 120° C. for 2 minutes using a hot plate to form a coating film. . Next, a resin film having a film thickness of 2 µm is obtained by post-baking using an oven in a nitrogen atmosphere, the temperature is raised from 30°C to 250°C at 10°C/min, and then heated at 250°C for 60 minutes, and the thickness T1 is measured. did. The obtained resin film was immersed for 2 minutes in a monoethanolamine-dimethyl sulfoxide mixed solution (mixing ratio: monoethanolamine: dimethyl sulfoxide = 7:3, manufactured by Tokyo Oka Kogyo Co., Ltd., "TOK106") at 40°C for 2 minutes, and then was immersed in pure water for 30 seconds Rinse and measure thickness T2. From the measured values of T1 and T2, swelling ratio (%): (T2 - T1)/T1 x 100 was computed, and it evaluated according to the following criteria.

A: The swelling ratio is 3% or less.

B: The swelling ratio exceeds 3% and 8% or less.

C: The swelling ratio exceeds 8%.

<Heat resistance (heat loss)>

Using a sputtering apparatus (manufactured by Shibaura Illetec, "i-Miller CFS-4EP-LL"), the resin compositions obtained in Examples and Comparative Examples were spin-coated on a silicon wafer on which an aluminum thin film was formed to a film thickness of 100 nm. After that, the silicon wafer was heated at 120° C. for 2 minutes using a hot plate (coating film formation step). Then, in a nitrogen atmosphere, after raising the temperature from 30°C to 250°C at 10°C/min, heat treatment was performed at 250°C for 60 minutes to obtain a resin film, and a laminate having a resin film having a film thickness of 10 µm on one side was obtained (curing). fair).

The obtained laminate was immersed in a 0.5 mol/L aqueous hydrochloric acid solution, and the aluminum thin film positioned between the silicon wafer and the resin film was dissolved in the aqueous hydrochloric acid solution, thereby peeling the resin film from the silicon wafer. Next, the peeled resin film was washed with water and dried. The resin film after drying is reached to 300°C under the condition of a temperature increase rate of 10°C/min in a nitrogen atmosphere using a differential thermogravimetric simultaneous measurement device (Seiko Instruments Co., Ltd., TG/DTA6200), and maintained at 300°C for 1 hour Measure the mass W0 of the sample at the time of reaching 300°C and the mass W1 of the sample at the end of holding at 300°C, respectively, and the value of the heating loss from these values: (W0 - W1)/W0 × 100 (%) It calculated and evaluated by the following reference|standards. It means that the resin film is excellent in heat resistance, so that there are few heating losses.

A: Heat loss at 300 degreeC is less than 4 %.

B: The loss on heating at 300°C is 4% or more and less than 8%.

C: The loss on heating at 300°C is 8% or more.

<Light transmittance>

The resin compositions obtained in Examples and Comparative Examples were coated on a glass substrate (Corning 1737, manufactured by Corning) by spin coating, and then heated and dried (pre-baked) at 120° C. for 2 minutes using a hot plate to have a film thickness of 2 μm. A coating film was formed (coating film formation process). Then, using an oven, in a nitrogen atmosphere, the temperature was raised from 30°C to 250°C at 10°C/min, and then post-baking heated at 250°C for 60 minutes to obtain a laminate comprising a resin film and a glass substrate ( curing process).

About the obtained laminated body, the light transmittance (%) in the light of wavelength 400nm was measured using the spectrophotometer V-560 (made by Nippon Kogyo Co., Ltd.).

Moreover, after heating (additional heating) the laminated body obtained above at 250 degreeC in atmospheric atmosphere for 1 hour, it carried out similarly to the above, and the light transmittance (%) in the light of wavelength 400nm was measured.

On the other hand, the light transmittance (%) of the resin film was calculated as a converted value when the thickness of the resin film was 2 µm by using the glass substrate to which the resin film was not attached as a blank, and evaluated according to the following criteria.

A: The light transmittance is 96% or more.

B: The light transmittance is 93% or more and less than 96%.

C: The light transmittance is less than 93%.

(Synthesis Example 1: Synthesis of cyclic olefin polymer (a-1) having a protonic polar group)

As the cyclic olefin polymer (a-1) having a protonic polar group, a polymer having an occupation ratio of a monomer unit having a protonic polar group of 60 mol% was obtained.

40 mol% of N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide as a cyclic olefin having an N-substituted imide group, and a protonic polar group 100 parts of a monomer mixture comprising 60 mol% of 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene as a cyclic olefin, 2 parts of 1,5-hexadiene; (1,3-dimethylimidazolin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (Org. Lett., Volume 1, page 953, was synthesized by the method described in 1999) ) 0.02 parts and 200 parts of diethylene glycol ethyl methyl ether were put into a glass pressure-resistant reactor substituted with nitrogen, and reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction solution.

