CN101644891B - Positively photosensitive insulating resin composition and cured object obtained therefrom - Google Patents

Abstract

The positive photosensitive insulating resin composition of the present invention at least includes (A) alkali-soluble resin containing phenolic hydroxyl group, (B) compound containing quinone diazide group, (C) crosslinked fine particles, (D) containing at least A compound of two alkyl etherified amino groups, (F) a solvent. The positive photosensitive insulating resin composition has excellent resolution, electrical insulation performance and thermal shock performance. The cured product of the present invention is obtained by curing the positive photosensitive insulating resin composition, and the cured product has good adhesiveness.

Description

Positive photosensitive insulating resin composition and cured product thereof

This application is the international application number PCT/JP 03/00260, the international application date is January 15, 2003. After the PCT international application entered the Chinese national phase, the application number is 03800281.7, and the invention name is "positive photosensitive insulating resin composition" and its cured products” is a divisional application of the invention patent application.

technical field

The present invention relates to a positive photosensitive insulating resin composition for producing products such as interlayer insulating films (passivation films), surface protective films (protective films), or insulating films for high-density mounting boards. More specifically, the present invention relates to a positive-type photosensitive insulating resin composition capable of being cured to obtain a product having excellent electrical insulation properties, thermal shock properties and adhesive properties as a resist of an inherent film with good resolution; The invention also relates to cured products obtained from said compositions.

technical background

Polyimide resins with excellent heat resistance and mechanical properties are widely used in the production of interlayer insulating films and surface protective films for semiconductor elements of electronic equipment. In order to improve the yield and accuracy of forming the film, many studies have been made to impart good photosensitivity to polyimide resins, that is, photosensitive polyimide resins. For example, negative photosensitive polyimide resins have been put into practical use. The negative photosensitive polyimide resin is prepared by introducing a photo-crosslinkable group into a polyimide precursor through an ester bond or an ion bond. Regarding the positive photosensitive polyimide resin, compositions comprising a polyimide precursor and an o-quinonediazide compound are disclosed in JP-A-5(1993)-5996 and JP-A-2000-98601 . However, negative photosensitive polyimide resins have problems in resolution and film formation, and positive photosensitive polyimide resins have problems in heat resistance, electrical insulation performance and adhesion to substrates. Although there are many other patent applications in this field, those patent applications do not lead to a satisfactory solution to meet the demands of the trend towards high integration, small thickness semiconductor components. In addition, these resin compositions have disadvantages such as curing resulting in reduced thickness (volume shrinkage) and involving multiple stages of baking and environmental control. Due to these problems, it has been pointed out that these resin compositions are disadvantageous for industrial production.

Contents of the invention

The present invention aims to solve the aforementioned problems in the prior art. Accordingly, an object of the present invention is to provide a positive photosensitive insulating resin composition having good resolution and capable of being cured to obtain a product having excellent properties such as electrical insulation, thermal shock and adhesive properties. The cured product is suitable for use in components such as interlayer insulating films and surface protection films of semiconductor elements.

Another object of the present invention is to provide a cured product obtained by curing the above composition.

The inventors of the present invention earnestly studied to solve the above-mentioned problems. As a result, a positive photosensitive insulating resin composition having excellent properties has been found.

The first positive photosensitive insulating resin composition of the present invention comprises:

(A) alkali-soluble resins containing phenolic hydroxyl groups,

(B) quinonediazide-containing compounds,

(C) cross-linked fine particles,

(D) compounds containing at least two alkyletherified amino groups per molecule, and

(F) Solvent.

The first resin composition preferably contains the following materials based on 100 parts by weight of the alkali-soluble resin (A) with phenolic hydroxyl groups:

10-50 parts by weight of quinonediazide-containing compound (B),

1-50 parts by weight of crosslinked fine particles (C), and

1-100 parts by weight of the compound (D) containing at least two alkyl-etherified amino groups per molecule.

The second positive photosensitive insulating resin composition of the present invention comprises:

(A) alkali-soluble resins containing phenolic hydroxyl groups,

(B) quinonediazide-containing compounds,

(C) cross-linked fine particles,

(D) compounds containing at least two alkyletherified amino groups per molecule,

(E) thermal acid generators, and

(F) Solvent.

