JPH07271036A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin compsn. provided with photosensitivity without deteriorating superior characteristics peculiar to cyclo-olefin resin and to obtain a cured body of the compsn. CONSTITUTION:This photosensitive resin compsn. contains cyclo-olefin resin having cyclic reactive groups and a photoreactive substance which reacts with the cyclo-olefin resin under irradiation with active light and forms a crosslinked compd. This photosensitive resin compsn. is crosslinked by irradiation with active light to obtain a photocrosslinked cured body and this cured body is further crosslinked by heating to obtain a crosslinked cured body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative photosensitive resin composition having excellent heat resistance, solvent resistance, low water absorption, electric insulation and adhesion.

[0002]

2. Description of the Related Art Recently, cyclic olefin resins, which have been widely used in various fields, have high heat resistance,
Due to its excellent electrical insulation properties such as low water absorption and low dielectric constant, it has been attracting attention as an insulating material for increasing the speed, reliability, and density of electric circuits. In order to further enhance its usefulness, it has been desired to impart photosensitivity to these cyclic olefin resins. Conventionally, as an example of imparting photosensitivity to a cyclic olefin resin, a polymer obtained by ring-opening polymerization of a norbornene derivative is used, and an aromatic bisazide compound (EP-14031) is added to the polymer.
9), a photosensitive polymer comprising a photopolymerization initiator, a sensitizer, and a copolymerization monomer (JP-A 61-23618) is disclosed. However, since the ring-opening polymers of these norbornene derivatives essentially have many unsaturated bonds in the molecule, there is a problem that they are not sufficiently resistant to oxidative deterioration and heat resistance.

[0003]

Therefore, the present inventors have found that the cyclic olefin resin has high heat resistance, low water absorption,
As a result of extensive studies on a method for imparting photosensitivity without impairing good electric insulation properties such as low dielectric constant, a cross-linking compound was obtained by reacting the cyclic olefin resin with a cyclic reactive group with the cyclic olefin resin. By evenly dispersing the photoreactive substance that generates the, by exposure to actinic light, it was found that photosensitivity can be imparted without impairing the excellent properties of the cyclic olefin resin, and the present invention has been completed. It was

[0004]

Thus, the first aspect of the present invention
Is a cyclic olefin resin (A) having a cyclic reactive group
To the negative type by uniformly dispersing the photoreactive substance (B), which reacts with the cyclic olefin resin by irradiation with actinic rays to form a cross-linking compound, and optionally a sensitizer and other additives. A photosensitive resin composition is provided. A second aspect of the present invention is characterized by providing a photocrosslinking cured product by crosslinking the first photosensitive resin composition by irradiation with actinic rays. The third aspect of the present invention is to heat the second photocrosslinking cured product,
It is characterized by providing a crosslinked cured product which is further crosslinked. In the present invention, first, the above-mentioned component (A) and (B)
It may be considered that the composition comprising the components is first heat-cured and then photocrosslinked to obtain a crosslinked cured product, but in this case, there is a problem that a pattern cannot be formed by a solvent developing method, which is not preferable. The photo-crosslinked cured product of the present invention,
When the component (B) is irradiated with actinic rays, it is crosslinked mainly by reacting with a part of the component (A) which is not a cyclic reactive group or with a part of the cyclic reactive group, thereby imparting photosensitivity. It is speculated that the photocrosslinking cured product may further improve the heat resistance due to further reaction of the components (A) and (B) including the cyclic reactive group by heating. In order to impart photosensitivity, a certain amount of the component (B) is necessary with respect to the component (A), and the amount is preferably 1 to 2
0 parts by weight.

Cyclic Olefin Resin Having Cyclic Reactive Group The thermoplastic cyclic olefin resin having a cyclic reactive group used in the present invention is a resin having a cyclic reactive group inside the molecular chain, in the side chain or at the terminal part. , Number average molecular weight 5,000
200,000 (GPC analysis value using cyclohexane as a solvent),
It is preferably from 8000 to 100,000, and the cyclic reactive group content is based on the total number of monomer units of the polymer.
0.5 to 50 mol%, preferably 1 to 30 mol%
The thermoplastic cyclic olefin-based resin of is preferably used. The thermoplastic cyclic olefin-based resin having a cyclic reactive group used in the method of the present invention can be produced by a known method, and can be mainly produced by the following method.

(I) Grafting of an olefin-containing cyclic reactive monomer A ring-opening polymer obtained by polymerizing a cyclic olefin monomer by a known ring-opening polymerization method using titanium, tungsten or an aluminum compound as a catalyst. A cyclic olefin resin produced by hydrogenation by a conventional hydrogenation method, a cyclic olefin monomer and an unsaturated monomer such as ethylene, by a known method with a transition metal compound / aluminum compound catalyst, etc. A cyclic olefin obtained by addition polymerization of a polymer obtained by addition polymerization and / or a hydrogenated product thereof, or a cyclic olefin monomer with a transition metal compound / aluminum compound catalyst or a palladium catalyst by a known method. At least one resin selected from the group of resins, using an olefin-containing cyclic reactive monomer It can be prepared by raft modified. This graft reaction can be carried out by a known method, and a cyclic olefin polymer having a cyclic reactive group can be obtained by a solution method or a melting method using a radical generator such as peroxide. (Ii) Copolymerization of olefin-containing cyclic reactive monomer The addition of the cyclic olefin monomer of (i) above or the addition of the cyclic olefin monomer and the above unsaturated monomer such as ethylene by a known method. At the time of copolymerization, a cyclic olefin resin having a cyclic reactive group is obtained by using an olefin-containing cyclic reactive monomer as a copolymerization monomer. As the olefin-containing cyclic reactive monomer used at this time, a compound used in graft modification is preferably used. This makes it possible to obtain a target cyclic olefin resin having a cyclic reactive group.

