CN116333303A - Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof - Google Patents
Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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Abstract
The invention discloses an alkali aqueous development photosensitive adhesive film resistant to mold pressing and application thereof. The photosensitive adhesive film is prepared from the photosensitive resin composition, and the photosensitive resin composition comprises the following components in parts by mass: 100 parts of polyamic acid ester resin, 30-60 parts of photo-induced cross-linking agent, 0.1-15 parts of photoinitiator, 0.1-5 parts of polymerization inhibitor, 87-390 parts of inorganic filler, 1-5 parts of dispersing agent and 100-300 parts of solvent; the preparation method comprises the following steps: reacting dianhydride with an alcohol compound containing unsaturated double bonds to obtain diester diacid; the diester diacid reacts with an acyl chloride reagent to obtain the corresponding diester diacid chloride; performing polycondensation reaction on diester diacid chloride and diamine solution I; and after the polycondensation reaction is carried out for 3-8 hours, adding a diamine solution II into the reaction system for continuous polycondensation reaction. The invention ensures that 100% of film transfer rate of the film can be ensured when the film is transferred from the support film to the wafer by adjusting the resin structure, and simultaneously ensures the stiffness of the film when the film is molded, ensures that the film is not collapsed when the film is molded, and ensures the formation of a hollow cavity.
Description
Technical Field
The invention relates to an alkali aqueous development photosensitive adhesive film resistant to mold pressing and application thereof, and belongs to the technical field of high polymer materials and semiconductor packaging.
Background
With the continuous upgrading and updating of electronic products, the emerging markets of smart phones, 5G, AI and the like put higher requirements on packaging technologies, so that the packaging technologies are developed towards high integration, three-dimensional, superfine pitch interconnection and the like. Among them, the filter and other devices require hollow-structured electronic components. Currently, such hollow-structured photosensitive solid adhesive films are generally formed by pressing an alkali water-soluble resin and an inorganic filler into a film shape, then directly serving as a cover, covering the substrate wall to form a hollow structure, and then performing photolithography and other treatments.
Chinese patent application (CN 113646882 a) discloses a photosensitive resin composition which can improve the high sensitivity of the cap portion of a hollow structure and can be well patterned by photolithography. Chinese patent application (CN 115236938A) discloses a negative photosensitive polyamic acid ester resin composition, and preparation and application thereof, wherein the negative photosensitive polyamic acid ester resin composition is suitable for manufacturing a hollow cavity similar to a filter which needs photoetching development, and the invention solves the problems that an opening formed by a photosensitive adhesive after photoetching development of a photosensitive solid adhesive film is small in size and large in size, and the electric performance reliability of a later process is affected. However, the compression molding resistance of the hollow-structured cap is not currently concerned. Therefore, the prior photosensitive resin composition needs to be improved, so that when the photosensitive resin composition is used as a cover with a hollow structure, the problem of mold pressing resistance in a mold pressing process is solved on the basis that the film transfer rate of a film can be 100% when the film is adhered.
Disclosure of Invention
The invention aims to provide an alkali aqueous development photosensitive adhesive film resistant to mold pressing, which has the film transfer rate reaching 100% in the application process and has stronger mold pressing resistance in the curing process at 250 ℃.
The invention firstly provides a preparation method of polyamide acid ester resin, which comprises the following steps:
s1, reacting dianhydride with an alcohol compound containing unsaturated double bonds to obtain diester diacid;
s2, reacting the diester diacid with an acyl chloride reagent to obtain corresponding diester diacid chloride;
s3, carrying out polycondensation reaction on the diester diacid chloride and a diamine solution I;
the diamine solution I is a diamine solution containing hydroxyl;
the diamine containing hydroxyl is at least one of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 3' -dihydroxybenzidine and aromatic diamine shown in the following structure:
s4, after the polycondensation reaction is carried out for 3-8 hours, adding a diamine solution II into the reaction system of the step S3 to continue the polycondensation reaction, and obtaining the polyamide acid ester resin after solid precipitation;
the diamine solution II is a triazine diamine solution;
The triazine diamine is at least one of triazine diamine, benzomelamine and 6-methyl-1, 3, 5-triazine-2, 4-diamine;
preparing the diamine solution I and the diamine solution II by NMP;
the molar ratio of the hydroxyl group-containing diamine to the triazine-based diamine may be 1:0.4 to 0.8, such as 1:0.4 or 1:0.8; experiments prove that if the usage amount of the triazine diamine is too small, the collapse of the cavity span cover with the thickness of 250 mu m can be caused, and the normal photoetching development can be influenced by too large usage amount.
