TW202026762A - Photosensitive resin composition and application thereof - Google Patents

Abstract

The present invention provides a photosensitive resin composition comprising (a) a polyamide ester represented by formula (1), (b) a polyimide, (c) a photo radical initiator, (d) a radical polymerizable compound, and (e) a solvent for dissolving the photosensitive polyimide

Description

Photosensitive resin composition and its application

The present invention relates to a photosensitive resin composition, and particularly relates to a photosensitive resin composition with low dielectric loss.

In response to high-frequency wireless transmission and high-speed communication data, high-frequency chips and high-frequency substrates are the focus of the industry in the future. High-frequency high-speed transmission needs to ensure the integrity of the transmission signal, so in the high-frequency (1GHz or higher) region, materials with low dielectric loss factors are required. In addition, the electronic design of printed circuit boards and semiconductors, along with technological development and product demand, requires the characteristics of higher performance, smaller volume, and higher wiring density.

The photosensitive resin composition has been widely used as a cured film in various electronic components or devices. It has excellent characteristics such as flexibility, good mechanical properties and good electrical properties, and is affected by semiconductor chips (such as integrated circuits). Circuit (IC) or Printed Circuit Board (PCB) related industries are preferred. Among them, photosensitive polyimide is the most widely used, such as polyacryloyl or acrylic groups. Because of the development of photosensitive resins for high-frequency and high-speed transmission, a photosensitive polyimide polymer with a low dielectric loss tangent is an expected issue in the industry.

In view of this, the object of the present invention is to provide a cured film with a low dielectric constant and a low dielectric loss tangent.

(1)， 其中，A來源為四羧酸二酐，B來源為二胺，m為1-10000中之正整數，R¹ 及R² 係各自獨立為(甲基)丙烯醯氧基烷基或烷基，且(甲基)丙烯醯氧基烷基係占R¹ 及R² 整體之50-100莫耳%，其限制條件為該四羧酸二酐不包含均苯四甲酸二酐。To achieve the above objective, the present invention provides a resin composition comprising: (a) polyamide ester, which is represented by formula (1); (b) polyimide; (c) photoradical Starter; (d) radical polymerizable compound; (e) solvent to dissolve the polyimide,

(1), wherein the source of A is tetracarboxylic dianhydride, the source of B is diamine, m is a positive integer from ^{1 to 10,000,} and R ¹ and R ² are each independently a (meth)acryloyloxyalkyl group Or an alkyl group, and the (meth)acryloxyalkyl group accounts for 50-100 mol% of the entire R ¹ and R ² , and the restriction condition is that the tetracarboxylic dianhydride does not contain pyromellitic dianhydride.

Preferably, the tetracarboxylic dianhydride is 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride (HQDEA), 4,4'-bis(3,4-dicarboxyphenoxy) )Biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4-(hexafluoroisopropylene)diphthalic anhydride (BPADA), ethylene glycol double dehydrated trimellitate (TMEG), propylene glycol bis (trimellitic anhydride) (TMPG), 1,2-propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), 2-methyl- 1,3-propanediol bis (trimellitic anhydride), dipropylene glycol bis (trimellitic anhydride), 2-methyl-2,4-pentanediol bis (trimellitic anhydride), diethylene glycol bis (trimellitic anhydride), tetraethylene glycol bis (trimellitic anhydride), Hexaethylene glycol bis (trimellitic anhydride), neopentyl glycol bis (trimellitic anhydride), hydroquinone bis (trimellitic anhydride) (TAHQ), hydroquinone bis (2-hydroxyethyl) ether bis (trimellitic anhydride), 2-benzene -5-(2,4-Hydroxy)-1,4-hydroquinone bis(trimellitic anhydride), 2,3-dicyanohydroquinone cyclobutane-1,2,3,4-tetracarboxylic dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA), bicyclo[2.2.1]heptane- 2,3,5,6-tetracarboxylic dianhydride (BHDA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BOTDA), bicyclo[2.2. 2] Octane-2,3,5,6-tetracarboxylic dianhydride (BODA), 2,3,5-tricarboxy-cyclopentylacetic dianhydride, bicyclo[2.2.1]heptane-2,3 ,5-Tricarboxy-6-acetic acid dianhydride, decahydro-1,4,5,8-dimethanol naphthalene-2,3,6,7-tetracarboxylic dianhydride, butane-1,2,3,4 -Tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, or a combination of any two or more of the aforementioned tetracarboxylic dianhydrides.

Preferably, the diamine is 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane (BAPP), 2,2-bis(4-aminobenzene) Base) hexafluoropropane (APHF), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethylbenzidine (m-tolidine), 1,3-bis(3 -Aminophenoxy)benzene (TPE-M), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene, 1, 4-bis(4-aminophenoxy)benzene (TPE-Q), 5-amino-2-(p-aminophenyl)benzoxazole (5-ABO), 6-amino-2-(p-aminobenzene) Yl)benzoxazole (6-ABO) or a combination of any two or more of the aforementioned diamines.

(2)， 其中，C來源為四羧酸二酐，D來源為二胺，n為1-5000中之正整數。Preferably, the polyimide is represented by formula (2):

(2), wherein the source of C is tetracarboxylic dianhydride, the source of D is diamine, and n is a positive integer from 1 to 5000.

， 其中，R⁴ 及R⁵ 係各自獨立為烷基、烯基、炔基、芳香基或雜環基。Preferably, at least one of the C and the D has a structure of at least one of the following divalent groups:

, Wherein R ⁴ and R ⁵ are each independently an alkyl group, an alkenyl group, an alkynyl group, an aromatic group or a heterocyclic group.

Preferably, the radically polymerizable compound is a compound having at least two (meth)acrylate groups.

Preferably, the glass transition temperature of the cured film formed by the resin composition is 200-230°C.

Preferably, the cured film formed by the resin composition has a dielectric loss factor less than 0.015.

The present invention also provides a cured film, which is formed by curing the aforementioned resin composition.

Preferably, the cured film has a glass transition temperature of 200-230°C.