Then, the obtained polymerization reaction solution is put in an autoclave, stirred at 150° C. and 4 MPa hydrogen pressure for 5 hours to perform a hydrogenation reaction, and contains a hydrogenated polymer as a cyclic olefin polymer (a-1) having a protonic polar group. A polymer solution was obtained. The polymerization conversion ratio of the obtained cyclic olefin polymer (a-1) was 99.7%, the polystyrene conversion weight average molecular weight was 7,150, the number average molecular weight was 4,690, molecular weight distribution was 1.52, and the hydrogenation rate was 99.7%. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (a-1) was 34.4 mass %.

(Synthesis Example 2: Synthesis of cyclic olefin polymer (a-2) having a protonic polar group)

As the cyclic olefin polymer (a-2) having a protonic polar group, a polymer having a occupancy ratio of a monomer unit having a protonic polar group of 70 mol% was obtained.

N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyi as a cyclic olefin having an N-substituted imide group in the monomer mixture used for the polymerization reaction The polymer obtained by changing the mixing ratio of the amide and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene as a cyclic olefin having a protonic polar group (a In -2), the occupancy ratio of the monomer unit derived from 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene in -2) is 70 mol%, 1, A cyclic olefin polymer (a-2) was obtained in the same manner as in Synthesis Example 1, except that the compounding quantity of 5-hexadiene was 2.7 parts. The polymerization conversion ratio of the obtained cyclic olefin polymer (a-2) was 99.7%, the polystyrene conversion weight average molecular weight was 5,390, the number average molecular weight was 3,480, the molecular weight distribution was 1.55, and the hydrogenation rate was 99.7%. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (a-2) was 34.4 mass %.

(Synthesis Example 3: Synthesis of cyclic olefin polymer (a-3) having a protonic polar group)

As the cyclic olefin polymer (a-3) having a protonic polar group, a polymer having an occupation ratio of a monomer unit having a protonic polar group of 50 mol% was obtained.

N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyi as a cyclic olefin having an N-substituted imide group in the monomer mixture used for the polymerization reaction The polymer obtained by changing the mixing ratio of the amide and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene as a cyclic olefin having a protonic polar group (a In -3), the occupancy ratio of the monomer unit derived from 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene in -3) is 50 mol%, 1, A cyclic olefin polymer (a-3) was obtained in the same manner as in Synthesis Example 1, except that the compounding amount of 5-hexadiene was 2.7 parts. The polymerization conversion ratio of the obtained cyclic olefin polymer (a-3) was 99.7%, the polystyrene conversion weight average molecular weight was 4,310, the number average molecular weight was 2,890, molecular weight distribution was 1.49, and the hydrogenation rate was 99.7%. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (a-3) was 34.4 mass %.

(Synthesis Example 4: Synthesis of cyclic olefin polymer (a-4) having no protonic polar group)

Tetracyclo[6.5.0.1 ^2,5 .0 ^8,13 ]trideca-3,8,10,12-tetraene (MTF) 80 mole parts, N-(4-phenyl)-(5-norbornene-2 ,3-dicarboxyimide) (NBPI) 20 mol parts, 1-hexene 6 mol parts, anisole 590 mol parts, and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1, as a ruthenium-based polymerization catalyst) 0.015 mol part of 3-dimethyl-4-imidazolin-2-ylidene) (tricyclohexyl phosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) was put into a pressure-resistant glass reactor substituted with nitrogen, and 80 was stirred under stirring. A polymerization reaction was carried out at deg. C for 1 hour to obtain a solution of a ring-opened polymer. As a result of measuring this solution by gas chromatography, it was confirmed that no monomer remained substantially, and the polymerization conversion ratio was 99% or more.

Next, the solution of the obtained ring-opened polymer was thrown into the autoclave equipped with the stirrer which carried out nitrogen substitution, and it stirred at 150 degreeC and 7 MPa of hydrogen pressures for 5 hours, and hydrogenated reaction was performed. The obtained hydrogenation reaction solution was concentrated to obtain a solution of a cyclic olefin polymer (a-4) having no protonic polar group (solid content concentration: 55.5%). The obtained cyclic olefin polymer (a-4) having no protonic polar group had a weight average molecular weight of 50,000, a number average molecular weight of 20,000, and a hydrogenation rate of 97%.

