JPH07104474A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To improve heat resistance, solvent resistance, water resistance or the like by containing annular olefin resin with a silicon compound residue containing a hydrolytic group, and a photo-reactive substance to generate a bridged compound via reaction with the resin. CONSTITUTION:In annular olefin resin (A) having a hydrolytic silicon group, a photo-reaction substance (B) to generate a bridged compound due to reaction with the resin (A) upon exposure to an activated beam, and a sensitizer and other additives as necessary are evenly dispersed. The (B) component is preferably 1 to 20 pts.wt. for the (A) component. The (A) component is resin having a silicon compound residue containing a hydrolytic group inside a molecular chain, at a side chain or at the end of a chain, and a number average molecular weight is between 5000 and 20000 (GPC analysis value using cyclohexane as solvent). Also, the resin preferably has a silicon content between 0.05 and 10% on the basis of polymer weight. Furthermore, an aromatic bisdiazo compound, optical diamine generating agent or the like can be mentioned as the (B) component.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a negative photosensitive resin composition having excellent heat resistance, solvent resistance, water resistance, electrical 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-140319), a photopolymerization initiator, and a sensitizer are used. , A copolymerization monomer (JP-A-61-2
3618) has been 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 a low dielectric constant, as a result, a cyclic olefin resin having a hydrolyzable group-containing silicon group was added to the cyclic olefin resin. By uniformly dispersing a photoreactive substance that reacts with a cross-linking compound to form a cross-linking compound, it was found that the photosensitivity can be imparted by irradiation with actinic rays without impairing the excellent properties of the cyclic olefin resin. It came to completion.

[0004]

Thus, the first aspect of the present invention
Is a photoreactive substance (B) that reacts with a cyclic olefin resin (A) having a hydrolyzable group-containing silicon compound residue by irradiation with actinic rays to form a cross-linked compound, and A negative photosensitive resin composition is provided by uniformly dispersing a sensitizer and other additives as needed.

A second aspect of the present invention is characterized in that a photocrosslinking cured product is provided by crosslinking the first photosensitive resin composition by irradiation with actinic rays.

Further, a third aspect of the present invention is characterized in that the second photo-crosslinked cured product is heated to provide a further cured crosslinked cured product. In the present invention, it is conceivable that the composition comprising the components (A) and (B) is first heat-cured and then photocrosslinked to obtain a crosslinked cured product. However, there is a problem that a pattern cannot be formed by the method.

The photocrosslinking cured product of the present invention is the above (B).
When the component is exposed to actinic rays, it cross-links mainly with a part of the component (A) which is not a hydrolyzable group-containing silicon compound residue or with a part of the hydrolyzable group-containing silicon compound residue. It is speculated that photosensitivity may be imparted to the photocrosslinking cured product, and the heat resistance of the photocrosslinking cured product may be further improved by the reaction of the hydrolyzable group-containing silicon compound residue.
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 20 parts by weight.

Cyclic Olefin Resin Having Hydrolyzable Group-Containing Silicon Compound Residue The hydrolyzable group used in the present invention has the ability to generate a hydroxyl group by hydrolysis. The cyclic olefin-based resin having a hydrolyzable group-containing silicon compound residue has a hydrolyzable group-containing silicon compound residue inside the molecular chain,
A resin having a side chain or a terminal portion, having a number average molecular weight of 500
0 to 200,000 (GPC analysis value using cyclohexane as a solvent), preferably 8,000 to 100,000, and the silicon content is 0.05 to 10%, preferably 0.1 to 5 based on the weight of the polymer. %, The cyclic olefin resin can be preferably used. The cyclic olefin resin having a hydrolyzable group-containing silicon compound residue 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) Hydrolyzable group-containing silicon monomer (c)
By a known ring-opening polymerization method, a ring-opening polymer obtained by polymerizing the cyclic olefin monomer with a titanium or tungsten compound as a catalyst is hydrogenated by a conventional hydrogenation method. Hydrogenated cyclic olefin resin, a polymer obtained by addition-polymerizing the cyclic olefin monomer and an unsaturated monomer such as ethylene with a transition metal compound / aluminum compound catalyst and the like by a known method, and / or the same. At least one selected from the group consisting of hydrogenated products or cyclic olefin resins obtained by addition-polymerizing a cyclic olefin monomer by a known method using a transition metal compound / aluminum compound catalyst or a palladium catalyst. The resin is a hydrolyzable group-containing silicon monomer (c) [included in the general formula (1) , Which is a type of monomer that is polymerized by a carbon-carbon unsaturated bond contained in this monomer]. The graft reaction can be carried out by a known method, and a cyclic olefin polymer having a hydrolyzable group-containing silicon compound residue can be obtained by a solution method or a melting method using a radical generator such as peroxide. .