Examples of the cyclic olefin monomer used in the production of these thermoplastic cyclic olefin resins include the following. Monomers known in JP-A-3-14882, JP-A-3-122137, JP-A-2-227424, JP-A-2-276842 and the like, and examples thereof include norbornene, its alkyl, alkylidene, aromatic substituted derivatives and substitution thereof. Or polar group substitution products such as halogen, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group and silyl group of unsubstituted olefin, for example, 2-norbornene, 5-methyl-2-norbornene, 5, 5-dimethyl-2-norbornene, 5-
Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2.
-Norbornene, 5-phenyl-2-norbornene, 5
-Phenyl-5-methyl-2-norbornene, etc .; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, 1,4: 5,8-dimethano-1,2,3,4,4
a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-ethyl-1,4: 5,8-dimethano-1,
4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,
2, 3, 4, 4a, 5, 5a, 6, 9, 9a, 10, 1
0a-dodecahydro-2,3-cyclopentadienoanthracene and the like; adducts of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,4,4a, 4b, 5, 8,
8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like can be mentioned. Further, in addition polymerization, as the olefinic monomer which can be copolymerized, in addition to ethylene, for example, propylene,
1-butene, 3-methyl-1-butene, 1-pentene,
Α-olefins such as 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-icosene; Cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, styrene, α-methylstyrene, 3a,
5,6,7a-Tetrahydro-4,7-methano-1H-
Non-crosslinked cycloolefins such as indene and styrenes; 1,4-hexadiene, 1,6-octadiene, 2
-Methyl-1,5-hexadiene, 6-methyl-1,5
-Heptadiene, 7-methyl-1,6-octadiene,
Cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene,
Non-conjugated dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene, divinylbenzene, 1,5-hexadiene, norbornadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-
Examples include trienes such as isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,5-octatriene and 1,4,9-decatriene.

Examples of the olefin-containing cyclic reactive monomer include those having a structure represented by the following formula (3) or (4).