The second resin composition preferably contains the following substances based on 100 parts by weight of the alkali-soluble resin (A) with phenolic hydroxyl groups:

10-50 parts by weight of quinonediazide-containing compound (B),

1-50 parts by weight of crosslinked fine particles (C),

1-100 parts by weight of a compound (D) containing at least two alkyl-etherified amino groups per molecule, and

0.1-10 parts by weight of thermal acid generator (E).

In these resin compositions, the crosslinked fine particles (C) preferably have an average particle diameter of 30 to 50 nm.

The cured products of the present invention can be obtained by curing these positive photosensitive insulating resin compositions.

Description of drawings

Fig. 1 is a sectional view of an evaluation sample used for testing thermal shock performance.

Fig. 2 is a plan view of the evaluation sample shown in Fig. 1 .

In these figures:

1 evaluation substrate

2 substrates

3 copper foil

Detailed ways

The positive photosensitive insulating resin composition and its cured product will be described in detail below.

<Positive Photosensitive Insulating Resin Composition>

The first resin composition comprises:

(A) alkali-soluble resins containing phenolic hydroxyl groups,

(B) quinonediazide-containing compounds,

(C) cross-linked fine particles,

(D) compounds containing at least two alkyletherified amino groups per molecule, and

(F) Solvent.

The second resin composition includes:

(A) alkali-soluble resins containing phenolic hydroxyl groups,

(B) quinonediazide-containing compounds,

(C) cross-linked fine particles,

(D) compounds containing at least two alkyletherified amino groups per molecule,

(E) thermal acid generators, and

(F) Solvent.

These compositions may optionally contain another additive such as epoxy compounds, adhesion aids and leveling agents.

(A) Alkali-soluble resins containing phenolic hydroxyl groups

The phenolic hydroxyl group-containing alkali-soluble resin (A) (hereinafter referred to as "phenolic resin (A)") used in the present invention is preferably but not limited to novolac resin. The novolak resin can be obtained by condensation of phenol and aldehyde in the presence of a catalyst.

Phenols that can be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, 1,2,3-glucinol, α-naphthol and β-naphthol.

Exemplary aldehydes include formaldehyde, paraformaldehyde, acetaldehyde and benzaldehyde. Specific examples of the novolak resin include a phenol/formaldehyde condensation novolac resin, a cresol/formaldehyde condensation novolac resin, and a phenol-naphthol/formaldehyde condensation novolak resin.

In addition to the novolac resin, the phenolic resin (A) includes polyhydroxystyrene and its copolymers, phenol/xylylene dimethyl alcohol condensation resin, cresol/xylylene dimethyl alcohol condensation resin and phenol/bicyclic Pentadiene condensation resin.

In the present invention, in addition to the above-mentioned phenol resin (A), a low-molecular-weight phenol compound (hereinafter referred to as "phenol compound (a)") can be used together with the above-mentioned phenol resin (A). Exemplary phenolic compounds (a) include 4,4-dihydroxydiphenylmethane, 4,4-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1-bis(4-methane phenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1, 4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3 -Dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane and 1,1 , 2,2-Tetrakis(4-hydroxyphenyl)ethane. The content of the phenolic compound (a) is preferably 0-40% by weight based on the total amount of the phenolic resin (A) and the phenolic compound (a), more preferably 0-30% by weight, most preferably 5-20% by weight.

The phenolic resin (A) must have a weight average molecular weight of at least 2000, more preferably 2000 to about 20000, in consideration of the resolution, thermal shock property and heat resistance of the finally obtained insulating film.

Said resin composition preferably comprises 30-90% by weight of the composition amount without solvent (F), better 30-80% by weight, most preferably 40-70% by weight of phenolic resin (A) (and the combination Phenolic compounds used (a)). When the content of the phenolic resin (A) is within the above range, the resin composition can form a film having sufficient developability in an alkaline aqueous solution.