(Example 1)

291 parts of a solution of the cyclic olefin polymer (a-1) having a protonic polar group obtained in Synthesis Example 1 (100 as a cyclic olefin polymer (A-1) in which the proportion of monomer units having a protonic polar group is 51 mol% or more) Part), a compound as a crosslinking agent (B) which is a mixture of a compound satisfying the following formula (1-α) and a compound satisfying the following formula (1-β) (manufactured by PRINTEC, “Techmore VG3101L”, formula (1- Compound of α): Compound of formula (1-β) = 9:1 (by mass)) 10 parts, organosiloxane polymer as a surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KP-341”) 0.1 part, as an antioxidant 2 parts of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name "Irganox1010FF", manufactured by BASF), glycidoxypropyl as a silane coupling agent 2 parts of trimethoxysilane (manufactured by XIAMETER, product name "OFS-6040"), and 41 parts of diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Company, product name "EDM-S") as a solvent were mixed and dissolved, It filtered through the filter made from polytetrafluoroethylene with a pore diameter of 0.45 micrometers, and the resin composition was prepared.

And various evaluations were performed according to the above about the resin film formed using the obtained resin composition. A result is shown in Table 1.

[Formula 17]

(Examples 2 to 3, 7 to 9)

Except having changed as the compounding quantity of a crosslinking agent (B) and the compounding quantity of a solvent were respectively shown in Table 1, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 4)

The compounding quantity of a crosslinking agent (B) and the compounding quantity of a solvent are respectively changed as shown in Table 1, and as a compound which has two or more alkoxymethyl groups, N,N,N',N',N'',N''- A resin composition was prepared in the same manner as in Example 1 except that 15 parts of hexamethoxymethylmelamine (product name "Nikalac MW-100LM", manufactured by Sanwa Chemical Co., Ltd.) was blended.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 5)

A cyclic olefin polymer (A-1) in which the occupancy ratio of the monomer unit having a protonic polar group is 51 mol% or more, the polymer synthesized in Synthesis Example 2 above, wherein the occupancy ratio of the monomer unit having a protonic polar group is 70 mol% (a-2) was used, and except having changed the compounding quantity of a crosslinking agent (B) and a solvent as shown in Table 1, respectively, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 6)

Instead of the predetermined cyclic olefin polymer (A-1), a polyamideimide resin (A-2) having a protonic polar group was used. As the polyamideimide resin (A-2), 229 parts of a mixed solution of propylene glycol methyl ether acetate and n-butanol of a polyamideimide resin having a branched structure (manufactured by DIC, Unidic EMG-793, branched type having a carboxyl group) A resin composition was prepared in the same manner as in Example 1 except that 100 parts) was used as the polyamideimide resin (a-5) and the compounding amounts of the crosslinking agent (B) and the solvent were changed as shown in Table 1, respectively. .

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Examples 10 to 11)

Except having changed as the compounding quantity of a crosslinking agent (B), antioxidant (C), and the compounding quantity of a solvent were respectively shown in Table 1, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 12)

4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 6-diazo-5,6 as radiation-sensitive compound (D) -Dihydro-5-oxo-1-naphthalenesulfonic acid chloride (1,2-naphthoquinonediazide-5-sulfonic acid chloride) ester (2.0 moles) (manufactured by Miwon Specialty Chemicals, product name “TPA-520”) 20 parts were mix|blended, and except having changed as the compounding quantity of a crosslinking agent (B) and a solvent were respectively shown in Table 1, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 13)

Without mixing the antioxidant (C), except having changed the compounding quantity of a crosslinking agent (B) and a solvent as shown in Table 1, respectively, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 14)

As the polymer (A) having a protonic polar group, a prescribed cyclic olefin polymer (A-1) and a prescribed polyamideimide resin (A-2) were used in the compounding ratios shown in Table 1. In addition, as shown in Table 1, the compounding quantity of a solvent was changed. Except for these points, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Example 15)

The compounding quantity of a crosslinking agent (B) and the compounding quantity of a solvent are respectively changed as shown in Table 1, and as a compound which has two or more alkoxymethyl groups, N,N,N',N',N'',N''- 15 parts of hexamethoxymethylmelamine (product name "Nikalac MW-100LM", manufactured by Sanwa Chemical Co., Ltd.) is blended, and 4,4'-[1-[4-[1-[4-] as a radiation-sensitive compound (D)) Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid chloride (1,2-naphthoquinonediazide-5 A resin composition was prepared in the same manner as in Example 1 except that 20 parts of an ester (2.0 moles) (manufactured by Miwon Specialty Chemicals, product name “TPA-520”) of -sulfonic acid chloride) was blended.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Comparative Example 1)

The crosslinking agent (B) is not blended, but instead of the crosslinking agent (B), a polyfunctional epoxy compound having a different structure from the butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (di A resin composition was prepared in the same manner as in Example 1 except that 30 parts of the cell company make, product name "Epolide GT401")) was blended, and the blending amount of the solvent was changed as shown in Table 1.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Comparative Example 2)