The application of two diamines ensures the alkaline water solubility of the polyamide acid ester resin, and simultaneously, the influence of other ions on the photosensitive adhesive film is not introduced;
the molar ratio of the dianhydride to the diamine is 1: 1.01-1.025, wherein the diamine comprises the diamine containing hydroxyl and the triazine diamine.
In order to keep the adhesiveness of the photosensitive film, the transfer rate can reach 100% when the film is transferred to a wafer, and meanwhile, the resin modulus and the anti-molding property are improved, wherein the dianhydride adopts a mixture of flexible dianhydride and rigid dianhydride, and the molar content of the flexible dianhydride in the mixture is more than or equal to 50%;
preferably, the molar ratio of the flexible dianhydride to the rigid dianhydride may be 1:0.5 to 0.9, such as 1:0.5 or 1:0.9; experiments have shown that if the amount of the flexible dianhydride is too large, it can lead to collapse of the 250 μm cavity span lid, and if the amount of the rigid dianhydride is too large, it can lead to a reduced film transfer rate.
Preferably, the flexible dianhydride is selected from at least one of hexafluorodianhydride (6 FDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), bisphenol a dianhydride (BPADA), 4 diphenyl ether dianhydride (ODPA) and diphenyl sulfide dianhydride (TDPA).
Preferably, the rigid dianhydride is selected from at least one of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 2,3',3,4' -biphenyl tetracarboxylic dianhydride (α -BPDA), pyromellitic anhydride (PMDA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, and 1,2,3, 4-cyclopentatetracarboxylic dianhydride.
Preferably, the alcohol compound containing unsaturated double bond is selected from at least one of 2-hydroxy-3-phenoxypropyl methyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and 2-hydroxyethyl methacrylate;
preferably, the acid chloride reagent is selected from thionyl chloride.
Preferably, each reaction in step S1-3 may be performed under conventional conditions in the art, e.g., the reaction in step S1 may be performed at 40-80℃for 5-20 hours; the reaction in the step S2 can be carried out at 0-10 ℃ for 2-5 h, and the reaction in the step S3 can be carried out at 20-40 ℃ for 3-8 h; the reaction in the step S4 can be carried out for 3-8 hours at 20-40 ℃.
Preferably, in step S4, the reaction system is mixed with a poor solvent to precipitate a solid resin, which is then washed and dried.
The molecular weight of the polyamide acid ester resin provided by the invention is 15000-40000, and the film forming property and the photoetching developing property of the adhesive film can be maintained.
On the basis of the polyamic acid ester resin, the invention provides a photosensitive resin composition which comprises the following components in parts by mass:
100 parts by mass of the polyamic acid ester resin, 30-60 parts by mass of a photo-induced cross-linking agent, 0.1-15 parts by mass of a photoinitiator, 0.1-5 parts by mass of a polymerization inhibitor, 87-390 parts by mass of an inorganic filler, 1-5 parts by mass of a dispersing agent and 100-300 parts by mass of a solvent;
the photosensitive resin composition preferably comprises any one of the following components in parts by mass:
1) 100 parts by mass of the polyamic acid ester resin, 40 parts by mass of a photo-crosslinking agent, 1 part by mass of a photoinitiator, 0.15 part by mass of a polymerization inhibitor, 143-332 parts by mass of an inorganic filler, 1 part by mass of a dispersing agent and 150-260 parts by mass of a solvent;
2) 100 parts by mass of the polyamic acid ester resin, 40 parts by mass of a photo-crosslinking agent, 1 part by mass of a photoinitiator, 0.15 part by mass of a polymerization inhibitor, 143 parts by mass of an inorganic filler, 1 part by mass of a dispersing agent and 150 parts by mass of a solvent;
3) 100 parts by mass of the polyamic acid ester resin, 40 parts by mass of a photo-crosslinking agent, 1 part by mass of a photoinitiator, 0.15 part by mass of a polymerization inhibitor, 214 parts by mass of an inorganic filler, 1 part by mass of a dispersing agent and 200 parts by mass of a solvent;
4) 100 parts by mass of the polyamic acid ester resin, 40 parts by mass of a photo-crosslinking agent, 1 part by mass of a photoinitiator, 0.15 part by mass of a polymerization inhibitor, 332 parts by mass of an inorganic filler, 1 part by mass of a dispersing agent and 260 parts by mass of a solvent.