[Chemical 3] (In the formula, X is a group independently selected from the group consisting of —O—, —NR—, and —CR ₂ —, and R is a group selected from hydrogen, an aliphatic group, or an aromatic group. The aliphatic group or aromatic group may contain a functional group as a substituent.R ¹ , R ² , R ³ and R ^{4 each} have an unsaturated carbon-carbon double bond. And an aliphatic group, an aromatic group which may have an unsaturated carbon / carbon double bond, and a hydrogen group, which are independently selected from the group consisting of these aliphatic groups and aromatic groups. the may contain as a substituent a functional group, also R ^1, R ^2, R ^3, R ⁴ good also form a ring with its one .R or R ^1, R ^2, R ³ ,
Examples of the functional group for R ⁴ include an ester group and / or an ether group. ) Specific examples of these olefin-containing cyclic reactive monomers include 4-acryloxymethyl-1,3-dioxolan-2-one and 4-methacryloxymethyl-1,3-
Dioxolan-2-one, 5-methacryloxymethyl-5-methyl-1,3-dioxan-2-one, 5-methacryloxymethyl-5-ethyl-1,3-dioxan-2-one, 4- Aryloxymethyl-1,3-dioxolan-2-one, 4- (2'-methylallyloxy) methyl-1,3-dioxolan-2-one, 5-allyloxymethyl-5-methyl-1,3- Dioxan-2-one, 5- (2'-methylallyloxy) methyl-5-methyl-1,3-dioxolan-2-one, 4- (5'-norbornene-2'-methyloxymethyl) -1,3- Dioxolan-2-one, 4- (3'-butenyl) -1,3
-Dioxolan-2-one, 1,2-carbonate-4
-Vinylcyclohexane, 4-vinyl-1,3-dioxolan-2-one, 4-vinyl-4-methyl-1,3-
Dioxolan-2-one, 4-allyl-1,3-dioxolan-2-one, 4- (2'-allylphenoxymethyl) -1,3-dioxolan-2-one, 5- (2'-
Allylphenoxymethyl) -5-methyl-1,3-dioxan-2-one, 4- (4'-isopropenylphenoxymethyl) -1,3-dioxolan-2-one, 5-
(4'-isopropenylphenoxymethyl) -5-methyl-1,3-dioxan-2-one, 4- (5'-norbornene-2'-carboxymethyl) -1,3-dioxolan-2-one, 5 -(5'-norbornene-2'-
Carboxymethyl) -5-methyl-1,3-dioxan-2-one and other cyclic carbonates; 4-acryloxymethyl-1,3-oxazolidin-2-one, 4-acryloxymethyl-3-methyl-1 , 3-oxazolidin-2-one, 4-acryloxymethyl-3-phenyl-
1,3-oxazolidin-2-one, 4-methacryloxymethyl-1,3-oxazolidin-2-one, 4-
Methacryloxymethyl-3-methyl-1,3-oxazolidin-2-one, 4-methacryloxymethyl-3
-Phenyl-1,3-oxazolidin-2-one, 4-
Aryloxymethyl-1,3-oxazolidin-2-one, 4-allyloxymethyl-3-phenyl-1,3-oxazolidin-2-one, 4-allyloxymethyl-3-
Methyl-1,3-oxazolidin-2-one, 4-
(2'-Methylallyloxymethyl) -1,3-oxazolidin-2-one, 4- (2'-methylallyloxymethyl) -3-phenyl-1,3-oxazolidin-2-one, 4-vinyl- 1,3-oxazolidin-2-one,
4-vinyl-3-phenyl-1,3-oxazolidine-
2-one, 4-vinyl-4-methyl-1,3-oxazolidin-2-one, 4-vinyl-4-methyl-3-phenyl-1,3-oxazolidin-2-one, 4-allyl-1, 3-oxazolidin-2-one, 4-allyl-3
-Phenyl-1,3-oxazolidin-2-one, 4-
(3'-butenyl) -1,3-oxazolidin-2-one, 4- (3'-butenyl) -3-methyl-1,3-oxazolidin-2-one, 4- (2'-allylphenoxymethyl) -1,3-oxazolidin-2-one, 4-
(2'-allylphenoxymethyl) -3-methyl-1,
3-oxazolidin-2-one, 4- (2'-allylphenoxymethyl) -3-phenyl-1,3-oxazolidin-2-one, 4- (4'-isopropenylphenoxymethyl) -1,3-oxazolidine -2-on, 4-
(4'-isopropenylphenoxymethyl) -3-methyl-1,3-oxazolidin-2-one, 4- (4'-
Isopropenylphenoxymethyl) -3-phenyl-
1,3-oxazolidin-2-one, 4- (5'-norbornene-2'-carboxymethyl) -1,3-oxazolidin-2-one, 4- (5'-norbornene-2 '
-Carboxymethyl) -3-methyl-1,3-oxazolidin-2-one, 4- (5'-norbornene-2'-
Oxazolidinones such as carboxymethyl) -3-phenyl-1,3-oxazolidin-2-one; 5-hexene-4-olide, 6-heptene-5-olide, 3-
Examples thereof include lactones such as vinyl-4-butanolide, 3-vinyl-5-pentanolide, 5-allyloxy-4-pentanolide, 9-deceno-5-olide, and among these, 4-aryloxymethyl-1 , 3-Dioxolan-2-one, 4-vinyl-1,3-dioxolan-2-one, 1,2-carbonate-4-vinylcyclohexene, 4- (2'-allylphenoxymethyl)-
1,3-dioxolan-2-one, 4-allyloxymethyl-3-phenyl-1,3-oxazolidin-2-one, 4- (2'-allylphenoxymethyl) -3-phenyl-1,3-oxazolidine 2-one and the like are preferably used.

As the thermoplastic cyclic olefin resin having a cyclic reactive group of the present invention, the cyclic reactive group-containing cyclic olefin resin obtained by the above various methods can be used alone or in combination. Further, the thermoplastic cyclic olefin-based resin having a cyclic reactive group may be a mixture of a cyclic olefin-containing cyclic olefin resin and a cyclic olefin-free cyclic olefin resin. Further, the thermoplastic cyclic olefin-based resin having these cyclic reactive groups may contain a functional group such as a hydroxyl group, an ester group, an organic silicon group and a carboxylic acid group in addition to the cyclic reactive group, and if desired, Various additives such as a phenol-based or phosphorus-based antiaging agent; a phenol-based heat deterioration inhibitor; an amine-based antistatic agent; and the like may be added.
Further, other resins within the range not impairing the object of the present invention,
It is also possible to use a mixture of rubber, filler and the like.

Photoreactive substance The photoreactive substance used in the present invention is a g-ray or h-ray.
The substance is not particularly limited as long as it is a substance that reacts with the cyclic olefin resin by irradiation with active rays such as ultraviolet rays such as rays and i rays, far ultraviolet rays, x rays, and electron rays to form a crosslinking compound, Examples thereof include aromatic bisazide compounds and photodiamine generators.

(I) Aromatic bisazide compound Specific examples of the aromatic bisazide compound include 4,4 '
-Diazidochalcone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) 4-methylcyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-di Azidobenzophenone, 4,4'-diazidodiphenyl, 2,2 '
-Diazidostilbene, 4,4'-diazide-3,3 '
-Dimethyldiphenyl, 2,7-diazidofluorene,
Typical examples are 4,4'-diazidodiphenylmethane and the like. These may be used alone or in combination of two or more.