Without blending the crosslinking agent (B), instead of this, 30 parts of a bisphenol A type epoxy compound (manufactured by Mitsubishi Chemical, "jER828EL"), which is a polyfunctional epoxy compound having a structure different from that of the crosslinking agent (B), is blended, and the solvent Except having changed the compounding quantity as shown in Table 1, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Comparative Example 3)

Instead of the solution of the predetermined cyclic olefin polymer (A-1), a solution of the polymer (a-3) obtained according to Synthesis Example 3 (polymer ( 100 parts) was used as a-3), and except having changed the compounding quantity of a crosslinking agent (B) and a solvent as shown in Table 1, respectively, it carried out similarly to Example 1, and prepared the resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

(Comparative Example 4)

Instead of the solution of the predetermined cyclic olefin polymer (A-1), a solution of the cyclic olefin polymer (a-4) having no protonic polar group obtained according to Synthesis Example 4 (100 parts as polymer (a-4)) ) was used, the amount of the crosslinking agent (B) having a predetermined structure was changed to 30 parts, and the solvent was changed to 310 parts of anisole, in the same manner as in Example 1, to prepare a resin composition.

And the same evaluation as Example 1 was performed using the obtained resin composition. A result is shown in Table 1.

From Table 1, according to the resin compositions of Examples 1 to 15 containing a predetermined polymer (A) having a protonic polar group and a crosslinking agent (B) satisfying a specific structure, ITO wrinkle suppression performance, chemical resistance, and heat resistance It turns out that this excellent resin film was able to be formed. In addition, from Table 1, in the case of Comparative Examples 1 and 2 using a resin composition not containing a crosslinking agent (B) that satisfies a specific structure, all of ITO wrinkle suppression performance, chemical resistance, and heat resistance were combined at a high level. It turns out that the resin film could not be formed. Further, from Table 1, in Comparative Example 3 using a cyclic olefin polymer having a occupancy ratio of monomer units having a protonic polar group of less than 51 mol%, and Comparative Example 4 using a cyclic olefin polymer having no protonic polar group, the obtained Although the heat resistance of the resin film was excellent, it can be seen that the ITO wrinkle suppression performance and chemical resistance were low.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, the resin film excellent in ITO wrinkle suppression performance, chemical-resistance, and heat resistance can be formed.

Moreover, according to this invention, the high-performance electronic component provided with the resin film formed using the resin composition of this invention can be provided.

Moreover, according to this invention, the manufacturing method of the resin film which can manufacture efficiently the resin film of this invention using the resin composition of this invention can be provided.

Claims (11)

A resin composition comprising a polymer (A) having a protonic polar group and a crosslinking agent (B) containing a compound represented by the following formula (1), wherein the polymer (A) having a protonic polar group comprises:
It contains the cyclic olefin polymer (A-1) having a protonic polar group, and the occupancy ratio of the monomer unit having a protonic polar group is 51 mol% or more, and
One containing polyamideimide resin (A-2) having a protonic polar group
satisfying at least one of
resin composition.
[Formula 1]

[In formula (1), a plurality of Rs each independently represent any one of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and a plurality of R ¹ are each independently a hydrogen atom; represents either an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m, n, p, and q represent an integer of 0 to 4, respectively.] The method of claim 1,
The resin composition which further contains a phenolic antioxidant (C). 3. The method of claim 2,
The resin composition in which content of the said phenolic antioxidant (C) with respect to 100 mass parts of polymers (A) which has the said protonic polar group is 0.3 mass part or more and 15 mass parts or less. 4. The method according to any one of claims 1 to 3,
The resin composition wherein the polymer (A) having a protonic polar group is a cyclic olefin polymer having a carboxyl group. 5. The method according to any one of claims 1 to 4,
The polymer (A) having a protonic polar group is a cyclic olefin polymer (A-1) having the protonic polar group,
The resin composition, wherein the cyclic olefin polymer (A-1) having a protonic polar group is a ring-opening polymer. 6. The method according to any one of claims 1 to 5,
The resin composition in which content of the said crosslinking agent (B) with respect to 100 mass parts of polymers (A) which has the said protonic polar group is 5 mass parts or more and 160 mass parts or less. 7. The method according to any one of claims 1 to 6,
The resin composition which further contains at least one of the compound which has two or more alkoxymethyl groups, and the compound which has two or more methylol groups. 8. The method according to any one of claims 1 to 7,
The resin composition which further contains a radiation-sensitive compound (D). 9. The method of claim 8,
The said radiation-sensitive compound (D) is a quinonediazide compound, The resin composition. An electronic component provided with the resin film which consists of the resin composition in any one of Claims 1-9. The manufacturing method of a resin film including the process of heating the coating film formed using the resin composition in any one of Claims 1-9 at 100 degreeC or more.