Preferably, the photocrosslinker is selected from at least one of 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl methacrylate, ethylene glycol diethyl ether acrylate and polyethylene glycol methacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tri (2-hydroxyethyl) isocyanurate triacrylate and tricyclodecanedimethanol diacrylate.
Preferably, the photoinitiator is selected from at least one of benzophenone, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzil derivatives, benzoin derivatives, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime and 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime.
Preferably, the polymerization inhibitor is at least one selected from hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-t-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2, 6-di-t-butylp-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol.
Preferably, the inorganic filler is selected from at least one of silica, mica powder and alumina;
the silica is preferably an angular silica (commercially available) having a size of 1 to 6 μm, preferably 1 to 3 μm;
the mica powder is preferably a dry-process mica powder (commercially available) having a size of 1 to 6 μm, preferably 1 to 3 μm;
the size of the alumina is 1-6 mu m, preferably 1-3 mu m;
the inorganic filler accounts for 50-70%, preferably 50-60%, 60-70%, 50%, 60% or 70% of the total solid matter.
The dispersing agent is an adhesion promoter with epoxy groups, and can be specifically selected from one or a mixture of more of KH560, self-poly (propylene glycol) diglycidyl ester, polyethylene glycol diglycidyl ester, 1,3, 5-triglycidyl-triazinetrione, 4, 5-epoxycyclohexane-1, 2-diglycidyl ester, aliphatic epoxy resin, bisphenol A diglycidyl ether and the like.
Preferably, the solvent is selected from at least one of N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethylsulfoxide, tetramethylurea, γ -butyrolactone, ethyl lactate, propylene glycol methyl ether acetate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, and butyl acetate.
In the photosensitive resin composition, the invention further provides a photosensitive adhesive film which is prepared from the photosensitive resin composition and is resistant to the alkaline aqueous development of mold pressing.
The anti-molding alkaline aqueous development photosensitive adhesive film can be prepared according to the following method:
s I, coating: coating the photosensitive resin composition on the surface of a support film;
s II, pre-baking: baking the photosensitive resin composition on the surface of the support film to form a photosensitive solid adhesive film with the support film;
And S III, laminating a protective film: attaching the protective film to the photosensitive solid adhesive film to obtain an alkaline water-based developed negative photosensitive solid adhesive film;
the supporting film and the protecting film are made of PET or PP;
the thickness of the supporting film is 10-250 mu m, and the thickness of the protecting film is 5-250 mu m;
the baking conditions were as follows: baking in a hot plate, a baking oven or a baking channel at 60-120 ℃ for 1-60 min;
the bonding conditions are as follows: the temperature is 50-100 ℃, and the pressure is 0.1-0.5 MPa.
The photosensitive adhesive film with the alkaline aqueous development can pass through a cover with a hollow structure for preparing electronic components, has strong compression molding resistance when being solidified at 250 ℃, and has 100 percent of film transfer rate when being adhered;
the electronic component may be a filter or the like.
The invention has the following beneficial technical effects:
the invention ensures that 100% of film transfer rate of the film can be ensured when the film is transferred from the support film to the wafer by adjusting the resin structure, and simultaneously ensures that the film has stiffness when in mould pressing, does not collapse when in mould pressing, and ensures that a hollow cavity is formed.
Drawings
FIG. 1 is a photograph of a photoresist film of example 1 after being developed, cured and molded.
FIG. 2 is a photograph of the photoresist film of example 3 after being developed, cured and molded.
FIG. 3 is a photograph of comparative example 1 film after photo-resist development curing and post-molding.
FIG. 4 is a photograph of a comparative example 4 film after photo-resist development curing and post-molding.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1,
In this example, 4-diphenyl ether dianhydride (ODPA): 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) =1: 0.9;2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane: triazine diamine = 1:0.8, wherein the rigid dianhydride is the maximum amount, the triazine diamine is the maximum amount, and the inorganic filler accounts for 50% of the total solid mass; the molar ratio of dianhydride to diamine is 1:1.015.