(Ii) Photodiamine generator As specific examples of the photodiamine generator, aromatic polyamine or aliphatic polyamine o-nitrobenzyloxycarbonyl carbamate, 2,6-dinitrobenzyloxycarbonyl carbamate or α, α-dimethyl-
Examples thereof include 3,5-dimethoxybenzyloxycarbonyl carbamate compound, and specifically, hexamethylenediamine, diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1. 0 ^2,6 ]
Aliphatic polyamines such as decane, triethylenetetramine, 1,3- (diaminomethyl) cyclohexane,
4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, α,
α-bis (4-aminophenyl) -1,4-diisopropylbenzene, o-nitrobenzyloxycarbonylcarbamate, 2,6-dinitrobenzyloxycarbonylcarbamate or α, α-dimethyl of aromatic polyamines such as phenylenediamine A -3,5-dimethoxybenzyloxy carbonyl carbamate body is mentioned.
These may be used alone or in combination of two or more.

The amount of these photoreactive substances added is not particularly limited, but the reaction with the cyclic olefin resin is efficiently carried out, the developing characteristics are maintained well, and the physical properties of the resulting crosslinked resin are impaired. From the viewpoints of lack of cost and economy, it is 0.1 per 100 parts by weight of cyclic olefin resin
It is used in the range of -30 parts by weight, preferably 1-20 parts by weight. If the amount of the photoreactive substance added is too small, the reaction with the cyclic olefin resin is unlikely to occur, and sufficient sensitivity and contrast cannot be obtained, and if it is too large, the electrical properties of the crosslinked resin portion, low water absorption, etc. This is not preferable because the characteristics of (3) are degraded.

If desired, a sensitizer, a storage stabilizer, etc. may be added to the photosensitive resin composition of the present invention.
Examples of the sensitizer include benzophenone, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, carbonyl compounds such as p, p'-tetramethyldiaminobenzophenone and chloranil, nitrobenzene, p-dinitrobenzene, Nitro compounds such as 2-nitrofluorene, aromatic hydrocarbons such as anthracene and chrysene, sulfur compounds such as diphenyl disulfide, nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyano Examples thereof include nitrogen compounds such as ethylene, but are not limited thereto. Examples of storage stabilizers include hydroquinone, methoxyphenol, p
-T-butylcatechol, 2,6-di-t-butyl-p
-Hydroxy aromatic compounds such as cresol, benzoquinones, quinones such as p-toluquinone, phenyl-α-
Amines such as naphthylamine, 4,4′-thiobis (6-t-butyl-3-methylphenol), 2,2 ′
-Thiobis (4-methyl-6-t-butylphenol)
Examples thereof include, but are not limited to, sulfur compounds.

A curing agent which reacts with the cyclic reactive group may be added to assist the crosslinking reaction by these photoreactive substances. For example, a compound which can react with the cyclic reactive group by heating is added. As a compound which can be combined with a bisazide compound or a photodiamine generator, hexamethylenediamine, diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5,2,1,0 ^{2 , 6} ] Decane, 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylmethane, α, α'-bis (4-aminophenyl) -1,3
Polyamines such as diisopropylbenzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, diaminodiphenylsulfone, triethylenetetraamine, 1,3- (diaminomethyl) cyclohexane and phenylenediamine; Polyamides such as nylon-6, nylon-66, nylon-610, nylon-11, nylon-612, nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide, etc. These may be used alone or as a mixture of two or more. The mixing amount of the curing agent is not particularly limited, but from the standpoint of efficiently assisting the crosslinking reaction, improving physical properties of the obtained crosslinked product, and economical efficiency, the cycloolefin resin 100
0.1 to 30 parts by weight, preferably 1 to 2 parts by weight
Used in the range of 0 parts by weight.

When an aromatic bisazide compound is used as a photoreactive compound, an olefinic compound may be added as a crosslinking aid, and depending on the combination, the resolution and the pattern shape can be further improved. is there. Examples of such olefinic compounds include 1,4
-Hexadiene, 1,6-octadiene, 2-methyl-
1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-
2-norbornene, 5-methylene-2-norbornene,
Dienes such as 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, divinylbenzene, 1,5-hexadiene, norbornadiene, cyclooctadiene, 3-vinylcyclohexene; 2,3 -Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-
Trienes such as norbornene, 2-propenyl-2,5-norbornadiene, 1,3,5-octatriene, 1,4,9-decatriene, myrcene, 1,5,9-cyclododecatriene; diallyl phthalate, Examples include allylic crosslinking aids such as triallyl cyanurate and triallyl isocyanurate; and the like. These may be used alone or as a mixture of two or more. The compounding amount of the cross-linking aid is not particularly limited, but from the viewpoint of efficiently assisting the cross-linking reaction, improving the physical properties of the resulting cross-linked product, and economical efficiency, the cyclic olefin resin 1
0.1 to 30 parts by weight, preferably 1
Used in the range of up to 20 parts by weight.