Preferably, the hardened film has a dielectric loss factor less than 0.015.

The present invention also provides a method for manufacturing a hardened film, which includes the following steps: coating the aforementioned resin composition on a substrate; and sequentially pre-baking, exposing, developing, and post-baking the composition.

The present invention also provides an interlayer insulating film and a circuit board protective film including the aforementioned cured film.

The photosensitive resin composition of the present invention is a combination of the aforementioned components (a) to (e), and a cured film with low dielectric loss can be obtained from the composition.

(1)， 其中，A來源為四羧酸二酐，B來源為二胺，m為1-10000中之正整數，R¹ 及R² 係各自獨立為(甲基)丙烯醯氧基烷基或烷基，且(甲基)丙烯醯氧基烷基係占R¹ 及R² 整體之50-100莫耳%，其限制條件為該四羧酸二酐不包含均苯四甲酸二酐。The present invention provides a photosensitive resin composition comprising: (a) polyamide ester, which is represented by formula (1); (b) polyimide; (c) photoradical initiator; (d) Radical polymerizable compound; (e) Solvent to dissolve the polyimide,

(1), wherein the source of A is tetracarboxylic dianhydride, the source of B is diamine, m is a positive integer from ^{1 to 10,000,} and R ¹ and R ² are each independently a (meth)acryloyloxyalkyl group Or an alkyl group, and the (meth)acryloxyalkyl group accounts for 50-100 mol% of the entire R ¹ and R ² , and the restriction condition is that the tetracarboxylic dianhydride does not contain pyromellitic dianhydride.

In the present invention, the polyamide ester represented by formula (1) can be selected by monomers of tetracarboxylic dianhydride derived from A and diamine derived from B to increase the non-polar group (such as alkane) in the structure. , Halothane) structure, or use ethers, esters, or a planar aromatic ring structure to increase crystallinity and reduce the proportion of imine groups in the overall formula, which can reduce the dielectric constant and dielectric constant. The characteristics of the electrical loss tangent.

In formula (1), m is a positive integer from 1 to 10,000, such as: 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000. In some embodiments, m is between any two values mentioned above. In the formula (1), R ¹ and R ² are each independently a (meth)acryloxyalkyl group or an alkyl group, and the (meth)acryloxyalkyl group accounts for the whole of R ¹ and R ² 50-100 mol%, such as: 55-95 mol%, 60-90 mol%, 65-85 mol%. In other words, the alkyl group accounts for 0-50 mol% of the entire R ¹ and R ² , such as: 5-45 mol%, 10-40 mol%, 15-35 mol%.

In a preferred embodiment, the polyamide ester represented by formula (1) is obtained by the reaction of tetracarboxylic dianhydride, alcohol compound and diamine. Examples of the alcohol compound can be methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. These alcohol compounds can be used alone or in a mixture of two or more (such as two, three, or four).

In the present invention, an alkyl group refers to a straight or branched chain alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.

In formula (1), the tetracarboxylic dianhydride is preferably 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride (HQDEA), 4,4'-bis(3,4- Dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4-(hexafluoroisopropylene) Phthalic anhydride (BPADA), ethylene glycol double dehydrated trimellitate (TMEG), propylene glycol bis (trimellitic anhydride) (TMPG), 1,2-propylene glycol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), 2-methyl-1,3-propanediol bis (trimellitic anhydride), dipropylene glycol bis (trimellitic anhydride), 2-methyl-2,4-pentanediol bis (trimellitic anhydride), diethylene glycol bis (trimellitic anhydride), tetraethylene glycol Bis (trimellitic anhydride), hexaethylene glycol bis (trimellitic anhydride), neopentyl glycol bis (trimellitic anhydride), hydroquinone bis (trimellitic anhydride) (TAHQ), hydroquinone bis (2-hydroxyethyl) ether bis (trimellitic anhydride) ), 2-Phenyl-5-(2,4-Hydroquinone)-1,4-hydroquinone bis(trimellitic anhydride), 2,3-dicyanohydroquinone cyclobutane-1,2,3,4- Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA), bicyclo[2.2. 1]Heptane-2,3,5,6-tetracarboxylic dianhydride (BHDA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BOTDA) , Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride (BODA), 2,3,5-tricarboxy-cyclopentylacetic dianhydride, bicyclo[2.2.1]heptan Alkane-2,3,5-tricarboxy-6-acetic acid dianhydride, decahydro-1,4,5,8-dimethanol naphthalene-2,3,6,7-tetracarboxylic dianhydride, butane-1, 2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride or any two or more of the aforementioned tetracarboxylic dianhydrides (such as: two, three, four Species, five species) combination.

In formula (1), the diamine is preferably 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane (BAPP), 2,2-bis (4-Aminophenyl)hexafluoropropane (APHF), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethylbenzidine (m-tolidine), 1, 3-bis(3-aminophenoxy)benzene (TPE-M), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy) )Benzene, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 5-amino-2-(p-aminophenyl)benzoxazole (5-ABO), 6-amino-2 -(P-Aminophenyl)benzoxazole (6-ABO) or a combination of two or more of the aforementioned diamines (such as two, three, four, five).

The polyimine of the present invention is a solvent-soluble polyimine that is chemically or thermally closed by the reaction of diamine and tetracarboxylic dianhydride. The solvent can be ethyl acetate, n-butyl acetate , Γ-butyrolactone, ε-caprolactone, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, cyclopentan Ketone, N-methylpyrrolidone, dimethylformamide, dimethylsulfide, N,N-dimethylacetamide or a combination of two or more of the aforementioned solvents. The solution solid content of the solvent-soluble polyimide usually accounts for 5% to 70% by weight of the solvent, more preferably 10% to 50% by weight. More specifically, generally, the diamine and tetracarboxylic dianhydride are dissolved in an organic solvent, and the resulting solution is placed under controlled temperature conditions under stirring until the polymerization of the tetracarboxylic dianhydride and the diamine is completed to obtain poly The imine precursor (ie, polyamic acid), and the solution of the polyamide acid obtained therefrom, usually has a concentration of 5% to 35% by weight, more preferably 10% to 30% by weight. When the concentration is within this range, an appropriate molecular weight and solution viscosity can be obtained. The polymerization method is not particularly limited, and the order of addition, the monomer combination and the amount of addition thereof are also not particularly limited. For example, the polyimide system of the present invention can produce random polymerization or sequential polymerization of block components by a conventional polymerization method.