(B) Compounds containing quinonediazide groups

The quinonediazide group-containing compound (B) used in the present invention (hereinafter referred to as "quinonediazide compound (B)") is formed from 1,2-naphthoquinonediazide-4-sulfonic acid or 1 , an ester formed between 2-naphthoquinonediazido-5-sulfonic acid and a compound containing at least one phenolic hydroxyl group. The compound containing at least one phenolic hydroxyl group is not particularly limited, preferably the compound has a structure represented by any of the following chemical formulas:

Wherein X ₁ -X ₁₀ respectively represent a hydrogen atom, an alkyl group containing 1-4 carbon atoms, an alkoxy group containing 1-4 carbon atoms or a hydroxyl group, however, the condition is that at least one of X ₁ -X ₅ is a hydroxyl group ; A is a single bond, O, S, CH ₂ , C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , C=O or SO ₂ ;

Wherein X ₁₁ -X ₂₄ has the same definition as X ₁ -X ₁₀ , they may be the same or different, however, the condition is that at least one of X ₁₁ -X ₁₅ is a hydroxyl group; R ₁ -R ₄ represent a hydrogen atom or contain 1- Alkyl group of 4 carbon atoms;

Wherein X ₂₅ -X ₃₉ has the same definition as X ₁ -X ₁₀ , they may be the same or different, however, the condition is that at least one of X ₂₅ -X ₂₉ is a hydroxyl group, and at least one of X ₃₀ -X ₃₄ is a hydroxyl group; R ₅ Represents a hydrogen atom or an alkyl group containing 1-4 carbon atoms;

Wherein X ₄₀ -X ₅₈ has the same definition as X ₁ -X ₁₀ , they may be the same or different, however, the condition is that at least one of X ₄₀ -X ₄₄ is a hydroxyl group, at least one of X ₄₅ -X ₄₉ is a hydroxyl group, and X ₅₀ At least one of -X ₅₄ is a hydroxyl group; R ₆ -R ₈ respectively represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms;

The definitions of X ₅₉ -X ₇₂ are the same as those of X ₁ -X ₁₀ , and they may be the same or different, provided that at least one of X ₅₉ -X ₆₂ is a hydroxyl group, and at least one of X ₆₃ -X ₆₇ is a hydroxyl group.

Examples of the quinonediazido compound (B) include 1,2-naphthoquinonediazido-4-sulfonic acid or 1,2-naphthoquinonediazido-5-sulfonic acid and 4,4-dihydroxy Diphenylmethane, 4,4-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4-tetrahydroxybenzophenone, 2,3,4, 2,4-pentahydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane Alkane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl] Benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 1,1-bis(4-hydroxyphenyl)-1- Esters of [4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane.

The resin composition preferably comprises 10-50 parts by weight with 100 parts by weight of phenolic resin (A) (or when combined, the total amount of phenolic resin (A) and phenolic compound (a)), more preferably 15-30 parts by weight Parts of quinonediazide-based compound (B). When the content of the quinonediazide-based compound (B) is lower than the above lower limit, the remaining percentage of unexposed areas on the film will decrease, and the image designed with the pattern mask cannot be accurately obtained. When the content of the quinonediazide-based compound (B) exceeds the above upper limit, graphics may be deteriorated, and the composition may foam during curing.

(C) Cross-linked fine particles

The crosslinked fine particles (C) may be any particles provided that the polymer particles constituting the particles have polymer particles whose Tg is not higher than 0°C. The crosslinked fine particles (C) are preferably crosslinkable monomers containing at least two unsaturated polymerizable groups (hereinafter referred to as "crosslinkable monomers") and one or more selected It is obtained by copolymerizing different monomers (hereinafter referred to as "different monomers"), and the Tg of the resulting crosslinked fine particle (C) copolymer is lower than 0°C. In addition to containing polymerizable groups, the different monomers preferably also contain functional groups, such as carboxyl groups, epoxy groups, amino groups, isocyanate groups or hydroxyl groups, and the Tg of the crosslinked fine particle (C) copolymer produced is not higher than 0 ℃.

Exemplary crosslinkable monomers include compounds with multiple polymerizable unsaturated groups such as divinylbenzene, diallyl phthalate, ethylene glycol di(meth)acrylate, di(meth) Propylene glycol acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate . Among them, divinylbenzene is preferable.

When preparing the crosslinked fine particles (C), the crosslinkable monomer is preferably used in an amount of 1-20% by weight, more preferably 2-10% by weight, based on the total amount of all monomers to be copolymerized.