The photosensitive resin composition of the present invention comprises a cyclic olefin resin having a cyclic reactive group and a photoreactive substance which reacts with the cyclic olefin resin upon irradiation with actinic rays to form a cross-linked compound. It is added uniformly. As a method for uniformly dispersing a photoreactive compound or a sensitizer and other additives in a cyclic olefin resin having a cyclic reactive group, a solvent is prepared by dissolving, mixing and dispersing in a resin solution. There are methods of removing the resin, mixing and dispersing the resin in a molten state, and the like. As a method of using these photosensitive resin compositions, they are usually used by being applied in a state of being dissolved in a solvent. The solvent is not particularly limited as long as it dissolves the resin and the photoreactive compound, but for example, toluene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, decalin, cyclohexane, tetralin, methylcyclohexane, etc. are used. be able to. The photocrosslinking cured product of the present invention is obtained by irradiating a photosensitive resin composition with an actinic ray to crosslink it. The actinic ray is a ray that activates the photoreactive compound, and is, for example, ultraviolet rays such as g rays, h rays, and i rays, far ultraviolet rays, x rays, and electron rays. As a method for obtaining a photo-crosslinked cured product, for example, a solution of a photosensitive resin composition is applied to a target substrate, dried and prebaked to obtain a coating film, and the coating film surface is irradiated with an actinic ray through a mask. Then, post-baking is performed if necessary, and then development and rinsing are performed to obtain a desired pattern. The crosslinked cured product of the present invention is obtained by heating the photocrosslinked cured product and further crosslinking. By further cross-linking the photo-crosslinked cured product in this way, the heat resistance can be further improved. The heating temperature varies depending on the types of the photosensitive resin composition and the photoreactive compound, but is usually 30 to
The temperature is 400 ° C, preferably 50 to 350 ° C, more preferably 100 to 300 ° C. The heating time is several seconds to 24 hours, preferably about 5 minutes to 10 hours. The photo-crosslinked cured product and the crosslinked cured product of the present invention thus obtained,
It has a low water absorption rate of 0.1% or less, an insulation resistance of 10 ¹⁵ to 10 ¹⁷ Ω, and a dielectric constant of 2.3 from 1 MHz.
3.0, dielectric loss tangent at 1 MHz is 0.0001 to 0.01
And has excellent electrical characteristics. In addition to being excellent in heat resistance and crack resistance, it is also excellent in adhesion to inorganic materials such as silicon and metals. Such a crosslinked molded article of the present invention can be used as a photocrosslinking cured product and a crosslinked cured product as an electrical insulating component such as a thin film interlayer insulating film. When used as a thin film interlayer insulating film, a solution of a photosensitive resin composition is applied to a substrate by a spin coating method or the like, then exposed and developed to form a pattern, heated and crosslinked, and then plated or sputtered. Form metal wiring. The insulating film may be a single layer or a multi-layer, but in the case of forming a multi-layer, the above operation may be repeated. The thickness of the interlayer insulating film is usually 50
It is set to be not more than μm. Polyimide is generally used as the thin film interlayer insulating film, but the dielectric constant of polyimide is usually 3.5 or more. In contrast,
The crosslinked cured product of the present invention has a dielectric constant of 3.0 or less and is excellent in insulation.

The present invention will be described more specifically below with reference to Reference Examples, Examples and Comparative Examples. The insulation resistance, dielectric constant, dielectric loss tangent, and water absorption rate are JIS K 6911.
It was measured by. Regarding the solvent resistance, the photosensitive resin composition solution was applied onto a silicon wafer to give a film thickness of 10 to 20.
The coating was applied by spin coating so as to have a thickness of about μm, and the coating was subjected to a crosslinking reaction at 250 ° C. for 3 hours. The cyclic reactive group content was measured by ¹ H-NMR.

Reference Example-1 6-methyl-1,4,5,8-dimethano-1,2,3,3
4,4a, 5,8,8a-octahydronaphthalene (M
TD) is subjected to ring-opening polymerization by a known method and hydrogenated to obtain a cyclic olefin resin [glass transition temperature 152 ° C., hydrogenation ratio approximately 100%: number average molecular weight approximately 28,000 (polystyrene conversion)] 50. Parts by weight and 4-allyloxy-1,3-
10 parts by weight of dioxolan-2-one, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3
By mixing 2 parts by weight and melt-kneading at 260 ° C. using a twin-screw extruder having a diameter of 30 mm, 51 parts of cyclic carbonate-modified cyclic olefin resin A was obtained [glass transition temperature 154 ° C., number average Molecular weight about 26,000
0 (polystyrene conversion)]. The cyclic carbonate group content of the obtained modified polymer was 5.1 mol% based on the total number of monomer units in the polymer.

Reference Example-2 An oxazolidinone-modified cyclic compound was prepared in the same manner as in Reference Example-1, except that 15 parts by weight of 4-allyloxymethyl-3-phenyl-1,3-oxazolidin-2-one was used as the modifying monomer. Olefin resin B was obtained [glass transition temperature 150 ° C., number average molecular weight 27,000 (converted to polystyrene)]. The oxazolidinone group content of the resulting modified polymer was 5.5 based on the total number of monomer units in the polymer.
It was mol%.

Reference Example-3 50 parts by weight of the cyclic olefin resin used in Reference Example-1 and 4- (3-butenyl) -1,3-dioxolane-2
14 parts by weight of -one and 3 parts by weight of dicumyl peroxide were dissolved in 120 parts by weight of cyclohexane and reacted at 150 ° C. for 3 hours in an autoclave, and then the reaction product solution was added in 240 parts by weight of isopropyl alcohol. Pour into
Solidified. The coagulated cyclic carbonate modified polymer was added to 10
It was vacuum dried at 0 ° C. for 5 hours to obtain 50 parts of cyclic carbonate-modified cyclic olefin resin C [glass transition temperature 15
4 ° C., number average molecular weight about 27,000 (polystyrene conversion)]. The cyclic carbonate group content of the obtained modified polymer was 6.0 mo based on the total number of monomer units in the polymer.
It was 1%.