The preparation method of the polyimide precursor (ie, polyimide) to form polyimine by ring closure is not particularly limited. More specifically, a chemical method of ring closure can be used, that is, under nitrogen or oxygen, pyridine, triethylamine or N,N-diisopropylethylamine, etc., which are not limited as alkaline reagents, and as dehydrating reagents The acetic anhydride is added to the polyimide acid. After the reaction is completed, the colloid is washed and filtered with water to obtain the polyimide powder. In addition, the closed loop method of heating can be used to add polyamide acid to an azeotropic reagent (such as toluene or xylene, but not limited to this), and increase the temperature to 180°C. The boiling reagent is removed, and after the reaction is over, the solvent-soluble polyimide can be prepared. In the process of preparing solvent-soluble polyimide, other reagents can be added to improve the reaction efficiency, including but not limited to: catalysts, inhibitors, azeotropic agents, leveling agents or any two or more of these reagents (such as: three , Four) combination.

(2)， 其中，C來源為四羧酸二酐，D來源為二胺，n為1-5000中之正整數。，諸如：500、1000、1500、2000、2500、3000、3500、4000、4500。於一些實施態樣中，n係介於前述任兩個數值之間。In the present invention, the polyimide is preferably represented by formula (2):

(2), wherein the source of C is tetracarboxylic dianhydride, the source of D is diamine, and n is a positive integer from 1 to 5000. , Such as: 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500. In some embodiments, n is between any two of the aforementioned values.

In the present invention, the polyimide represented by formula (2) is obtained by the polymerization reaction of tetracarboxylic dianhydride and diamine. That is, in formula (2), C is a tetravalent organic group derived from tetracarboxylic dianhydride, and D is a divalent organic group derived from diamine.

In formula (2), the tetracarboxylic dianhydride is not particularly limited, but based on the consideration of exhibiting low dielectric loss, the tetracarboxylic dianhydride is preferably 3,3',4,4'-biphenyl Tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, bis(3,4-dicarboxyphenyl) ) Methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,3-bis(3 ,4-Dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, ethylene glycol bis(trimellitic anhydride) (TMEG), propylene glycol bis(trimellitic anhydride) (TMPG) , 1,2-propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), 2-methyl-1,3-propanediol bis (trimellitic anhydride), dipropylene glycol bis (trimellitic anhydride), 2-methyl-2,4- Pentylene glycol bis (trimellitic anhydride), diethylene glycol bis (trimellitic anhydride), tetraethylene glycol bis (trimellitic anhydride), hexaethylene glycol bis (trimellitic anhydride), neopentyl glycol bis (trimellitic anhydride), hydroquinone bis (2-hydroxy Ethyl) ether bis(trimellitic anhydride), 2-phenyl-5-(2,4-diamino)-1,4-hydroquinone bis(trimellitic anhydride), 2,3-dicyanohydroquinone cyclobutane-1 ,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2 .1]Heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2. 2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxy-cyclopentylacetic dianhydride, bicyclo[2.2.1]heptane-2,3,5- Tricarboxy-6-acetic acid dianhydride, decahydro-1,4,5,8-dimethanol naphthalene-2,3,6,7-tetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic A combination of acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, or any two or more of the aforementioned tetracarboxylic dianhydrides (such as: two, three, four, five) .

In formula (2), the diamine may be an aromatic diamine or an aliphatic diamine. Based on the consideration of exhibiting low dielectric loss, the aromatic diamine is preferably 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-methylene diphenylamine , 4,4'-methylenediphenylamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(tri Fluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dihydroxybenzidine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4 -Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4 -Aminophenoxy)phenyl]propane, 2,2-bis[ 4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3 -Bis[4-(3-aminophenoxy)benzyl]benzene, 4,4'-diaminobenzylaniline, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro A combination of any two or more of propane, 5-amino-2-(p-aminophenyl)benzoxazole, 6-amino-2-(p-aminophenyl)benzoxazole or the aforementioned aromatic diamines. In addition, based on the consideration of exhibiting low dielectric loss, the aliphatic diamine is preferably 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, or a combination thereof.

其中，R⁴ 及R⁵ 係各自獨立為烷基、烯基、炔基、芳香基或雜環基。In formula (2), it is preferable that at least one of C and D has a structure of at least one of the following divalent groups:

Wherein, R ⁴ and R ⁵ are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

In the present invention, commercially available soluble polyimine can be used, for example, trade names "PIAD100H", "PIAD100L", "PIAD200" (manufactured by Arakawa Chemical).

The polyimide addition amount in the present invention is preferably 10% by weight to 100% by weight of the main resin (ie polyamide ester), more preferably 20% by weight to 80% by weight, particularly preferably 30% by weight to 70% by weight. weight%.

The photo radical initiator in the present invention may be an initiator commonly used in conventional photosensitive resin compositions. Examples of photoradical initiators include, but are not limited to: oxime compounds such as oxime derivatives; ketone compounds (including acetophenones, benzophenones and thioxanthones); triazine compounds; benzoin Compounds; metallocene compounds; triazine compounds; phosphine compounds and combinations of any two or more of the foregoing compounds (such as three, four, or five). From the viewpoint of exposure sensitivity, the photoradical initiator is preferably an acylphosphine compound or an oxime compound.

Examples of oxime compounds such as oxime derivatives include, but are not limited to: O-oxime-based compounds, 2-(orthobenzyloxime)-1-[4-(phenylthio)phenyl]-1,2 -Octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone, O -Ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, or a combination of any two or more of the foregoing compounds (such as three, four, or five). Examples of compounds based on O-oxime include but are not limited to: 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4 -Yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1- (4-Phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1 -Oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-but-1-oxime-O-acetate, or a combination of any two or more of the foregoing compounds. Examples of phosphine compounds include: bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2,4,6-trimethylbenzyl-diphenylphosphine oxide or The combination, but not limited to this.