Examples of such different monomers include:

Diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene and 1,3-pentadiene;

Unsaturated nitrile compounds such as (meth)acrylonitrile, α-chloroacrylonitrile, α-chloromethacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, nitrile crotonate, Nitrile cinnamate, dinitrile itaconate, dinitrile maleate and dinitrile fumarate;

Unsaturated amides such as (meth)acrylamide, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-hexamethylene Methylbis(meth)acrylamide, N-methylol(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N,N'-bis(2-hydroxyethyl) ) (meth)acrylamide, crotonamide and cinnamamide;

(Meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylate ) lauryl acrylate, polyethylene glycol (meth)acrylate and polypropylene glycol (meth)acrylate;

Aromatic vinyl compounds such as styrene, alpha-methylstyrene, o-methoxystyrene, p-hydroxystyrene and p-isopropenylphenol;

Epoxy (meth)acrylate obtained by reacting diglycidyl ether of bisphenol A, diglycidyl ether of ethylene glycol, etc. with (meth)acrylic acid, hydroxyalkyl (meth)acrylate, etc.; and polyurethane (meth)acrylate obtained by reacting hydroxyalkyl (meth)acrylate and polyisocyanate;

Unsaturated compounds with epoxy groups such as glycidyl (meth)acrylate and (meth)allyl glycidyl ether;

Unsaturated acid compounds such as (meth)acrylic acid, itaconic acid, β-(meth)acryloyloxyethylsuccinate, β-(meth)acryloyloxyethylmaleate, β-(meth) base) acryloyloxyethyl phthalate, β-(meth)acryloyloxyethyl hexahydrophthalate;

Amino-containing unsaturated compounds such as dimethylamino(meth)acrylate and diethylamino(meth)acrylate;

Unsaturated compounds containing amido groups such as (meth)acrylamide and dimethyl(meth)acrylamide; and

Hydroxyl-containing unsaturated compounds such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate.

Among these different monomers, butadiene, isoprene, (meth)acrylonitrile, (meth)acrylic acid, styrene alkyl ester, p-hydroxystyrene, p-isopropenylphenol, (meth) Glycidyl acrylate, (meth)acrylic acid, hydroxyalkyl (meth)acrylate, etc.

As different monomers it is preferred to use at least one diene compound, especially butadiene. Based on the total amount of all monomers to be copolymerized, the amount of the diene compound is preferably 20-80 wt%, most preferably 30-70 wt%.

When a diene compound such as butadiene is copolymerized in the above ratio based on the total amount of all monomers, the crosslinked fine particles (C) can be obtained as rubbery soft fine particles. In addition, the amounts of the above-mentioned different monomers will result in excellent crack resistance and durability of the final cured film.

The average particle diameter of the crosslinked fine particles (C) is preferably 30-500 nm, more preferably 40-200 nm, most preferably 50-120 nm. The diameter of the crosslinked fine particles (C) can be controlled by any method. For example, when the particles (C) are synthesized by emulsion polymerization, the particle size can be controlled by adjusting the amount of emulsifier to adjust the number of capsules formed during emulsion polymerization, but not limited to this method.

The amount of the crosslinked fine particles (C) is preferably 1-50 parts by weight based on 100 parts by weight of the phenolic resin (A) (or when used in combination, the total amount of the phenolic resin (A) and the phenolic compound (a)), More preferably, it is 5-30 parts by weight. When the content of the crosslinked fine particles (C) is lower than the above lower limit, the finally obtained cured film has poor thermal shock property. Whereas a content exceeding the above upper limit may result in a decrease in the resolution and heat resistance of the cured film, and may also result in a decrease in the compatibility and dispersibility of the obtained particles with other components.

(D) Compounds (curing agents) containing at least two alkyl etherified amino groups per molecule

The compound (D) containing at least two alkyl etherified amino groups per molecule (hereinafter referred to as "curing agent (D)") acts as a crosslinking agent (curing agent) in the reaction with the phenolic resin (A) . Examples of curing agents (D) include nitrogen-containing compounds such as (poly)methylolated melamines, (poly)methylolated glycolurils, (poly)methylolated glycolurils, (poly)methylolated methylated benzoguanamines and (poly)methylolated ureas. Exemplary alkyl groups include methyl, ethyl, butyl, and mixtures thereof. The curing agent may contain an oligomer component obtained by partial self-condensation of nitrogen-containing compounds. Examples of such curing agents include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril and tetrabutoxymethylated glycoluril. These curing agents (D) may be used alone or in combination of two or more.