Reference Example-4 A lactone-modified cyclic olefin system was used in the same manner as in Reference Example-3 except that 16 parts by weight of 5-hexene-4-olide was used as the modifying monomer and 4 parts by weight of dicumyl peroxide was used as the peroxide. Resin D was obtained (glass transition temperature 149 ° C., number average molecular weight about 26,000 (in terms of polystyrene)). The lactone group content of the obtained modified polymer was 6.1 mol% based on the total number of monomer units in the polymer.

Reference Example-5 Ethylene and M produced according to the method known in Reference Example-1
Random addition copolymer with TD [ethylene composition 50%,
Glass transition temperature 141 ° C, number average molecular weight 30,000
(Polystyrene conversion)] was used in the same manner as above, except that the starting resin was used to obtain cyclic carbonate-modified cyclic olefin resin E [glass transition temperature 140 ° C., number average molecular weight 28,000 (polystyrene conversion)]. The cyclic carbonate group content of the obtained modified polymer was 4.0 mol% based on the total number of monomer units in the polymer.

Reference Example-6 50 parts by weight of the raw material resin used in Reference Example-5 and 4-allyloxymethyl-3-phenyl-1,3-as a modifying monomer
An oxazolidinone-modified cyclic olefin resin F was obtained in the same manner as in Reference Example 3 except that 23 parts by weight of oxazolidin-2-one was used [glass transition temperature 145 ° C.,
Number average molecular weight 26,500 (in terms of polystyrene)]. The oxazolidinone group content of the obtained modified polymer was 4.5 mol% based on the total number of monomer units in the polymer.

Reference Example-7 In Reference Example-2, MTD and dicyclopentadiene (DC
P) a hydrogenated product of a copolymer obtained by ring-opening polymerization of a mixed monomer (MTD / DCP = 70/30 molar ratio) [glass transition temperature 133 ° C., hydrogenation rate almost 100%, number average molecular weight 2
7,000 (in terms of polystyrene)] was used in the same manner as above as the raw material resin to obtain cyclic carbonate-modified cyclic olefin resin G [glass transition temperature 135
C., number average molecular weight 26,000 (in terms of polystyrene)]. The cyclic carbonate group content of the obtained modified polymer was 7.0 mo based on the total number of monomer units in the polymer.
It was 1%.

Reference Example-8 MTD, ethylene and 4- (3-butenyl) -1,3-
Dioxolan-2-one (BDO) was used as a monomer component, VO (OEt) Cl ₂ and ethylaluminum sesquichloride were used as catalysts for random copolymerization by a known method, and the composition ratio of each monomer unit in the polymer was [ (MTD / ethylene / BDO = 45/50/5 molar ratio)
To obtain a cyclic carbonate group-containing cyclic olefin resin H (glass transition temperature 140 ° C., number average molecular weight 30,000).
0 (polystyrene conversion)]. The modified carbonate obtained had a cyclic carbonate group content of 9.5 mol% based on the total number of MTD skeletons in the polymer.

[0027]

【Example】

Example 1 30 parts by weight of the cyclic carbonate-modified cyclic olefin resin A obtained in Reference Example-1 and 1.5 parts by weight of 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone were dissolved in 100 parts by weight of xylene. Then, the mixture was filtered with a Millipore filter having a pore diameter of 0.22 μm to obtain a negative photosensitive resin composition. This solution was applied onto a silicon wafer using a spinner and then prebaked at 80 ° C. for 40 seconds to obtain a coating film having a film thickness of 5 μm. The light intensity at 365 nm is 5 mW / cm using a test pattern manufactured by Toppan Printing Co., Ltd.
After irradiating the ultraviolet ray of ² for 30 seconds and developing with cyclohexane, it was found that a pattern of 5 μm could be resolved. Then 250 in an oven under nitrogen
Curing was performed by heating at ℃ for 3 hours. This pattern was heated under nitrogen at 300 ° C. for 10 minutes, but no dripping of the pattern or film loss was observed. The evaluation of the adhesiveness by the goggles test was 100/100, which was sufficient adhesiveness. As a result of measuring the physical properties of the crosslinked cured product, the water absorption rate was 0.07%, the insulation resistance was 3 × 10 ¹⁶ Ω, and the dielectric constant and dielectric loss tangent at 1 MHz were 2.6 and 0.0005, respectively. .