The content of the photo-radical initiator is 0.1% to 30% by weight, preferably 1% to 20% by weight of the main resin (ie, polyurethane). When the content of the photo-radical initiator is within the range, it will be fully cured during the exposure during the pattern formation process to ensure excellent reliability, and the pattern can have better resolution and close contact heat resistance Resistance, light resistance and chemical resistance.

The photo radical initiator can be used together with a photosensitizer. The photosensitizer can be excited by absorbing light, causing a chemical reaction, and then transferring its energy. Examples of photosensitizers include, but are not limited to: tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetraalkyl-3-mercaptopropionate, and the like. These photosensitizers can be used alone or in combination of two or more (such as three).

The radically polymerizable compound is a photoradical crosslinking agent, and its kind is not particularly limited. Preferably, the type of the photocrosslinking agent depends on the type of polyamide ester, soluble polyimide and/or photo radical initiator. In a preferred embodiment of the present invention, the radically polymerizable compound is a compound having at least two (meth)acrylate groups, such as a compound having two (meth)acrylate groups, a compound having three A compound with one (meth)acrylate group, a compound with four (meth)acrylate groups, a compound with five (meth)acrylate groups, or a compound with six (meth)acrylate groups. Examples of the compound having at least two (meth)acrylate groups include but are not limited to: ethylene glycol dimethacrylate; EO modified diacrylate of bisphenol A (n=2-50) (EO is cyclic Oxyethane, n is the number of moles of ethylene oxide added); EO modified diacrylate of bisphenol F; Aronix M-210®, M-240® and/or M-6200® (East Asia Synthetic Chemical Industrial Co., Ltd.); KAYARAD HDDA®, HX-220®, R-604® and/or R-684® (Nippon Kayaku Co., Ltd.); V-260®, V-312® and/or V- 335HP® (Osaka Organic Chemical Ind., Ltd.); BLEMMER PDE-100®, PDE-200®, PDE-400®, PDE-600®, PDP-400®, PDBE-200A®, PDBE-450A®, ADE -200®, ADE-300®, ADE-400A®, ADP-400® (NOF Co., Ltd.); trimethylolpropane triacrylate (TMPTA); methylol propane tetraacrylate; glycerol trihydroxy Propyl ether triacrylate; triethoxy trimethylolpropane triacrylate; trimethylolpropane trimethacrylate; tris(2-hydroxyethyl) isocyanate triacrylate (THEICTA); pentaerythritol triacrylate Esters; pentaerythritol hexaacrylate; Aronix M-309®, M-400®, M-405®, M-450®, M-710®, M-8030® and/or M-8060® (Toa Synthetic Chemical Industry Co., Ltd. Company); KAYARAD DPHA®, TMPTA®, DPCA-20®, DPCA-30®, DPCA-60® and/or DPCA-120® (Nippon Kayaku Corporation); V-295®, V-300®, V -360®, V-GPT®, V-3PA® and/or V-400® (Osaka Yuki Kayaku Kogyo Co., Ltd.) etc.

In the photosensitive resin composition, from the viewpoint of good radical polymerizability and heat resistance, the content of the radical polymerizable compound is preferably 1% by mass to 50% with respect to the total solid content of the photosensitive resin composition quality%. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. The radical polymerizable compound can be used alone or in combination of two or more (such as three, four, and five). In addition, the mass ratio of the polyamide ester to the radical polymerizable compound is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and particularly preferably 90/10 to 50/50. If the mass ratio of the polyamide ester and the radical polymerizable compound is within the above range, a cured film with more excellent curability and heat resistance can be formed. In the present invention, the radically polymerizable compound may be used singly or in combination of two or more (such as three, four, or five). When two or more types are used, it is preferable that the total amount falls within the aforementioned range.

When the content of the radically polymerizable compound is within the above range, the crosslinking bond generated by the radical reaction initiated by the photo radical initiator and UV radiation irradiation can improve the pattern forming ability. In addition, exposure and curing can sufficiently occur during pattern formation, and the contrast of the alkaline developer can be improved.

The solvent used in the present invention is not particularly limited, as long as it can dissolve the polyimide. Specific examples of the solvent include but are not limited to: ethyl acetate, n-butyl acetate, γ-butyrolactone, ε-caprolactone, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethyl acetate Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol Monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, cyclopentanone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfide or N,N-dimethyl ethyl Diamide (DMAc). These solvents can be used alone or in combination of two or more (such as two, three or four). From the viewpoint of improving the coating surface state, it is preferable to use a mixture of two or more solvents. When the photosensitive resin composition contains a solvent, from the viewpoint of coatability, the content of the solvent is preferably 5 mass% to 80 mass% of the total solid content of the photosensitive resin composition, more preferably 5 mass% ~70% by mass, particularly preferably 10% to 60% by mass. The solvent may be only one type or two or more types. When two or more solvents are contained, the total amount is preferably within the stated range.

In the range that does not affect the effect of the present invention, the photosensitive resin composition of the present invention is added with or without additives, depending on the application requirements of the user. Examples of the additives include, but are not limited to: higher fatty acid derivatives, surfactants, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomeration agents, leveling agents, or both of these additives A combination of more than one species. When blending these additives, it is preferable to set the total blending amount to 10% by mass or less of the solid content of the photosensitive resin composition.

In the preparation of the interlayer insulating film and the protective film of the present invention, the photosensitive resin composition can be coated on a substrate by a coating method such as spin coating or cast coating, and then subjected to a prebake method. The solvent is removed to form a pre-baked coating film. Among them, the pre-bake conditions vary according to the types and mixing ratios of the ingredients. Usually the temperature is between 80 and 120°C for 5 to 15 minutes. After pre-baking, the coating film is exposed under a photomask. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line. The ultraviolet irradiation device can be (ultra) high pressure mercury lamp and metal halide light. Then, it is immersed in a developing solution at a temperature of 20-40°C for 1 to 2 minutes to remove unnecessary parts and form a specific pattern. Specific examples of the developer include but are not limited to: for example, methanol, ethanol, propanol, isopropanol, butanol, ethyl acetate, n-butyl acetate, γ-butyrolactone, ε-caprolactone, diethyl Glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, cyclopentanone, N-methylpyrrolidone, dimethyl methyl ketone Amine, dimethyl sulfide, N,N-dimethyl acetamide or a combination of any two or more of these organic solvents.