The amount of the curing agent (D) is preferably 1-100 parts by weight based on 100 parts by weight of the phenolic resin (A) (or when used in combination, the total amount of the phenolic resin (A) and the phenolic compound (a)). Preferably it is 5-50 parts by weight. When the content of the curing agent (D) is lower than the above lower limit, the curing cannot proceed sufficiently, so that the obtained cured product has poor electrical insulation properties. Whereas the content exceeding the above upper limit may result in lowered patterning performance and heat resistance.

(E) thermal acid generator

The thermal acid generator (E) used in the present invention (hereinafter referred to as "acid generator (E)") may be any compound that generates an acid at a suitable temperature such as 50-250° C., examples of which include sulfonium salts , diazonium salts, halogen-containing compounds and sulfonate compounds, but not limited to these compounds. The acid generator acts as a catalyst to accelerate the reaction between the alkyl ether group of the curing agent (D) and the phenolic resin (A).

Examples of the acid generator (E) include benzylmethylphenylsulfonium hexafluoroantimonate, benzylmethylphenylsulfonium hexafluorophosphate, benzylmethylphenylsulfonium tetrafluoroborate, trifluoromethanesulfonic acid Benzylmethylphenylsulfonium, benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate, benzyl(4-hydroxyphenyl)methylsulfonium hexafluorophosphate, benzyl(4-hydroxyphenyl)tetrafluoroborate Phenyl)methylsulfonium, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, phenyldiazonium hexafluoroantimonate, phenyldiazonium hexafluorophosphate, benzenediazonium tetrafluoroborate, three Benzenediazonium fluoromethanesulfonate, naphthalenediazonium hexafluoromethanesulfonate, and naphthalenediazonium trifluoromethanesulfonate.

The amount of the acid generator (E) is based on 100 parts by weight of the phenolic resin (A) (or when used in combination, the total amount of the phenolic resin (A) and the phenolic compound (a)), preferably 0.1-10 parts by weight, More preferably, it is 0.5-5 parts by weight. When the content of the acid generator (E) is lower than the above lower limit, the finally obtained cured product has poor solvent resistance. On the other hand, a content exceeding the above upper limit may result in a decrease in electrical insulation properties.

(F) solvent

The solvent (F) is added to the resin composition to enhance processability or to control the viscosity or storage stability of the composition. Examples of solvent (F) include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

Cellosolves such as ethyl cellosolve and butyl cellosolve;

Carbitols such as butyl carbitol;

Lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;

Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate esters and isobutyl propionate;

Other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and acetone ethyl acetate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

Amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone; and

Lactones such as gamma-butyrolactone.

These solvents (F) may be used alone or in combination of two or more.

(G) Other additives

The above resin composition may further include other additives such as epoxy compounds, adhesion aids and leveling agents. Exemplary epoxy compounds include novolac epoxies, bisphenol epoxies, cycloaliphatic epoxies, and aliphatic epoxies. These additives are used within the range that does not impair the properties of the composition.

<cured product>

The first positive photosensitive insulating resin composition includes: phenolic resin (A), quinone diazide compound (B), crosslinked fine particles (C), curing agent (D), solvent (F) and optional Other additives (G). This resin composition has excellent resolution, and a cured product obtained from the resin composition has excellent electrical insulation, thermal shock and adhesive properties, and curing shrinkage.

The second positive photosensitive insulating resin composition comprises: phenolic resin (A), quinone diazide compound (B), crosslinked fine particles (C), curing agent (D), acid generator (E), solvent (F) and optionally further additives (G). This resin composition has excellent resolution, and a cured product obtained from the resin composition has excellent electrical insulation, thermal shock properties, adhesive properties and cure shrinkage, and solvent resistance.

Therefore, these resin compositions are suitably used as materials for producing interlayer insulating films and surface protective films for semiconductor elements.