(Ii) Copolymerization of a cyclic olefin monomer (a) having a hydrolyzable group-containing silicon compound residue. The copolymerization of the cyclic olefin-based monomer (a) having a hydrolyzable group-containing silicon compound residue [included in the general formula (1)] and the cyclic olefin monomer (b) is A cyclic olefin-based monomer having a hydrolyzable group-containing silicon compound residue which can be carried out by a known method
A cyclic olefin polymer having a hydrolyzable group-containing silicon compound residue can be obtained by hydrogenating a ring-opening polymer obtained by subjecting (a) to ring-opening polymerization.

(Iii) Hydrosilylation Reaction of Silicon Compound (d) Having Hydrolyzable Group and Hydrogen Group In a ring-opening polymer of a cyclic olefin monomer obtained by a known method, a platinum catalyst is present. A hydrolyzable group-containing silicon compound (d) having a hydrolyzable group and a hydrogen group (which is included in the general formula (2)) is hydrolyzed. A hydrolyzable group-containing silicon compound residue is obtained by introducing a hydrogen compound-containing residue and hydrogenating the resulting ring-opening polymer having a hydrolyzable group-containing silicon compound residue by a known method. It is possible to obtain a cyclic olefin polymer having Of the silicon compounds having a hydrolyzable group and a hydrogen group (d), preferred compounds include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethylmethoxysilane and dimethylethoxysilane. , Trimethoxysilane, triethoxysilane and the like.

Examples of the cyclic olefin-based monomer (b) used for producing the cyclic olefin-based resin having a hydrolyzable group-containing silicon compound residue include the following. That is, Japanese Patent Laid-Open Nos. 3-14882 and 3-12
2137, JP-A-2-227424, JP-A-2-276.
Known monomers such as 842, norbornene, its alkyl, alkylidene, aromatic substituted derivatives and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups, amide groups of these substituted or unsubstituted olefins, Substituted polar groups such as imide group and silyl group, 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-1,2,3,4,4a,
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, 10,10a
-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, 8
a, 9a-octahydrofluorene, 5,8-methano-
1,2,3,4,4a, 5,8,8a-octahydro-
2,3-cyclopentadienonaphthalene and the like can be mentioned.

As the olefinic monomer (e) which can be copolymerized during the addition polymerization, other than ethylene, for example, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3 -Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1
Α-olefins such as -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
-Cycloolefins and styrenes without crosslinks such as methano-1H-indene; 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-
Non-conjugated dienes such as norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, divinylbenzene, 1,5-hexadiene, norbornadiene;
2,3-diisopropylidene-5-norbornene, 2-
Ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,
Trienes such as 3,5-octatriene and 1,4,9-decatriene may be mentioned.

Hydrolyzable group-containing silicon monomer [above (a)
And (c) are included in the general formula