Example 2 30 parts by weight of the cyclic carbonate-modified cyclic olefin resin A obtained in Reference Example-1 and 1.5 parts by weight of bis (2-nitrobenzyloxycarbonyl) hexane-1,6-diamine were added to 100 parts by weight of xylene. Pore size 0.22μ
The mixture was filtered through a Millipore filter of m to obtain a negative photosensitive resin composition. This solution was applied on a silicon wafer using a spinner and then prebaked at 80 ° C. for 90 seconds to obtain a coating film having a film thickness of 5 μm. Using a test pattern manufactured by Toppan Printing Co., Ltd., the light intensity at 365 nm is 5 mW / c.
After irradiating with m ² of ultraviolet rays for 30 seconds, baking was performed at 110 ° C. for 1 minute, and then development was performed using cyclohexane, and it was found that a 6 μm pattern could be resolved. Then, it was heated in an oven under nitrogen at 250 ° C. for 3 hours to be cured. This pattern under nitrogen 30
After heating at 0 ° C. for 10 minutes, no pattern dripping or film loss was observed. The evaluation of the adhesiveness by the goggles test was 100/100, which was sufficient adhesiveness. Also,
Physical property of cross-linked cured product is 0.06%, insulation resistance is 4 × 10
The dielectric constant and dielectric loss tangent at ¹⁶ Ω and 1 MHz are 2.
It was 5, 0.0002.

Example 3 The photosensitive resin composition solution used in Example 1 was applied onto a silicon wafer using a spinner, and then applied at 80 ° C. for 9 hours.
Pre-baking was performed for 0 seconds to obtain a coating film having a film thickness of 15 μm. Then, using a TETOS pattern mask for forming a via hole, an ultraviolet ray having a light intensity of 5 mW / cm ² at 365 nm was used.
After irradiation for 2 seconds, develop with cyclohexane, and
A via hole having a diameter of μm was formed. After that, heating and curing were performed in an oven under nitrogen at 250 ° C. for 3 hours. Next, the entire surface was plated with copper to form a copper layer having a film thickness of 5 μm, a resist was applied, and post-exposure development was performed using a mask for a wiring pattern. This was immersed in an aqueous solution of ammonium persulfate to etch copper, and the resist was peeled off to form a copper wiring. The photosensitive resin composition used previously was applied again to this, and the same operation was repeated to prepare a circuit board model of two insulating layers and two wiring layers. When creating this model, the various solvents used,
There was no problem such as cracking due to repeated coating of resin. Also, the circuit board should be soldered at 300 ° C
Even after contacting for a minute, no abnormality such as peeling of the copper wiring, blistering or peeling was observed.

Examples 4 to 12 As shown in Tables 1 to 4, the combination and mixing amount of the cyclic olefin resin and the photoreactive compound were changed, and Example 1 was changed.
Alternatively, the same process as in 2 was performed. The results are shown in Tables 1 to 4.

[0031]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example resin Photoreactive compound Method Resolution Heat resistance Heat resistance ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 4 A 4,4′-bisazidostilbene 1 5 μm ○ (30) (1.1) 5 B bis (2-nitrobenzyloxy 2 6 μm ○ (30) carbonyl) hexane-1,6-diamine (1.9) 6 B 2,6-bis (4′-azidobenzal) 1 5 μm ○ (30) -4-Methylcyclohexanone (1.5) 7 C 2,6-bis (4'-azidobenzal) 1 5 μm ○ (30) -4-Methylcyclohexanone (1.8) 8 D 2,6-bis (4 ' -Azidobenzal) 15 μm ○ (30) -4-Methylcyclohexanone (1.8) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ ・ Numbers in parentheses for resin and photoreactive compound are heavy. Representing the department. -Xylene (80 parts by weight) was used as the solvent. -Adhesion was 100/100 and good.

[0032]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example resin Photoreactive compound Method Resolution Resistance Solder Heat resistance ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 9 E 2,6-bis (4 ′ -Azidobenzal) 15 μm ○ (30) -4-Methylcyclohexanone (1.1) 10 F 2,6-Bis (4'-azidobenzal) 15 μm ○ (30) -4-Methylcyclohexanone (1.2) 11 G 2,6- Bis (4′-azidobenzal) 15 μm ○ (30) -4-Methylcyclohexanone (2.3) 12 H 2,6-bis (4′-azidobenzal) 15 μm ○ (30) -4-Methylcyclohexanone (2.4) ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ・ The figures in () for resin and photoreactive compound are Represents parts by weight. -Xylene (80 parts by weight) was used as the solvent. -Adhesion was 100/100 and good.

[0033]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example resin Photoreactive compound Dielectric water absorption Insulation resistance Dielectric constant (%) (Ω / cm) Tangent ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 4 A 4,4′-bisazidostilbene 2.5 0.05 4 × 10 ¹⁶ 0.0002 (30) (1.1) 5 B bis (2-nitrobenzyloxy 2.6 0.07 2 × 10 ¹⁶ 0.0006 (30) carbonyl) hexane-1,6-diamine (1.9) 6 B 2,6-bis (4′-azidobenzal) 2.6 0.07 3 × 10 ¹⁶ 0.0005 (30) -4-methylcyclohexanone (1.5) 7 C 2,6-bis (4′-azidobenzal) 2.7 0.09 2 × 10 ¹⁶ 0.001 (30) -4-Methylcyclohexanone (1.8) 8 D 2,6-bis (4'-azidobenzal) 2.6 0.06 4 × 10 ¹⁶ 0.0007 (30) -4-Methylcyclohexanone (1.8) ━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━ ・ Numbers in parentheses in the items of resin and photoreactive compound represent parts by weight. -Xylene (80 parts by weight) was used as the solvent. -Adhesion was 100/100 and good.