When using the developer composed of the above organic solvent, it is usually washed with an organic solvent after development, and then dried with compressed air or compressed nitrogen. Next, a postbake treatment is performed using a heating device such as a hot plate or an oven, and the temperature of the postbake treatment is usually 180 to 250°C. After the above processing steps, a protective film can be formed.

The substrate is not particularly limited in the present invention, and can be selected according to subsequent requirements. The substrate can be copper, graphite, aluminum, iron, copper alloy, aluminum alloy, iron alloy, silicon wafer, plastic material, etc.

The substrate can also be used in liquid crystal displays such as alkali-free glass, soda lime glass, strengthened glass (Pyrex glass), quartz glass, glass with transparent conductive film attached to the surface, or used for solid-state photographic elements And other photoelectric conversion element substrates (such as silicon substrates), etc.

The device with interlayer insulating film and protective film includes an interlayer insulating film and protective film as described above and the above-mentioned substrate.

The device with interlayer insulating film and protective film includes, but is not limited to, a carrier board, a display device, a semiconductor device, a printed circuit board, or an optical waveguide.

Therefore, the present invention also provides a cured film formed by curing the aforementioned resin composition. In a preferred embodiment, the cured film preferably has a glass transition temperature of 200-230°C. The cured film of the present invention preferably has a dielectric loss factor of less than 0.015, more preferably has a dielectric loss factor of 0.01, and particularly preferably has a dielectric loss factor of 0.002 to 0.009.

The present invention also provides an interlayer insulating film and a circuit board protective film including the aforementioned cured film. Examples of the interlayer insulating film include, but are not limited to: an interlayer insulating film for a rewiring layer or an interlayer insulating film for a carrier-like board.

The present invention also provides a method for manufacturing a hardened film, which includes the following steps: coating the aforementioned resin composition on a substrate; and sequentially pre-baking, exposing, developing, and post-baking the composition.

In order to highlight the effectiveness of this case, the inventors have completed the examples and comparative examples according to the methods set out below. The following examples and comparative examples are all experimental data of the inventor and are not in the category of prior art. The following examples and comparative examples will further illustrate the present invention. However, these examples and comparative examples are not intended to limit the scope of the present invention. Anyone familiar with the technical field of the present invention can make changes and changes without departing from the spirit of the present invention. Modifications fall within the scope of the present invention.

Synthesis example 1 : Polyurethane ( A1 ) Is synthesized by propylene glycol bis(trimellitic anhydride ) (TMPG) , 2,2'- double ( Trifluoromethyl ) Benzidine (TFMB) And methacrylic acid -2- Hydroxyethyl (HEMA) From the reaction

In a four-neck flask, 16.97 g (40.0 millimoles) of propylene glycol bis(trimellitic anhydride) (TMPG), 10.94 g (84.0 millimoles) of 2-hydroxyethyl methacrylate (HEMA), 0.04 g (0.4 Millimoles) of hydroquinone, 3.16 g (84.0 millimoles) of pyridine and 80 mL of tetrahydrofuran were added in sequence, stirred at 50°C for 3 hours, and a transparent solution was obtained a few minutes after heating. The reaction mixture was cooled to room temperature. Then, the reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C±4°C, 11.9 g (100.0 millimoles) of sulphurous chloride was added over 10 minutes. During the addition of sulphurous chloride, the viscosity increases. After diluting with 50 mL of dimethylacetamide, the reaction mixture was stirred at room temperature for 2 hours. Continue to maintain the temperature at -10°C±4°C, use 11.62 g (200.0 millimoles) of propylene oxide as a neutralizer to neutralize excess hydrochloric acid. Another 20 minutes will make 12.75 g (39.8 millimoles) of 2 A solution of 2'-bis(trifluoromethyl)benzidine (TFMB) dissolved in 100 mL of dimethylacetamide was added dropwise to the reaction mixture, and the reaction mixture was stirred for 15 hours at room temperature. After the reaction, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered out, poured into 4 liters of water again, and stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45° C. under reduced pressure for 3 days to obtain a powder of polyimide (HEMA-TMPG-TFMB PAE (A1)). The result of ¹ H-NMR measurement of the obtained A1 is shown below (the ratio of the hydrogen number is defined by the structural unit that is not repeated). ¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm): 11.10-11.07 (2 H, m, NH), 8.46-8.43 (2 H, m), 8.39-8.32 (2 H, m), 8.12 -8.01 (2 H, m), 7.60-7.38 (4 H, m), 7.30-7.23 (2 H, m), 4.49-4.30 (12 H, m), 2.49-2.40 (2 H, m), 1.84 -1.80 (6 H, m); FT-IR (cm ^-1 ): 2923, 2821 (CH), 1780 (C=O), 1725 (C=O), 1648 (CH2=CH), 1615, 1485, 1425, 1366, 1273, 1241, 1198, 1134, 1078, 842, 742.