## STR3 ## RR'R "SiY ... (1) R is a group having a polymerizable double bond, for example, vinyl group, allyl group, butenyl group, cyclohexenyl cyclopentadienyl. Group, CH ₂ = C (CH ₃ ) C
_{OO (CH 2) 3 -,} CH 2 = C (CH 3) COOCH 2 O
_{(CH 2) 3 -, CH} 2 = C (CH 3) COOCH 2 OCH 2
_{CH (OH) CH 2 O (} CH 2) 3 -, but like, especially a vinyl group is preferable. Y is a hydrolyzable organic group, for example, a halogen group such as a chlorine atom or a bromine atom; an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group; an acyloxy group such as a formyloxy group, an acetoxy group or a propionoxy group. Group; -ON = C (C
_{8 H 5) 2, -ON =} OCH 3 C 2 H 5, -ON = C (C
₈ H ₅₎ oxime groups such as _2; -NHCH _3, -NHC ₂
H _5, and a substituted amino group such as -NHC ₆ H ₅ and the like. R ′ and R ″ may be the same or different and each is an aliphatic unsaturated hydrocarbon group, a hydrocarbonoxy group, a hydroxyl group, a hydrolyzable group or an organic group having no olefinic unsaturated bond. Examples of the group selected from the group consisting of R and Y include groups similar to R and Y, and groups such as a methyl group, an ethyl group, a propyl group, a tetradecyl group, a phenyl group, a benzyl group, and a tolyl group.

Preferred hydrolyzable group-containing silicon monomer
As (c), vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylphenyldimethoxysilane or vinyltrimethoxysilane is particularly preferable.

The cyclic olefin-based monomer (a) having a residual chain of a hydrolyzable group-containing silicon compound is 3- (β-trichlorosilyl-ethyl) cyclooctene-1; 2-trichlorosilyl-5-norbornene. 2- (dichloromethylsilyl) -5-norbornene; 3-dibutylethoxysilyl-cyclopentene-1; 1-dimethylbromsilyl-cyclododecadien-4,8; 1-methyl-3-
Tributoxysilyl-cyclooctadiene-1,5; 5
-Triacetoxysilyl-cyclooctene-1; 4-cyclopropylchlorosilyl-cyclopentene-1; 2-
Examples thereof include dimethylmethoxysilyl-5-norbornene; 2-dimethylacetylsilyl-5-norbornene; 5,9-bis (trichlorosilyl) cyclododecene-1. Among these, 2-trichlorosilyl-5-norbornene, 2- (dichloromethylsilyl) -5-norbornene, 2-dimethylmethoxysilyl-5-norbornene and the like are preferably used.

The silicon compound having a hydrogen atom bonded to a silicon atom and a hydrolyzable group is, for example, a silicon compound represented by the following general formula (2).

Embedded image HSiA in _{3-x Y x ............ (2} ) formula, A is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
20 aryl group, an aralkyl group having 7 to 20 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a tetradecyl group, a phenyl group, a benzyl group, a tolyl group and the like are shown, and may be the same. It can be different. Y is a hydroxyl group or a hydrolyzable group, and the same structure as the hydrolyzable group represented by the formula (1) is exemplified, and when two or more are bonded, they may be the same or different, and x is 1 to
It is an integer of 3.

Specific examples of the silicon compound represented by the general formula (2) include halogenated silanes such as trichlorosilane, methyldichlorosilane and dimethylchlorosilane; trimethoxysilane, triethoxysilane, methyldimethoxysilane and phenyl. Alkoxysilanes such as dimethoxysilane and dimethylethoxysilane; Acyloxysilanes such as methyldiacetoxysilane; Ketoxymate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane; methyldi ( Isopropenyloxy)
Examples thereof include, but are not limited to, alkenyloxysilanes such as silane.

Of these silicon compounds, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, methyldiethoxysilane, methyldimethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, triethoxysilane, trimethoxysilane and the like are preferable. A cycloolefin polymer having a chlorosilyl group as a hydrolyzable group-containing silicon group throughout the present invention may be practically inconvenient because it hydrolyzes to generate hydrogen chloride gas or hydrochloric acid. Therefore, the chlorine atom of this chlorosilyl group is replaced with an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group,
It is preferably used after being converted into a hydroxyl group or the like.
Among these, an alkoxy group is particularly preferable because it has mild hydrolyzability and is easy to handle.