31.02g of 4, 4-diphenyl ether dianhydride, 26.48g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 49.45g of 2-hydroxyethyl methacrylate, 30.05g of pyridine and 230g N-methylpyrrolidone (NMP) were successively added to a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature for 6 hours to give the corresponding Diacid dimethacrylate. The diacid dimethacrylate solution was combined with 45.21g SOCl 2 Reacting for 2h at 0-10 ℃ and 4h at room temperature to obtain the corresponding diacyl chloride dimethacrylate.
In a 1L three neck round bottom flask (A) equipped with a mechanical stirrer, thermometer and nitrogen blanket, 39.19g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 100g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
In another 100mL three-necked round bottom flask B equipped with a mechanical stirrer, thermometer and nitrogen protection device, 8.89g of triazine diamine and 10g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
Adding the diamine solution in the three-neck round bottom flask (A) into the prepared diacid chloride dimethacrylate solution, and dripping for 1h; then, reacting for 6 hours at room temperature; adding diamine solution in the three-neck round bottom flask (B) for 0.2h; then, the reaction was carried out at room temperature for 4 hours.
The reaction solution was put into 10L of deionized water, and solid was precipitated, filtered and dried in vacuo to obtain a polyimide precursor resin having a resin molecular weight of 28000.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 150g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 143g of silica (size 1 to 3 μm) was added to the homogeneous solution, and stirred for 3 hours to form a homogeneous dispersion. 100g of polyamide acid resin is added into the uniform dispersion liquid, and the mixture is stirred to a homogeneous solution, thus obtaining the photosensitive resin composition.
In the photosensitive resin composition prepared in this example, the mass ratio of the polyamic acid resin, the photocrosslinker, the photoinitiator, the polymerization inhibitor, the inorganic filler, the dispersing agent and the solvent is 100:40:1:0.15:143:1:150.
the prepared photosensitive resin composition is coated on a supporting film PET to form a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 10 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
Tearing off the protective film, aligning the adhesive film with the structural wafer, attaching the photosensitive adhesive film on the structural wafer by using a film attaching machine, tearing off the supporting film, and transferring 100% of the photosensitive adhesive film to the structural wafer.
Exposing for 20s by using an ultraviolet lamp (i line and g line), developing by using 2.38% tetramethylammonium hydroxide, flushing by using deionized water, and baking (150 ℃/1h,200 ℃/1h,250 ℃/1 h) in a blast oven to obtain a cured open hole pattern and a cavity pattern, placing the cavity pattern into a molding press for molding test, wherein a 250 mu m cavity span cover is not collapsed, as shown in figure 1.
EXAMPLE 2,
In contrast to example 1, the amount of inorganic filler was adjusted to 60% of the total solids mass, the remainder being the same.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 200g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 214g of silica (size 1 to 3 μm) was added to the homogeneous solution, and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
In the photosensitive resin composition prepared in this example, the mass ratio of the polyamic acid resin, the photocrosslinker, the photoinitiator, the polymerization inhibitor, the inorganic filler, the dispersing agent and the solvent is 100:40:1:0.15:214:1:200.
the prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 8 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
The negative photosensitive solid adhesive film prepared by the embodiment can reach the cavity span of 250 mu m, the cover does not collapse, and the film transfer rate is 100%.
EXAMPLE 3,
In contrast to example 1, the amount of inorganic filler was adjusted to 70% of the total solids mass, the remainder being the same.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 260g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 332g of silica (size 1 to 3 μm) was added to the homogeneous solution, and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
In the photosensitive resin composition prepared in this example, the mass ratio of the polyamic acid resin, the photocrosslinker, the photoinitiator, the polymerization inhibitor, the inorganic filler, the dispersing agent and the solvent is 100:40:1:0.15:332:1:260.
the prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 5 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
The negative photosensitive solid film prepared in this example was molded to have a cavity cover with edge breakage, as shown in fig. 2, with a film transfer rate of 100%.
Comparative example 1,
In contrast to example 1, the amount of inorganic filler was adjusted to 40% of the total solids mass, the remainder being the same.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 140g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 95g of silica (1 to 3 μm in size) was added to the homogeneous solution and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
The prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 15 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
The negative photosensitive solid adhesive film prepared in this comparative example was subjected to 250 μm cavity span lid collapse, as shown in FIG. 3, with a film transfer rate of 100%.