The resin composition is coated on a substrate such as a silicon wafer on which a wiring pattern has been formed, and then the coated resin composition is dried so that the solvent and the like evaporate to form a thin film. Afterwards, the film is exposed through a photomask with a desired pattern, and the exposed film is developed in an alkaline developer. As a result of development, the exposed areas are dissolved and removed to obtain a film with the desired pattern. In addition, the film is heated to improve insulating properties, and thus a cured film can be produced.

The aforementioned coating of the resin composition on the substrate can be achieved by dip coating, spray coating, wire bar coating, roll coating, spin coating, curtain coating and the like. The thickness of the film can be appropriately controlled by selecting the coating method and adjusting the solid concentration and viscosity of the composition.

Exemplary radiation substances that can be used for the above exposure include ultraviolet rays, electron beams, and laser beams from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, and i-line steppers. . The radiation dose is appropriately determined according to the radiation source used or the thickness of the resin film. In the case of ultraviolet rays emitted from a high-pressure mercury lamp, the dose is approximately 1000-20000 J/m ² , and the film thickness is 5-50 µm.

Subsequently, the exposed film layer is developed in an alkaline developer to dissolve and remove the exposed area to form the desired pattern. Exemplary developing methods include shower development, spray development, immersion development, and stirring development. Development is usually performed at 20-40°C for about 1-10 minutes.

Examples of alkaline developers include alkaline aqueous solutions containing about 1 to 10% by weight of alkaline compounds such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline. The alkaline aqueous solution can be mixed with an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, or surfactants. The above-mentioned development with alkaline developer is followed by water washing and drying

The formed pattern is then cured by heat treatment so that the resulting cured film can sufficiently function as an insulating film. In the case of the second composition, the acid generator (E) is decomposed by heat treatment to form an acid. Due to the catalysis of this acid, the reaction between the curing agent (D) and the phenolic resin (A) is accelerated. The curing conditions are not particularly limited, and it depends on the use of the cured product, for example, the film can be cured by heating at 100-250° C. for 30 minutes to 10 hours. Heat treatment can also be carried out in a two-stage manner, so that the film is fully cured and deformation of the resulting pattern is avoided. For example, curing may be performed in such a manner that the resulting pattern is heated at 50-100°C for 10 minutes to 2 hours in the first stage, and heated at 100-250°C for 20 minutes to 8 hours in the second stage. Under the above curing conditions, heating can be carried out in conventional ovens, infrared ovens, and similar heating devices.

industrial application

The positive-type photosensitive insulating resin composition of the present invention has good resolution, and can obtain a cured product having excellent electrical insulation, thermal shock, and adhesive properties, especially excellent insulation and thermal shock .

Example

Hereinafter, the present invention will be described in detail through the following examples, but it should be noted that the present invention is by no means limited to these examples. Hereinafter, "parts" means parts by weight unless only stated.

The following is a description of the components used in Examples and Comparative Examples. The properties of the cured products obtained in these examples were evaluated according to the methods given below.

<component>

Phenolic resin (A):

A-1: A cresol novolac resin prepared from m-cresol and p-cresol at a molar ratio of 60/40 (weight average molecular weight based on polystyrene: 8700)

A-2: Cresol novolak resin prepared from m-cresol and p-cresol in a molar ratio of 50/50 (weight average molecular weight based on polystyrene: 7500)

A-3: polyhydroxystyrene (trade name: MARUKA LYNCUR S-2P, available from Maruzen Petrochemical Co., Ltd.)

Phenolic compound (a):

a-1: 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane

Quinone diazide compound (B):

B-1: 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane and 1,2- Condensate of naphthoquinonediazido-5-sulfonic acid with an average molar ratio of 1/2.0.

B-2: Condensate of 1,1-bis(4-hydroxyphenyl)-1-phenylethane and 1,2-naphthoquinonediazido-5-sulfonic acid at an average molar ratio of 1/1.5 .

Cross-linked fine particles (C):

C-1: Butadiene/hydroxybutyl methacrylate/methacrylic acid/divinylbenzene=60/32/6/2 (% by weight), average particle diameter=65nm

Curing agent (D):

D-1: Hexamethoxymethylated melamine (trade name: CYMEL300, available from Mitsui Cytec, Ltd.)