The cyclic olefin resin may contain a functional group such as a hydroxyl group, an ester group or a carboxylic acid group in addition to the residual chain of the hydrolyzable group-containing silicon compound, and if desired, a phenolic group, a phosphorus group or the like. Various additives such as anti-aging agents, thermal deterioration inhibitors such as phenols, antistatic agents such as amines, and the like may be added. Further, other resins, rubbers, fillers and the like can be mixed and used as long as the object of the present invention is not impaired.

Photoreactive Compound The photoreactive compound 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, For example, aromatic bisazide compounds, photodiamine generators, photoacid generators and the like can be mentioned.

(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 the photodiamine generator, aromatic amine or aliphatic amine o-nitrobenzyloxycarbonyl carbamate, 2,6-dinitrobenzyloxycarbonyl carbamate or α, α-dimethyl is used. Examples of the -3,5-dimethoxybenzyloxycarbonyl carbamate body and the like, specifically, aniline, cyclohexylamine, piperidine, hexamethylenediamine, triethylenetetramine, 1,3- (diaminomethyl) cyclohexane,
4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, phenylenediamine, o-nitrobenzyloxycarbonylcarbamate, 2,6-dinitrobenzyloxycarbonylcarbamate or α, α-dimethyl-3,5-dimethoxybenzyloxy A carbonyl carbamate body is mentioned. These may be used alone or in combination of two or more.

(Iii) Photo-acid generator The photo-acid generator is a substance which produces a Bronsted acid or a Lewis acid upon irradiation with actinic rays.
For example, onium salts, halogenated organic compounds, quinonediazide compounds, α, αbis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfone compounds, organic acid ester compounds,
Examples thereof include organic acid amide compounds and organic acid imide compounds. Specific examples of the onium salt include unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group,
Examples thereof include a diazonium salt, an ammonium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, an arsonium salt, and an oxonium salt having an aralkyl group, an aromatic group, and a heterocyclic group. Specific examples of the counter anion of these onium salts are not particularly limited as long as they are compounds capable of forming a counter anion, and boric acid, arsenic acid, phosphoric acid, antimonic acid, sulfonic acid, carboxylic acid, or these And the halides thereof. The halogenated organic compound is not particularly limited as long as it is a halide of an organic compound, various known compounds are possible, and specific examples thereof include a halogen-containing oxadiazole-based compound,
Halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing compounds Various compounds such as 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, and sulphenyl halide compounds can be mentioned. Further, as halogenated organic compounds, tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3-chloropropyl)
Phosphate, chlorotetrabromoethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A,
Tetrabromobisphenol A, bis (bromoethyl ether) tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,3-dibromopropyl) isocyanurate,
Halogen-containing flame retardants such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, dichlorodiphenyltrichloroethane, Benzene hexachloride, pentachlorophenol,
2,4,6-Trichlorophenyl-4-nitrophenyl ether, 2,4-dichlorofer-3'-methoxy-
4'-nitrophenyl ether, 2,4-dichlorophenoxyacetic acid, 4,5,6,7-tetrachlorophthalide, 1,1-bis (4-chlorophenyl) ethanol,
1,1-bis (4-chlorophenyl) -2,2,2-trichloroethanol, ethyl-4,4-dichlorobenzylate, 2,4,5,4'-tetrachlorodiphenyl sulfide, 2,4,5,5 Organic chloro-based pesticides such as 4'-tetrachlorodiphenyl sulfone are also included. Specific examples of the o-quinonediazide compound include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2
-Naphthoquinonediazide-5-sulfonic acid ester,
1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-6-sulfonic acid Esters, sulfonates of other quinonediazide derivatives, 1,2-benzoquinonediazide-4-
Sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-6-sulfonic acid chloride, 2,1-naphthoquinonediazide- 4-sulfonic acid chloride, 2,
Examples thereof include 1-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-6-sulfonic acid chloride, and sulfonic acid chlorides of other quinone azide derivatives. Specific examples of α, α bis (sulfonyl) diazomethane compounds include α, α having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group. Examples thereof include bis (sulfonyl) diazomethane. Specific examples of the α-carbonyl-α-sulfonyl-diazomethane compound include an α- having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group. Carbonyl-α-sulfonyl-diazomethane and the like can be mentioned. Specific examples of the sulfone compound include an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, sulfone compound having a heterocyclic group, and a disulfone compound. Specific examples of the organic acid ester include unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, carboxylic acid ester having a heterocyclic group, sulfonic acid ester and the like. To be Specific examples of the organic acid amide include unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, carboxylic acid amide having a heterocyclic group, sulfonic acid amide and the like. To be Specific examples of the organic acid imide include unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group,
Examples thereof include carboxylic acid imides having aromatic groups and heterocyclic groups, and sulfonic acid imides. These acid-cleavable compounds upon irradiation with actinic rays may be used alone or in combination of two or more.