Synthesis example 2 : Polyurethane ( A2 ) Is synthesized by 2,2- double [4-(3,4- Dicarboxyphenoxy ) Phenyl ] Propane dianhydride (BPADA) , 1,4- double (4- Aminophenoxy ) benzene (TPE-Q) And methacrylic acid -2- Hydroxyethyl (HEMA) From the reaction

In a four-necked flask, 20.82 g (40.0 millimoles) of BPADA, 10.94 g (84.0 millimoles) of HEMA, 0.04 g (0.4 millimoles) of hydroquinone, 3.16 g (84.0 millimoles) The pyridine and 80 mL of tetrahydrofuran were added sequentially, and stirred at 50°C for 3 hours to prepare the diester of propylene glycol bis(trimellitic anhydride) and 2-hydroxyethyl methacrylate. After chlorinating the obtained diester with sulfinous chloride, using the same method as in Synthesis Example 1, it was converted into poly(ethylene oxide) by 1,4-bis(4-aminophenoxy)benzene (TPE-Q). As the precursor of imine, a powder of polyamide ester (HEMA-BPADA-TPE-Q PAE (A2)) was obtained by the same method as in Synthesis Example 1. The result of ¹ H-NMR measurement of the obtained A2 is shown below (the hydrogen number ratio is defined by the structural unit that is not repeated). ¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm): 10.41-10.40 (2 H, m, NH), 8.30-8.24 (2 H, m), 7.98-7.85 (2 H, m), 7.78 -7.61 (6 H, m), 7.39-7.20 (8 H, m), 7.13-6.95 (12 H, m), 6.00-5.93 (2 H, m), 5.61-5.55 (2 H, m), 4.44 -4.41 (4 H, m), 4.27-4.17 (4 H, m), 1.81-1.68 (12 H, m); FT-IR (cm ^-1 ): 2927 (CH), 2824, 1726 (C=O ), 1651 (CH2=CH), 1615, 1483, 1435, 1370, 1132, 1078, 842, 743.

Synthesis example 3 : Polyurethane ( A3 ) Is synthesized by 2,2- double [4-(3,4- Dicarboxyphenoxy ) Phenyl ] Propane dianhydride (BPADA) , 2,2'- double ( Trifluoromethyl ) Benzidine (TFMB) ,Methacrylate -2- Hydroxyethyl (HEMA) And ethanol (EtOH) From the reaction

In a four-necked flask, 20.82 g (40.0 millimoles) of BPADA, 5.47 g (42.0 millimoles) of HEMA, 1.93 g (42.0 millimoles) of ethanol, and 0.04 g (0.4 millimoles) of p-benzene Diphenol, 3.16 g (84.0 millimoles) of pyridine and 80 mL of tetrahydrofuran were added sequentially, and stirred at 50°C for 3 hours to prepare a mixture of propylene glycol bis(trimellitic anhydride), 2-hydroxyethyl methacrylate and ethanol Diester. After chlorinating the obtained diester with sulfonium chloride, using the same method as in Synthesis Example 1, it was converted into polyamide by 2,2'-bis(trifluoromethyl)benzidine (TFMB) As the amine precursor, a powder of polyamide ester (1:1 HEMA-EtOH-BPADA-TFMB PAE (A3)) was obtained by the same method as in Synthesis Example 1. The result of ¹ H-NMR measurement of the obtained A3 is shown below (the hydrogen number ratio is defined by the structural unit that is not repeated). ¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm): 10.84-10.82 (2 H, m, NH), 8.28-8.26 (2 H, m), 7.98-7.85 (2 H, m), 7.77 -7.68 (2 H, m), 7.40-7.26 (8 H, m), 7.24-7.03 (6 H, m), 6.00-5.93 (1 H, m), 5.61-5.55 (1 H, m), 4.46 -4.41 (2 H, m), 4.27-4.18 (4 H, m), 1.81-1.76 (9 H, m), 1.12-1.08 (3 H, m); FT-IR (cm ^-1 ): 2927 ( CH), 1780, 1726 (C=O), 1650 (CH2=CH), 1615, 1484, 1434, 1370, 1132, 1078, 742.

Synthesis example 4 ：Polyimide (B1 ：Solvent-soluble polyimide ) The synthesis of propylene glycol bis(trimellitic anhydride ) (TMPG) versus 2,2'- double ( Trifluoromethyl ) Benzidine (TFMB) From the reaction

Put 62.12 g (0.194 millimolar) of TFMB and 500 g of DMAc into a three-necked flask. After stirring at 30°C until completely dissolved, 84.86 g (0.200 millimoles) of TMPG was added, followed by continuous stirring and reaction at 25°C for 24 hours to obtain a polyamide acid solution; then 23.00 g (0.290 Millimoles) of pyridine and 59.4 g (0.582 millimoles) of acetic anhydride, then continue to stir and react at 25°C for 24 hours. After the reaction, the polyimide was precipitated in 5 liters of water, and the water-polyimide mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide was collected by filtration, poured into 4 liters of water again, and stirred for 30 minutes, and then filtered again. Then, the obtained polyimide was dried at 45° C. under reduced pressure for 3 days to obtain a powder of dried polyimide (TMPG-TFMB PI (B1)). The result of ¹ H-NMR measurement of the obtained B1 is shown below (the ratio of the hydrogen number is defined by the structural unit that is not repeated). ¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm): 8.47-8.20 (4 H, m), 8.15-7.70 (6 H, m), 7.47-7.41 (2 H, m), 4.45-4.38 (4 H, m), 2.48-2.39 (2 H, m); FT-IR (cm ^-1 ): 3066, 2971, 1785, 1722, 1605, 1490, 1431, 1315, 1278, 1145, 840, 722.

Synthesis example 5 ：Synthesis of polyimide (B2 ：Soluble Polyimide ) , Which is by 2,2- double [4-(3,4- Dicarboxyphenoxy ) Phenyl ] Propane dianhydride (BPADA) , 2,2'- double ( Trifluoromethyl ) Benzidine (TFMB) , 2,2- double [4-(4- Aminophenoxy ) Phenyl ] Propane (BAPP) From the reaction

Put 15.53 g (0.0485 millimoles) of TFMB, 19.91 g (0.0485 millimoles) of BAPP, and 234 g of DMAc into a three-necked flask. After stirring at 30°C until completely dissolved, 52.04 g (0.100 millimoles) of BPADA was added, followed by continuous stirring and reacting at 25°C for 24 hours to obtain a polyamide acid solution; then 11.50 g (0.146 Millimoles) of pyridine and 29.7 g (0.291 millimoles) of acetic anhydride, then continue to stir and react at 25°C for 24 hours. After the reaction, the polyimide was precipitated in 5 liters of water, and the water-polyimide mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide was collected by filtration, poured into 4 liters of water again, and stirred for 30 minutes, and then filtered again. Then, the obtained polyimide was dried at 45° C. under reduced pressure for 3 days to obtain a powder of dried polyimide (BPADA-TFMB-BAPP PI (B2)). The result of ¹ H-NMR measurement of the obtained B2 is shown below (the ratio of the hydrogen number is defined by the structural unit that is not repeated). ¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm): 8.02-7.95 (8 H, m), 7.83-7.81 (2 H, m), 7.66-7.61 (2 H, m), 7.47-7.24 (22 H, m), 7.18-6.81 (16 H, m), 1.70-1.64 (18 H, m); FT-IR (cm ^-1 ): 3066, 2971, 1778, 1726, 1601, 1486, 1426, 1310, 1273, 1138, 1078, 840, 722.