Comparative example 2,
In this comparative example, 4-diphenyl ether dianhydride (ODPA): 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) =1: 1, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane: triazine diamine = 1:0.8, the amount of rigid dianhydride is increased compared to example 1.
In a 500ml three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 31.02g of 4,4 diphenyl ether dianhydride, 29.42g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 52.05g of 2-hydroxyethyl methacrylate, 31.63g of pyridine and 230g N-methylpyrrolidone (NMP) were successively added and stirred at room temperature for 6 hours to give the corresponding diacid dimethacrylate. The diacid dimethacrylate solution was combined with 47.59g SOCl 2 And (3) reacting for 2 hours at the temperature of 0-10 ℃ and reacting for 4 hours at room temperature to generate the corresponding diacyl chloride dimethacrylate.
41.25g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 100g of NMP were introduced into a 1L three-necked round bottom flask (A) equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
In another 100mL three-necked round bottom flask B equipped with a mechanical stirrer, thermometer and nitrogen protection device, 9.36g of triazine diamine and 10g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
Adding the diamine solution in the three-neck round bottom flask (A) into the prepared diacid chloride dimethacrylate solution, and dripping for 1h; then, reacting for 6 hours at room temperature; adding diamine solution in the three-neck round bottom flask (B) for 0.2h; then, the reaction was carried out at room temperature for 4 hours.
The reaction solution was put into 10L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polyimide precursor resin having a resin molecular weight of 30000.
The film transfer rate of the negative photosensitive solid adhesive film prepared in the comparative example is reduced to 80%.
Comparative example 3,
In this comparative example, 4-diphenyl ether dianhydride (ODPA): 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) =1: 0.9,2,2 bis (3-amino-4-hydroxyphenyl) hexafluoropropane: triazine diamine = 1:0.9, the amount of triazine diamine is increased compared with example 1; the molar ratio of dianhydride to diamine is 1:1.015.
in a 500ml three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 31.02g of 4,4 diphenyl ether dianhydride, 26.48g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 49.45g of 2-hydroxyethyl methacrylate, 30.05g of pyridine and 230g N-methylpyrrolidone (NMP) were successively added and stirred at room temperature for 6 hours to give the corresponding diacid dimethacrylate. The diacid dimethacrylate solution was combined with 45.21g SOCl 2 And (3) reacting for 2 hours at the temperature of 0-10 ℃ and reacting for 4 hours at room temperature to generate the corresponding diacyl chloride dimethacrylate.
In a 1L three neck round bottom flask (A) equipped with a mechanical stirrer, thermometer and nitrogen blanket, 37.17g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 100g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
In another 100mL three-necked round bottom flask B equipped with a mechanical stirrer, thermometer and nitrogen protection device, 10.15 triazine diamine and 10g NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
Adding the diamine solution in the three-neck round bottom flask (A) into the prepared diacid chloride dimethacrylate solution, and dripping for 1h; then, reacting for 6 hours at room temperature; adding diamine solution in the three-neck round bottom flask (B) for 0.2h; then, the reaction was carried out at room temperature for 4 hours.
The reaction solution was put into 10L of deionized water, and solid was precipitated, filtered and dried in vacuo to obtain a polyimide precursor resin having a resin molecular weight of 29000.
Since the amount of triazine diamine is too large, the alkaline water solubility of the resin is lowered, and normal photolithography development is not possible.
As is clear from examples 1 to 3 and comparative examples 1 to 3, an excessive amount of rigid dianhydride results in a decrease in film transfer rate, and an excessive amount of triazine diamine affects normal photolithography development. In the maximum range of the rigid dianhydride and the triazine diamine, the collapse of a cavity span cover of 250 mu m can be caused when the inorganic filler content is 40 percent along with the increase of the inorganic filler content, the photosensitive adhesive film can be normally used when the inorganic filler content reaches 50 percent and 60 percent, and the brittleness of the film can be increased when the inorganic filler content is increased to 70 percent, so that brittle fracture occurs during die pressing.