The addition amount of these photoreactive compounds 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 obtained crosslinked resin are impaired. From the standpoints of lack and economy, it is used in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the cyclic olefin resin. If the amount of the photoreactive compound added is too small, the reaction with the cyclic olefin resin is difficult to occur, and sufficient sensitivity and contrast cannot be obtained, and if it is too large, the electrical properties, water resistance, and moisture resistance of the crosslinked resin part It is not preferable because properties such as properties are deteriorated.

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.

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, tetracyanoethylene Examples thereof include, but are not limited to, nitrogen compounds.

Examples of storage stabilizers include hydroquinone, methoxyphenol, pt-butylcatechol,
Hydroxy aromatic compounds such as 2,6-di-t-butyl-p-cresol, quinones such as benzoquinone and p-toluquinone, amines such as phenyl-α-naphthylamine, 4,4′-thiobis (6-t -Butyl-3-methylphenol), 2,2'-thiobis (4-methyl-6)
Examples thereof include sulfur compounds such as -t-butylphenol), but are not limited thereto.

The negative photosensitive resin composition of the present invention is usually dissolved in a solvent before use. The solvent is not particularly limited as long as it dissolves the resin and the photoreactive compound, and examples thereof include toluene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, decalin, cyclohexane, tetralin, methylcyclohexane and trichloroethylene. Can be used.

This negative photosensitive resin composition solution is applied to a required substrate, dried and pre-baked, the coated surface is irradiated with light through a mask, post-baked if necessary, and then developed, By rinsing and curing
Create a desired pattern. Further, in order to further improve the heat resistance of the formed pattern, it is possible to carry out a heating cure, and the optimum conditions vary depending on the types of the photoreactive compound and the curing agent, but the temperature is 30 ° C to 400 ° C.
C., preferably 100.degree. C. to 350.degree. C., and the time is several seconds to 1 day, preferably about 10 minutes to 5 hours, but is not particularly limited thereto. Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples. The dielectric constant and water absorption rate are JIS C648.
1 was measured. The silicon content of each resin is ¹ H-N
It was measured by MR.

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
℃, hydrogenation rate almost 100%: number average molecular weight about 28,000
(In terms of polystyrene)] 50 parts by weight and vinyltriethoxysilane [corresponding to the monomer of (c)] 10 parts by weight,
By mixing 5 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and melt-kneading at 260 ° C. using a twin screw extruder with a diameter of 30 mm vent device, 51 parts by weight of a silicon-modified cyclic olefin resin A [corresponding to the resin of the above (i)] was obtained [glass transition temperature 155 ° C., number average molecular weight about 29,000 (in terms of polystyrene)]. The silicon content of the obtained modified polymer was 0.74% based on the weight of the polymer.

Reference Example-2 50 parts by weight of the cyclic olefin resin used in Reference Example-1 and 8 parts by weight of vinyltrimethoxysilane [corresponding to the monomer of the above (c)], 1.5 parts by weight of dicumyl peroxide. Parts were dissolved in 120 parts by weight of cyclohexane, reacted at 150 ° C. for 3 hours in an autoclave, and then the reaction product solution was poured into 240 parts by weight of isopropyl alcohol to solidify. The solidified silicon-modified polymer is vacuum dried at 100 ° C. for 5 hours to obtain a silicon-modified cyclic olefin resin B.
50 parts by weight of [corresponding to the resin (i) above] were obtained [glass transition temperature of 155 ° C., number average molecular weight of about 29,000 (polystyrene conversion)]. The silicon content of the obtained modified polymer was 0.74% based on the weight of the polymer.