D-2: Tetramethoxymethylated glycoluril (trade name: CYMEL1174, available from Mitsui Cytec, Ltd.)

Acid generator (E):

E-1: Benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate

E-2: benzyl(4-hydroxyphenyl)methylsulfonium hexafluorophosphate

Solvent (F):

F-1: ethyl lactate

F-2: 2-heptanone

Other additives (G)

G-1: Diethylene glycol diglycidyl ether

G-2: SAN-AID SI-150 (purchased from SANSHIN CHEMICAL IND.CO., Ltd.)

<Evaluation method>

Resolution:

The positive photosensitive insulating resin composition was spin-coated on a 6-inch silicon wafer. The coated resin composition was heated on a hot plate at 100° C. for 5 minutes to form a uniform film with a thickness of 10 μm. The film was then irradiated with ultraviolet light emitted from a high-pressure mercury lamp through a photomask with an etalon MA-150 (available from SussMicrotec). The dose at 350nm is between 3000 and 10000J/ ^m2 . Next, the exposed film was developed by immersing in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23°C for 2 minutes. The film was then washed with ultrapure water for 1 min to form a pattern. Resolution is evaluated based on the smallest size of the resulting pattern.

Electrical insulation properties (volume resistivity)

The positive photosensitive insulating resin composition is coated on a SUS substrate. The coated resin composition was heated on a hot plate at 100° C. for 5 minutes to form a uniform film with a thickness of 10 μm. The film was further heated in a convection oven at 170°C for 2 hours to obtain a cured film. The cured film was placed in a hot pot tester (ESPEC CORP.) at 121° C., 100% humidity, and 2.1 atmospheres for 168 hours. The volume resistivity of the interlayer was measured before and after the above treatment. The obtained results were compared with each other to determine the resistance performance.

Thermal shock performance:

The positive photosensitive insulating resin composition was coated on the evaluation substrate 1 to test its thermal shock performance. As shown in FIGS. 1 and 2 , an evaluation substrate 1 is composed of an evaluation substrate 2 and patterns of copper foil 3 . The coated resin composition was then heated on a hot plate at 100° C. for 5 minutes to prepare evaluation samples. The thickness of the resin film of the evaluation sample on the conductor of the evaluation substrate 1 was 10 µm. The resin coating was then placed in a convection oven at 170°C for 2 hours to obtain a cured film. The evaluation samples were then subjected to a thermal shock test using a thermal shock tester (ESPEC CORP.). During the test, a cycle of -55°C/30 minutes and 150°C/30 minutes is used as a cycle, and this cycle is repeated until cracks or similar defects appear on the cured film. Thermal shock performance is determined by the number of cycles.

Adhesive properties:

The positive-type photosensitive insulating resin composition is coated on a silicon wafer sprayed with SiO ₂ . The applied resin composition was heated on a hot plate at 100° C. for 5 minutes to prepare a sample of a uniform resin film having a thickness of 10 μm. The film was further heated in a convection oven at 170°C for 2 hours to obtain a cured film. The cured film was then placed in a pressure cooker (ESPEC CORP.) at 121° C., 100% humidity, 2.1 atmospheres for 168 hours. Adhesive properties before and after the above-mentioned treatment were measured by a cross-cut (adhesion) test method according to JIS K5400.

Curing Shrinkage:

The positive photosensitive insulating resin composition was spin-coated on a 6-inch silicon wafer. The applied resin composition was heated on a hot plate at 100° C. for 5 minutes to prepare a resin film sample of uniform thickness. The thickness of the resin film was measured at this stage as the thickness (A). The film was then placed in a convection oven at 170°C for 2 hours to obtain a cured film. The thickness of the cured film was measured as thickness (B). Curing shrinkage is calculated by heating with the following formula:

Curing shrinkage={1-(B)/(A)}×100

Solvent Resistance:

The positive photosensitive insulating resin composition was spin-coated on a 6-inch silicon wafer. The coated resin composition was heated on a hot plate at 100° C. for 5 minutes to prepare a uniform film sample having a thickness of 10 μm. The film was then heated in a convection oven at 170°C for 2 hours to obtain a cured film. The cured film samples were dipped in isopropanol at 60°C for 10 minutes. Then observe the surface of the cured film under an optical microscope, and evaluate its surface condition according to the following criteria:

AA: The surface is intact

BB: The surface is whitened or destroyed

<The first positive-type photosensitive insulating resin composition and its cured product>

<Example 1-5>

Mix phenolic resin (A), phenolic compound (a), quinonediazide compound (B), crosslinked fine particles (C), curing agent (D) and other additives (G) according to the mixing ratio shown in Table 1 The resin composition is prepared by dissolving in the solvent (F). Then the performance of the resin composition was tested with the above method, and the results are shown in Table 2.