EXAMPLE 4,
In this example, 4-diphenyl ether dianhydride (ODPA): 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) =1: 0.5,2,2 bis (3-amino-4-hydroxyphenyl) hexafluoropropane: triazine diamine = 1:0.4, wherein the flexible dianhydride is the maximum amount, the triazine diamine is the minimum amount, and the inorganic filler accounts for 50% of the total solid mass; the molar ratio of dianhydride to diamine is 1:1.015.
in one is provided withInto a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 31.02g of 4, 4-diphenyl ether dianhydride, 14.71g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 39.04g of 2-hydroxyethyl methacrylate, 23.73g of pyridine and 200g N-methylpyrrolidone (NMP) were successively added, and stirred at room temperature for 6 hours to give the corresponding diacid dimethacrylate. The diacid dimethacrylate solution was combined with 35.69g SOCl 2 Reacting for 2h at 0-10 ℃ and 4h at room temperature to obtain the corresponding diacyl chloride dimethacrylate.
In a 1L three neck round bottom flask (A) equipped with a mechanical stirrer, thermometer and nitrogen blanket, 39.83g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 100g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
In another 100mL three-necked round bottom flask B equipped with a mechanical stirrer, thermometer and nitrogen blanket, 4.83g of triazine diamine and 10g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
Adding the diamine solution in the three-neck round bottom flask (A) into the prepared diacid chloride dimethacrylate solution, and dripping for 1h; then, reacting for 6 hours at room temperature; adding diamine solution in the three-neck round bottom flask (B) for 0.2h; then, the reaction was carried out at room temperature for 4 hours.
The reaction solution was put into 10L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polyimide precursor resin having a resin molecular weight of 34000.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 150g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 143g of silica (size 1 to 3 μm) was added to the homogeneous solution, and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
In the photosensitive resin composition prepared in this example, the mass ratio of the polyamic acid resin, the photocrosslinker, the photoinitiator, the polymerization inhibitor, the inorganic filler, the dispersing agent and the solvent is 100:40:1:0.15:143:1:150.
the prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was put into a 80℃air-blast oven to bake for 25 minutes, thereby obtaining a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
Tearing off the protective film, aligning the adhesive film with the structural wafer, attaching the photosensitive adhesive film on the structural wafer by using a film attaching machine, tearing off the supporting film, and transferring 100% of the photosensitive adhesive film to the structural wafer.
Exposing for 20s by using an ultraviolet lamp (i line and g line), developing by using 2.38% tetramethylammonium hydroxide, flushing by using deionized water, and baking (150 ℃/1h,200 ℃/1h,250 ℃/1 h) in a blast oven to obtain a cured open hole pattern and a cavity pattern, placing the cavity pattern into a molding press for molding test, and collapsing the 250 mu m cavity span cover.
EXAMPLE 5,
In comparison with example 4, the amount of the inorganic filler was adjusted to 60%, and the rest was the same.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 200g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 214g of silica (size 1 to 3 μm) was added to the homogeneous solution, and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
In the photosensitive resin composition prepared in this example, the mass ratio of the polyamic acid resin, the photocrosslinker, the photoinitiator, the polymerization inhibitor, the inorganic filler, the dispersing agent and the solvent is 100:40:1:0.15:214:1:200.
the prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 22 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
The negative photosensitive solid adhesive film prepared in this example was subjected to 250 μm cavity span lid collapse with a film transfer rate of 100%.
EXAMPLE 6,
In comparison with example 4, the amount of the inorganic filler was adjusted to 70%, and the rest was the same.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 260g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 332g of silica (size 1 to 3 μm) was added to the homogeneous solution, and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
In the photosensitive resin composition prepared in this example, the mass ratio of the polyamic acid resin, the photocrosslinker, the photoinitiator, the polymerization inhibitor, the inorganic filler, the dispersing agent and the solvent is 100:40:1:0.15:332:1:260.
the prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 18 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
The 250 μm cavity span of the negative photosensitive solid adhesive film prepared in this example did not collapse, and the film transfer rate was 100%.
Comparative example 4,
In comparison with example 4, the amount of inorganic filler was adjusted to 80%, the remainder being the same.
1.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 0.15g of hydroquinone (polymerization inhibitor), 40g of ethoxylated trimethylol propane triacrylate (photocrosslinker), 1.0g of KH560 (dispersant) were added in this order to 260g of NMP in a thousands of ultra clean room equipped with a yellow light, and stirred at room temperature for 1 hour to form a homogeneous solution. 568g of silica (size 1 to 3 μm) was added to the homogeneous solution and stirred for 3 hours to form a homogeneous dispersion. 100g of the polyamic acid resin was added to the uniform dispersion, and stirred to a homogeneous solution.