Reference Example-3 Random addition copolymer of ethylene and MTD produced by a known method (ethylene composition 50%, glass transition temperature 141 ° C., number average molecular weight 30,000 (polystyrene conversion) is used as raw material resin. Except for doing
Silicon-modified cyclic olefin resin C
[Corresponding to the resin of (i) above] was obtained [glass transition temperature 1
42 ° C., number average molecular weight 30,000 (in terms of polystyrene)]. The silicon content of the obtained modified polymer was 0.70% based on the weight of the polymer.

Reference Example-4 Hydrogenated product of a copolymer obtained by ring-opening polymerization of a mixed monomer (MTD / DCP = 70/30 molar ratio) of MTD and dicyclopentadiene (DCP) [glass transition temperature 133 ℃,
A hydrogenation ratio of about 100% and a number average molecular weight of 27,000 (in terms of polystyrene) are used as the raw material resin, and the same procedure as in Reference Example-2 is performed to obtain a silicon-modified cyclic olefin resin D [(i) above]. [Corresponding to resin] was obtained (glass transition temperature 135 ° C., number average molecular weight 27,000 (in terms of polystyrene)). The epoxy oxygen content of the resulting modified polymer is
It was 1.0% based on the polymer weight.

Reference Example-5 Mixed monomer (MTD / MTD / 2-trichlorosilyl-5-norbornene [corresponding to the monomer of the above (a)]]
After the ring-opening polymerization of a silicon monomer (molar ratio = 95: 5) by a known method, the copolymer is treated with methanol to hydrogenate the copolymer having a trichloro group as a trimethoxy group to obtain a silicon-modified cyclic olefin resin E. [Equivalent to the resin of (ii) above]
[Glass transition temperature 150 ° C., hydrogenation rate almost 100%, number average molecular weight 26,000 (converted to polystyrene)] was obtained.
The silicon content of the obtained modified polymer was 0.8% based on the weight of the polymer.

Reference Example 6 MTD was subjected to ring-opening polymerization by a known method to obtain an MTD ring-opening polymer [glass transition temperature 160 ° C., number average molecular weight 20,0].
00]. 30 parts by weight of this ring-opening polymer was added to cyclohexane 2
It was dissolved in 100 parts by weight, and charged in an autoclave together with 1.0 part by weight of platinum / carbon (support amount: 2% by weight) and 1.5 parts by weight of methyldiethoxysilane [corresponding to the compound (d)]. The reaction was carried out at a temperature of 100 ° C. for 5 hours. After the reaction solution was filtered to remove the platinum catalyst, the filtrate was poured into 600 parts by weight of isopropanol to coagulate. The solidified silicon-modified polymer was vacuum dried at 100 ° C. for 5 hours to obtain 30 parts by weight of a silicon-modified ring-opening polymer (silicon-modified cyclic olefin polymer). Next, the obtained silicon-modified cyclic olefin polymer was dissolved in 200 parts by weight of cyclohexane, and palladium / carbon (support amount: 5% by weight)
Add 0.6 parts by weight, hydrogen pressure 70 kg / cm ² , temperature 1
Hydrogenation reaction was carried out at 40 ° C. for 4 hours. After the reaction solution was filtered to remove the palladium catalyst, the filtrate was poured into 600 parts by weight of isopropanol to coagulate. The solidified silicon-modified polymer was vacuum dried at 10 ° C. for 5 hours to obtain a silicon-modified cyclic olefin polymer F [corresponding to the resin of the above (iii)] [glass transition temperature 155 ° C., hydrogenation rate almost 1
00%, number average molecular weight 28,000 (polystyrene conversion)] was obtained. The silicon content of the obtained modified polymer was 0.4% based on the weight of the polymer.