Comparative synthesis example 1 : Polyurethane ( A4 ) Is synthesized by pyromellitic dianhydride (PMDA) , 2,2'- double ( Trifluoromethyl ) Benzidine (TFMB) And methacrylic acid -2- Hydroxyethyl (HEMA) From the reaction

In a four-neck flask, add 8.72 g (40.0 millimoles) of PMDA, 10.94 g (84.0 millimoles) of HEMA, 0.04 g (0.4 millimoles) of hydroquinone, 3.16 g (84.0 millimoles) ) Pyridine and 80 mL of tetrahydrofuran were added sequentially, and stirred at 50°C for 3 hours to prepare the diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate. After chlorinating the obtained diester with sulfonium chloride, using the same method as in Synthesis Example 1, it was converted into polyamide by 2,2'-bis(trifluoromethyl)benzidine (TFMB) As the amine precursor, a polyamide ester (HEMA-PMDA-TFMB PAE (A4)) was obtained by the same method as in Synthesis Example 1. The result of ¹ H-NMR measurement of the obtained A4 is shown below (the ratio of the hydrogen number is defined by the structural unit that is not repeated). ¹ H-NMR (500 MHz, DMSO-d ₆ , δ ppm): 11.10-11.02 (2 H, m, NH), 8.38-8.12 (4 H, m), 7.94 (2 H, s), 7.38 (2 H, s), 6.01-6.00 (2 H, m), 5.62-5.55 (2 H, m), 4.52-4.56 (4 H, m), 4.36-4.35 (4 H, m), 1.84-1.80 (6 H, m); FT-IR (cm ^-1 ): 2975 (CH), 1730, 1628 (CH2=C), 1605, 1548, 1499, 1446, 1306, 1262, 1113, 896, 845, 745.

Example 1-5 And comparative example 1-3 : Preparation of photosensitive resin composition

The components used in the photosensitive polyimide resin composition are as follows. The components described below were mixed with a solvent in the weight ratio shown in Table 1 to prepare a DMAc solution with a solid content of 30%, which is a coating solution for the photosensitive resin composition.

Ingredient A1: HEMA-TMPG-TFMB PAE

Composition A2: HEMA-BPADA-TPE-Q PAE

Composition A3:1:1 HEMA-EtOH BPADA-TFMB PAE

Component A4: HEMA PMDA-TFMB PAE (comparative synthesis example)

Ingredient B1: TMPG-TFMB PI

Ingredient B2: BPADA-TFMB-BAPP PI

Ingredient C: Irgacure OXE01 (BASF)

Ingredient D1: THEICTA (Aldrich)

Composition D2: TMPTA (Aldrich)

Ingredient D3: PDBE-450A (NOF)

Evaluation results

[Pattern Formation]

The photosensitive resin composition is coated on a copper foil substrate, and a 15μm film is produced by surface drying at 90°C for 5 minutes. After exposure through a photomask, the exposed photosensitive resin composition layer is subjected to 60 Development in seconds. Use the following criteria to evaluate whether the line width has good edge sharpness. The smaller the line width of the photosensitive resin composition layer is, the larger the difference in solubility between the light-irradiated portion and the non-light-irradiated portion in the developer solution becomes, and it is a better result. In addition, the smaller the change in line width with respect to the change in exposure energy, the wider the exposure latitude, which becomes a better result.

After observing the formed adhesive pattern with an optical microscope, set the case of forming a fine line pattern with line width/pitch width=15μm/15μm or less as A, and set the line width/pitch width=more than 15μm/15μm and 30μm/30μm The case of the following fine line pattern was set as B, and the pattern formation was evaluated. The evaluation results are shown in Table 1.

The dielectric constant, dielectric loss factor, linear thermal expansion coefficient, and glass transition temperature in Table 1 are obtained by coating, exposing, and developing the photosensitive resin composition to form a thin film after curing at 250°C. Measurement:

[Dielectric constant (Dk)]

Use a measuring instrument (brand: Agilent; model: HP4291), under the condition of 10GHz, using the IPC-TM-650-2.5.5.9 standard method for measurement.

[Dielectric loss factor (dissipation factor, Df)]

Use a measuring instrument (brand: Agilent; model: HP4291), under the condition of 10GHz, using the IPC-TM-650-2.5.5.9 standard method for measurement.

[Coefficient of thermal expansion (CTE)]

By thermomechanical analysis, in a load of 3g/film thickness of 20μm and a heating rate of 10°C/min, the average value calculated in the range of 50 to 200°C from the extension of the test piece is used as the linear thermal expansion coefficient. Materials with low linear thermal expansion can avoid excessive deformation during the heating and baking process of manufacturing circuit boards, so that the production line can maintain a high yield.

[Glass transition temperature (glass transition temperature, Tg)]

It was measured using a differential scanning calorimeter device (DSC-6220) manufactured by SII Nano Technology. In a nitrogen atmosphere, the film of the photosensitive resin composition was subjected to thermal history under the following conditions. The conditions of the thermal history are the first temperature increase (temperature increase rate 10°C/min), subsequent cooling (cooling rate 30°C/min), and then the second temperature increase (temperature increase rate 10°C/min). The glass transition temperature of the present invention reads and determines the value observed at the first heating or the second heating.