The prepared solution is coated on a supporting film PET to prepare a wet film by a knife coating mode. Then, the film was baked in a blowing oven at 80℃for 15 minutes to obtain a photosensitive solid film, and the film thickness was measured to be 40. Mu.m. And attaching a protective film on the surface of the solid adhesive film in a film coating mode, wherein the attaching pressure is 0.2MPa. An alkaline aqueous developed negative photosensitive solid film having a support film and a protective film was obtained.
Brittle fracture occurred in the middle of 250 μm cavity span of the negative photosensitive solid adhesive film prepared in this example, as shown in fig. 4.
Comparative example 5,
In this comparative example, 4-diphenyl ether dianhydride (ODPA): 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) =1: 0.4,2,2 bis (3-amino-4-hydroxyphenyl) hexafluoropropane: triazine diamine = 1:0.4, the inorganic filler represents 70% of the total solids mass, and the amount of flexible dianhydride is increased compared to example 6.
In a 500ml three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 31.02g of 4,4 diphenyl ether dianhydride, 11.77g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 36.44g of 2-hydroxyethyl methacrylate, 22.15g of pyridine and 200g N-methylpyrrolidone (NMP) were successively added and stirred at room temperature for 6 hours to give the corresponding diacid dimethacrylate. The diacid dimethacrylate solution was combined with 33.31g SOCl 2 Reacting at 0-10deg.C for 2h and at room temperature for 4h to obtain the corresponding diacid chloride diacidAnd (3) a methacrylate.
In a 1L three neck round bottom flask (A) equipped with a mechanical stirrer, thermometer and nitrogen blanket, 37.17g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 100g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
In another 100mL three-necked round bottom flask B equipped with a mechanical stirrer, thermometer and nitrogen blanket, 4.51 and 10g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
Adding the diamine solution in the three-neck round bottom flask (A) into the prepared diacid chloride dimethacrylate solution, and dripping for 1h; then, reacting for 6 hours at room temperature; adding diamine solution in the three-neck round bottom flask (B) for 0.2h; then, the reaction was carried out at room temperature for 4 hours.
The reaction solution was put into 10L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polyimide precursor resin having a resin molecular weight of 35000.
The negative photosensitive solid adhesive film prepared in this comparative example has a 250 μm cavity span lid collapse and a film transfer rate of 100%.
Comparative example 6,
In this comparative example, 4-diphenyl ether dianhydride (ODPA): 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) =1: 0.5,2,2 bis (3-amino-4-hydroxyphenyl) hexafluoropropane: triazine diamine = 1:0.3, the inorganic filler accounts for 70% of the total solid mass, and compared with the example 6, the amount of triazine diamine is reduced; the molar ratio of dianhydride to diamine is 1:1.015.
In a 500ml three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 31.02g of 4,4 diphenyl ether dianhydride, 11.77g of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 36.44g of 2-hydroxyethyl methacrylate, 22.15g of pyridine and 200g N-methylpyrrolidone (NMP) were successively added and stirred at room temperature for 6 hours to give the corresponding diacid dimethacrylate. The diacid dimethacrylate solution was combined with 33.31g SOCl 2 Reacting for 2 hours at the temperature of 0-10 ℃,reacting for 4 hours at room temperature to obtain the corresponding diacid chloride dimethacrylate.
In a 1L three neck round bottom flask (A) equipped with a mechanical stirrer, thermometer and nitrogen blanket, 42.89g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 100g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
In another 100mL three-necked round bottom flask B equipped with a mechanical stirrer, thermometer and nitrogen blanket, 3.90 and 10g of NMP were added and stirred to dissolve to form a homogeneous transparent diamine solution; the mixed diamine solution was cooled to below 10 ℃ using an ice bath.
Adding the diamine solution in the three-neck round bottom flask (A) into the prepared diacid chloride dimethacrylate solution, and dripping for 1h; then, reacting for 6 hours at room temperature; adding diamine solution in the three-neck round bottom flask (B) for 0.2h; then, the reaction was carried out at room temperature for 4 hours.
The reaction solution was put into 10L of deionized water, and solid was precipitated, filtered, and vacuum-dried to obtain a polyimide precursor resin having a resin molecular weight of 35000.
The negative photosensitive solid adhesive film prepared in this comparative example has a 250 μm cavity span lid collapse and a film transfer rate of 100%.