[0037]

【Example】

Example 1 Silicon modified cyclic olefin resin A3 obtained in Reference Example-1
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.
m coating film was obtained. 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 Then, it was heated in an oven under nitrogen at 250 ° C. for 3 hours to be cured. This pattern under nitrogen at 300 ℃
After heating for 10 minutes, no pattern dripping or film loss was observed. Further, the adhesiveness was evaluated to be 100/100 by the goggles test, which was sufficient.

Example 2 The negative photosensitive resin composition solution used in Example 1 was applied on a Teflon plate by a coating machine so as to have a thickness of 750 μm. 20 minutes at 60 ℃, 10 at 110 ℃
After leaving it to dry for 3 minutes, the light intensity at 365 nm is 5
Ultraviolet rays of mW / cm ² were irradiated for 5 seconds. After that, it was peeled off from the Teflon plate. The thickness of the obtained sheet is about 150μ.
It was m. Eight sheets of this are laminated and pressed at a pressing temperature of 20.
A sample was prepared by pressing for 1 hour at 0 ° C. and a pressing pressure of 40 kg / cm ² to a thickness of 1 mm and heat-sealing,
As a result of measuring physical properties, the water absorption rate was 0.02%, and the dielectric constant at 1 MHz was 2.3.

Example 3 Silicon modified cyclic olefin resin A3 obtained in Reference Example-1
After dissolving 0 parts by weight and 1.1 parts by weight of α, α'-dibromo-p-xylene in 100 parts by weight of xylene, the pore size was 0.2.
A negative photosensitive resin composition was obtained by filtering with a 2 μm Millipore filter. This solution was applied on a silicon wafer using a spinner and then prebaked at 80 ° C. for 5 minutes 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 was 5 mW /
After irradiating 30 cm ² of UV light for 1 second at 110 ℃
After baking for a minute and then developing with cyclohexane, 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. Then, in an oven under nitrogen 2
Curing was performed by heating at 50 ° C. for 3 hours. This pattern was heated under nitrogen at 300 ° C. for 10 minutes, but no dripping of the pattern or film reduction was observed. Further, the adhesiveness was evaluated to be 100/100 by the goggles test, which was sufficient.

Example 4 When the physical properties of a sample prepared in the same manner as in Example-2 were measured, the water absorption was 0.02% and the dielectric constant at 1 MHz was 2.3.

Examples 5 to 12 As shown in Tables 1 and 2, the same treatment as in Example 1 or 3 was carried out by changing the combination and the blending amount of the cyclic olefin resin and the photoreactive compound. The results are shown in Tables 1 and 2.

[Table 1] Example Resin * Photoreactive substance * Method Resolution 300 ° C Adhesion Heat resistance ━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━ 5 A 4,4'-bisazidostilbene 15 μm ○ ○ (30) (1.0) 6 A Bisphenol A 3 6 μm ○ ○ (30) Di-p-toluenesulfonate (0.4) 7 A bis (2-nitrobenzyloxy 3 6 μm ○ ○ (30) carbonyl) hexane-1,6-diamine (2.0) 8 B 2,6-bis (4′-azidobenzal) 15 μm ○ ○ (30) -4- Methylcyclohexanone (1.5) 9 C 2,6-bis (4'-azidobenzal) 15 μm ○ ○ (30) -4-Methylcyclohexanone (1.4) 10 D 2,6-bis (4'-azidobenzal) 15 μm ○ ○ (30) -4-Methylcyclohexanone (1.5) 11 E 2,6-bis (4'-azidobenzal) 15 μm ○ ○ (30) -4-Methylcyclohexanone (1.4) 12 F 2,6-bis (4'- Azido benzal) 1 5 m ○ ○ (30) -4- methyl cyclohexanone (1.5)