<Comparative Examples 1-4>

Dissolve phenolic resin (A), quinonediazide compound (B), crosslinked fine particles (C), curing agent (D) and other additives (G) in solvent (F) according to the mixing ratio shown in Table 1 Prepare the resin composition. Then the performance of the resin composition was tested with the above method, and the results are shown in Table 2.

<Second positive photosensitive insulating resin composition and cured product thereof>

<Example 6-10>

Phenolic resin (A), phenolic compound (a), quinone diazide compound (B), crosslinked fine particles (C), curing agent (D) and acid generator (E) are mixed according to the mixing ratio shown in Table 3 The resin composition is prepared by dissolving in the solvent (F). The performance of the resin composition was tested by the above method, and the results are shown in Table 4.

<Comparative Examples 5-9>

Dissolve phenolic resin (A), quinonediazide compound (B), crosslinked fine particles (C), curing agent (D) and acid generator (E) in solvent (F) according to the mixing ratio shown in Table 3 Prepare the resin composition. The performance of the resin composition was tested by the above method, and the results are shown in Table 4.

Claims (4)

1. positive photosensitive insulating resin composition, said resin combination comprises:

(A) alkali soluble resins of phenolic hydroxy group, the weight-average molecular weight of this resin is at least 2000;

(B) contain the compound of quinone diazido,

(C) crosslinked fine grained, said crosslinked fine grained (C) consumption is counted the 1-50 weight portion with the alkali soluble resins (A) of 100 weight portion phenolic hydroxy groups;

(D) per molecule contains the compound of the amino of two alkyl etherificates at least, and this compound (D) consumption is counted the 1-100 weight portion with the alkali soluble resins (A) of 100 weight portion phenolic hydroxy groups;

(E) hot acid agent, said hot acid agent (E) consumption is counted the 0.1-10 weight portion with the alkali soluble resins (A) of 100 weight portion phenolic hydroxy groups; With

(F) solvent,

Wherein, said hot acid agent comprises hexafluoro-antimonic acid benzyl aminomethyl phenyl sulfonium, hexafluorophosphoric acid benzyl aminomethyl phenyl sulfonium, tetrafluoro boric acid benzyl aminomethyl phenyl sulfonium, TFMS benzyl aminomethyl phenyl sulfonium, hexafluoro-antimonic acid benzyl (4-hydroxyphenyl) methyl sulfonium, hexafluorophosphoric acid benzyl (4-hydroxyphenyl) methyl sulfonium, tetrafluoro boric acid benzyl (4-hydroxyphenyl) methyl sulfonium, TFMS benzyl (4-hydroxyphenyl) methyl sulfonium, hexafluoro-antimonic acid benzene diazonium, hexafluorophosphoric acid benzene diazonium, tetrafluoro boric acid benzene diazonium, TFMS benzene diazonium, hexafluoro-antimonic acid naphthalene diazonium and TFMS naphthalene diazonium.

2. the described resin combination of claim 1 is characterized in that, in the alkali soluble resins (A) of 100 weight portion phenolic hydroxy groups, said resin combination comprises following material:

The compound that contains the quinone diazido (B) of 10-50 weight portion,

The crosslinked fine grained (C) of 5-30 weight portion,

The per molecule of 5-50 weight portion contain at least the amino of two alkyl etherificates compound (D) and

0.5-5 the hot acid agent (E) of weight portion.

3. the resin combination described in the claim 1 is characterized in that, the mean grain size of said crosslinked fine grained (C) is 30-500nm.

4. cured product, it is solidified by the described positive photosensitive insulating resin composition of claim 1 and obtains.

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