[0034]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example resin Photoreactive compound Dielectric water absorption Insulation resistance Dielectric constant (%) (Ω / cm) Tangent ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 9 E 2,6-bis (4′-azidobenzal) 2.4 0.02 8 × 10 ¹⁶ 0.0001 (30) -4-methylcyclohexanone (1.1) 10 F 2,6-bis (4′-azidobenzal) 2.5 0.05 5 × 10 ¹⁶ 0.0003 (30) -4-Methylcyclohexanone (1.2) 11 G 2,6-bis (4'-azidobenzal) 2.7 0.09 8 × 10 ¹⁶ 0.0018 (30) -4-Methylcyclohexanone (2.3) 12 H 2,6-bis ( 4'-azidobenzal) 2.8 0.10 1 × 10 ¹⁶ 0.0031 (30) -4-methylcyclohexanone (2.4) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━ ・ The figures in parentheses () for resin and photoreactive compound are parts by weight. It is. -Xylene (80 parts by weight) was used as the solvent. -Adhesion was 100/100 and good.

Comparative Example-1 6-Methyl-1,4,5,8-dimethano-1,2,3,3
Ring-opening polymerization of 4,4a, 5,8,8a-octahydronaphthalene was carried out by a known method to obtain a cyclic olefin ring-opening polymer (glass transition temperature 160 ° C., number average molecular weight about 2).
1,000). After dissolving 30 parts by weight of this polymer and 1.5 parts by weight of 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone in 80 parts by weight of xylene,
A negative photosensitive resin composition was obtained by filtering with a Millipore filter having a pore size of 0.22 μm. This solution is applied on a silicon wafer using a spinner and then at 90 ° C. for 90 minutes.
Prebaking was performed for 2 seconds to obtain a coating film having a film thickness of 5 μm. The test pattern manufactured by Toppan Printing Co., Ltd. was used to irradiate an ultraviolet ray having a light intensity at 365 nm of 5 mW / cm ² for 30 seconds, then developed with cyclohexane at 25 ° C. for 40 seconds, and then rinsed with n-hexane for 10 seconds. However, it was found that a 5 μm pattern could be resolved. Then, it was cured by heating in an oven under nitrogen at 25 ° C. for 3 hours. When this pattern was heated under nitrogen at 300 ° C. for 10 minutes, film loss was observed.

Comparative Example-2 6-methyl-1,4,5,8-dimethano-1,2,3,3
4,4a, 5,8,8a-octahydronaphthalene (M
TD) is subjected to ring-opening polymerization by a known method and hydrogenated to obtain a cyclic olefin resin (glass transition temperature 152 ° C.,
Hydrogenation rate is almost 100%, number average molecular weight is about 28,000) 3
0 parts by weight and 2,6-bis (4'-azidobenzal) -4
-Methylcyclohexanone 1.5 parts by weight of xylene 10
After dissolving in 0 part by weight, the mixture was filtered through a Millipore filter having a pore size of 0.22 μm to obtain a negative photosensitive resin composition. This solution was applied on a silicon wafer using a spinner and then prebaked at 80 ° C. for 90 seconds to give a film thickness of 5 μm.
A coating film of A test pattern manufactured by Toppan Printing Co., Ltd. was used to irradiate an ultraviolet ray having a light intensity at 365 nm of 5 mW / cm ² for 30 seconds, and then developed with cyclohexane to find that a pattern of 5 μm can be resolved. It was When this pattern was heated under nitrogen at 300 ° C. for 10 minutes, the pattern became blunt.

[0037]

[Effect] A photosensitive resin composition comprising a cyclic olefin group-modified cyclic olefin resin and a photoreactive substance can impart photosensitivity without impairing the characteristics of the cyclic olefin resin, and also has heat resistance. Can also be given.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location G03F 7/031 N12 7/40 501 H01L 21/027 (72) Inventor Yasuhiro Mitsuda Kawasaki, Kawasaki, Kanagawa Prefecture 1-2-1, Yokou, Ku, Japan Research & Development Center, ZEON Corporation

Claims (4)

[Claims] 1. A cyclic olefin resin (A) having a cyclic reactive group, and a photoreactive substance (B) which reacts with the cyclic olefin resin upon irradiation with actinic rays to form a cross-linking compound. A photosensitive resin composition comprising: 2. The cyclic reactive group is represented by the following formula (1): And the formula (2) (In the formula, X is a group independently selected from the group consisting of —O—, —NR—, and —CR ₂ —, and R is a group selected from hydrogen, an aliphatic group, or an aromatic group. The aliphatic group or aromatic group may contain a functional group as a substituent.R ¹ , R ² , R ³ and R ^{4 each} have an unsaturated carbon-carbon double bond. And an aliphatic group, an aromatic group which may have an unsaturated carbon / carbon double bond, and a hydrogen group, which are independently selected from the group consisting of these aliphatic groups and aromatic groups. May contain a functional group as a substituent, and R ¹ , R ² , R ³ and R ⁴ may combine with any one of them to form a ring.). The photosensitive resin composition according to claim 1, which is a group. 3. A photocrosslinking cured product obtained by crosslinking the photosensitive resin composition according to claim 1 by irradiation with actinic rays. 4. A crosslinked cured product obtained by further crosslinking by heating the photocrosslinking cured product according to claim 2.