Table 1 Example Comparative example 1 2 3 4 5 1 2 3 Formula composition Polyurethane A1 40 40 A2 40 40 A3 40 A4 40 40 80 Soluble Polyimide B1 40 40 40 40 B2 40 40 40 Light radical initiator C 4 4 4 4 4 4 4 4 Crosslinking agent D1 16 16 16 16 D2 16 16 D3 16 16 Exposure (mJ/cm ² ) 200 200 400 400 200 400 400 400 Evaluation results Pattern formation A A B A A A B A Glass transition temperature ( ^o C) 220 224 202 227 210 260 235 240 Coefficient of linear thermal expansion (ppm/ ^o C) 66 68 63 57 67 41 55 60 Dielectric constant (Dk) 2.82 2.59 2.89 2.92 2.70 3.14 2.75 2.69 Dielectric loss factor (Df) 0.0081 0.0079 0.0082 0.0085 0.0084 0.018 0.017 0.017 Note 1: The unit of formula composition in Table 1 is parts by weight.

As shown in Table 1, the cured film formed by the resin composition of Examples 1 to 5 has a glass transition temperature of 200-230°C, a linear expansion coefficient of approximately 55-70, and a significantly lower dielectric loss factor At 0.01.

In summary, the cured film formed by the resin composition of the present invention has a low dielectric constant and low dielectric loss tangent, and is suitable for carrier-like substrates, liquid crystal displays, organic electroluminescent displays, semiconductor devices or printing On substrates contained in circuit boards, etc.

However, the above are only the preferred embodiments of the present invention, and should not be used to limit the scope of implementation of the present invention, that is, as long as simple changes and modifications are made in accordance with the scope of the patent application and the description of the invention, they are still It belongs to the scope of the invention patent.

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Claims (14)

A photosensitive resin composition comprising: (a) polyamide ester, which is represented by formula (1); (b) polyimide; (c) photo radical initiator; (d) free Base polymerizable compound; (e) solvent to dissolve the polyimide,

(1), wherein the source of A is tetracarboxylic dianhydride, the source of B is diamine, m is a positive integer from ^{1 to 10,000,} and R ¹ and R ² are each independently a (meth)acryloyloxyalkyl group Or an alkyl group, and the (meth)acryloxyalkyl group accounts for 50-100 mol% of the entire R ¹ and R ² , and the restriction condition is that the tetracarboxylic dianhydride does not contain pyromellitic dianhydride. The resin composition according to claim 1, wherein the tetracarboxylic dianhydride is 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride (HQDEA), 4,4'-bis(3 ,4-Dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4-(hexafluoroisopropylene Base) diphthalic anhydride (BPADA), ethylene glycol double dehydrated trimellitate (TMEG), propylene glycol bis(trimellitic anhydride) (TMPG), 1,2-propylene glycol bis(trimellitic anhydride), butanediol bis( Trimellitic anhydride), 2-methyl-1,3-propanediol bis (trimellitic anhydride), dipropylene glycol bis (trimellitic anhydride), 2-methyl-2,4-pentanediol bis (trimellitic anhydride), diethylene glycol bis (trimellitic anhydride), Tetraethylene glycol bis(trimellitic anhydride), hexaethylene glycol bis(trimellitic anhydride), neopentyl glycol bis(trimellitic anhydride), hydroquinone bis(trimellitic anhydride) (TAHQ), hydroquinone bis(2-hydroxyethyl) ether Bis (trimellitic anhydride), 2-phenyl-5-(2,4-diamino)-1,4-hydroquinone bis(trimellitic anhydride), 2,3-dicyanohydroquinone cyclobutane-1,2,3 ,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA), bicyclic [2.2.1]Heptane-2,3,5,6-tetracarboxylic dianhydride (BHDA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BOTDA), bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride (BODA), 2,3,5-tricarboxy-cyclopentylacetic dianhydride, bicyclo[2.2. 1]Heptane-2,3,5-tricarboxy-6-acetic dianhydride, decahydro-1,4,5,8-dimethanol naphthalene-2,3,6,7-tetracarboxylic dianhydride, butane -1,2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride or a combination of any two or more of the aforementioned tetracarboxylic dianhydrides. The resin composition according to claim 1, wherein the diamine is 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane (BAPP), 2, 2-bis(4-aminophenyl)hexafluoropropane (APHF), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethylbenzidine (m-tolidine) , 1,3-bis(3-aminophenoxy)benzene (TPE-M), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-amino) Phenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 5-amino-2-(p-aminophenyl)benzoxazole (5-ABO), 6- Amino-2-(p-aminophenyl)benzoxazole (6-ABO) or a combination of any two or more of the aforementioned diamines. The resin composition according to claim 1, wherein the polyimide is represented by formula (2):

(2), wherein the source of C is tetracarboxylic dianhydride, the source of D is diamine, and n is a positive integer from 1 to 5000. The resin composition according to claim 4, wherein at least one of C and D has a structure of at least one of the following divalent groups:

, Wherein R ⁴ and R ⁵ are each independently an alkyl group, an alkenyl group, an alkynyl group, an aromatic group or a heterocyclic group. The resin composition according to claim 1, wherein the radically polymerizable compound is a compound having at least two (meth)acrylate groups. The resin composition according to claim 1, wherein the glass transition temperature of the cured film formed is 200 to 230°C. The resin composition according to claim 1, wherein the cured film formed thereon has a dielectric loss factor of less than 0.015. A cured film formed by curing the resin composition according to any one of claims 1 to 6. The cured film according to claim 9, which has a glass transition temperature of 200 to 230°C. The cured film according to claim 9, which has a dielectric loss factor less than 0.015. An interlayer insulating film including the cured film as described in claim 9. A protective film for a circuit board, comprising the hardened film as described in claim 9. A method for manufacturing a hardened film, which includes the following steps: Coating the resin composition according to any one of claims 1 to 8 on a substrate; and The composition is sequentially pre-baked, exposed, developed and post-baked.