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example resin * Photoreactive substance * Method Water absorption rate (%) Dielectric constant ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 5 A 4,4′- Bisazidostilbene 1 0.02 2.3 (30) (1.1) 6 A Bisphenol A 3 0.03 2.4 (30) Di-p-toluenesulfonate (0.4) 7 A Bis (2-nitrobenzyloxy 3 0.03 2.4 (30) Carbonyl) hexane- 1,6-diamine (2.0) 8 B 2,6-bis (4'-azidobenzal) 1 0.02 2.3 (30) -4-methylcyclohexanone (1.5) 9 C 2,6-bis (4'-azidobenzal) 1 0.02 2.3 (30) -4-Methylcyclohexanone (1.5) 10 D 2,6-bis (4'-azidobenzal) 1 0.03 2.4 (30) -4-Methylcyclohexanone (1.5) 11 E 2,6-bis (4'- Azidobenzal) 1 0.03 2.4 (30) -4-methylcyclohe Sanone (1.4) 12 F 2,6-bis (4'-azidobenzal) 1 0.02 2.3 (30) -4-methylcyclohexanone (1.5) ━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━ * The figures in parentheses in the items of resin and photoreactive substance represent parts by weight. Xylene (80 parts by weight) was used as the solvent.

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 was applied on a silicon wafer using a spinner and then prebaked at 80 ° C. for 5 minutes to obtain a coating film having a film thickness of 5 μm. 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 Then, it was heated in an oven under nitrogen at 250 ° C. for 3 hours to be cured. 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.

[0044]

According to the present invention, a novel silicon-modified photosensitive resin composition having excellent heat resistance, solvent resistance, water resistance, and electric insulation can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location G03F 7/004 503 7/008 7/028 7/075 511 H01L 21/027 (72) Inventor Mitsuda Yasuhiro 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Corporation Research and Development Center

Claims (8)

[Claims] 1. A cyclic olefin resin (A) having a hydrolyzable group-containing silicon compound residue, and a photoreactive substance which reacts with the cyclic olefin resin upon irradiation with actinic rays to form a cross-linking compound ( B) is contained, The photosensitive resin composition characterized by the above-mentioned. 2. The hydrolyzable group-containing silicon compound residue is represented by the following general formula (1): RR′R ″ SiY (1) (R is a group having a polymerizable double bond) , Y is a hydroxyl group or a hydrolyzable group, R ′ and R ″ may be the same or different, and each is an aliphatic unsaturated hydrocarbon group or a hydrocarbonoxy group, a hydroxyl group, a hydrolyzable group, Alternatively, the photosensitive resin composition according to claim 1, which is derived from a silicon compound containing a hydrolyzable group represented by (a group selected from organic groups having no olefinic unsaturated bond). 3. The hydrolyzable group-containing silicon monomer represented by the general formula is vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylphenyldimethoxysilane, 2-trichlorosilyl-.
5-norbornene, 2- (dichloromethylsilyl) -5
-Norbornene, 2-dimethylmethoxysilyl-5-norbornene selected from the group consisting of:
The photosensitive resin composition described. 4. The hydrolyzable group-containing silicon compound residue is represented by the general formula (2): embedded image HSiA _3-x Y _x ...... (2) (A is a group having 1 to 20 carbon atoms) Alkyl group, carbon number 6-20
And an aralkyl group having 7 to 20 carbon atoms,
They may be the same or different, Y is a hydroxyl group or a hydrolyzable group, and when two or more are bonded, they may be the same or different, and x is 1 to
The photosensitive resin composition according to claim 1, which is derived from a hydrolyzable group-containing silicon compound represented by the formula (3 is an integer of 3). 5. The silicon compound is trichlorosilane,
The photosensitive resin composition according to claim 4, which is selected from the group consisting of methyldichlorosilane, dimethylchlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, trimethoxysilane and triethoxysilane. object. 6. A cyclic olefin resin (A) having a hydrolyzable group-containing silicon compound residue is a resin having a hydrolyzable group-containing silicon compound residue in the molecular chain, in a side chain or at a terminal portion. The number average molecular weight is 5,000 to 200,000 (GPC analysis value using cyclohexane as a solvent), and the silicon content is 0.05 to 10% based on the weight of the polymer. The photosensitive resin composition described. 7. A photocrosslinking cured product obtained by crosslinking the photosensitive resin composition according to claim 1, 2, 3, 4, 5 or 6 by irradiation with actinic rays. 8. A crosslinked cured product obtained by further crosslinking the photocrosslinked cured product according to claim 7 by heating.