As is evident from examples 4-6 and comparative examples 4-6, too much flexible dianhydride and too little triazine diamine can result in collapse of the 250 μm cavity span lid. Within the scope of the flexible dianhydride and triazine diamine defined by the invention, the 250 μm cavity span cap does not collapse as the amount of inorganic filler increases to 70%. However, when the filler content reaches 80%, the brittleness of the film increases, and brittle fracture in the middle of the cavity occurs during molding.
EXAMPLE 7,
In this example, 31.02g of 4, 4-diphenyl ether dianhydride was replaced with 32.22g of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), and the remainder was the same as in example 1; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
EXAMPLE 8,
In this example 31.02g of 4, 4-diphenyl ether dianhydride was replaced with 44.42g of hexafluorodianhydride (6 FDA) and the remainder was the same as in example 1; the molar ratio of dianhydride to diamine is 1:1.015.
The cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
EXAMPLE 9,
In this example 31.02g of 4, 4-diphenyl ether dianhydride was replaced with 52.05g of bisphenol A dianhydride (BPADA) and the remainder was the same as in example 1; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
Examples 7-9 compare to example 1, with different flexible groups, better performance can be achieved at 70% filler content.
EXAMPLE 10,
In this example, 26.48g of 3,3', 4' -biphenyltetracarboxylic dianhydride was replaced with 19.63g of pyromellitic anhydride (PMDA), and the remainder was identical to that of example 1; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
EXAMPLE 11,
In this example, 26.48g of 3,3', 4' -biphenyltetracarboxylic dianhydride was replaced with 18.91g of 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, and the remainder was identical to that of example 1; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
EXAMPLE 12,
In this example, 26.48g of 3,3', 4' -biphenyltetracarboxylic dianhydride was replaced with 22.33g of bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, and the remainder was identical to that of example 1; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
Examples 10-12 compared to example 1, different rigid groups can achieve better performance at 50% filler content.
EXAMPLE 13,
In this example, 4.83g of triazine diamine was replaced with 8.14g of benzomelamine, the remainder being the same as in example 6; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
EXAMPLE 14,
In this example, 4.83g of triazine diamine was replaced with 5.44g of 6-methyl-1, 3, 5-triazine-2, 4-diamine, the remainder being the same as in example 6; the molar ratio of dianhydride to diamine is 1:1.015.
the cavity span cover of the negative photosensitive solid adhesive film 250 μm prepared in this example does not collapse, and the film transfer rate is 100%.
Comparative example 7,
In this comparative example, 4.83g of triazine diamine was replaced with 5.48g of 1,3, 5-triazine-2, 4, 6-triamine, and the remainder was the same as in example 1.
In the process of preparing the resin, the body type resin grows, and the resin cannot be normally synthesized.
Comparative example 8,
In this comparative example, 4.83g of triazine diamine was replaced with 4.18g of 2-amino-1, 3, 5-triazine, and the remainder was the same as in example 1.
The cavity span cover of the negative photosensitive solid adhesive film of 250 μm prepared in this comparative example does not collapse, and the film transfer rate is 60%.
As is clear from examples 13 to 14 and comparative examples 7 to 8, the triazine diamine within the scope of the present invention satisfies the object of the present invention. Other triazine diamines containing halogens and the like affect the reliability of the electrical properties of the materials and are therefore eliminated at the beginning of the design, while other triazine amines cause problems such as inability to synthesize resins and reduced film transfer rate.
Claims (10)
1. A method for preparing a polyamic acid ester resin, comprising the steps of:
s1, reacting dianhydride with an alcohol compound containing unsaturated double bonds to obtain diester diacid;
s2, reacting the diester diacid with an acyl chloride reagent to obtain corresponding diester diacid chloride;
s3, carrying out polycondensation reaction on the diester diacid chloride and a diamine solution I;
the diamine solution I is a diamine solution containing hydroxyl;
the diamine containing hydroxyl is at least one of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 3' -dihydroxybenzidine and aromatic diamine shown in the following structure:
S4, after the polycondensation reaction is carried out for 3-8 hours, adding a diamine solution II into the reaction system of the step S3 to continue the polycondensation reaction, and obtaining the polyamide acid ester resin after solid precipitation;
the diamine solution II is a triazine diamine solution;
the triazine diamine is at least one of triazine diamine, benzomelamine and 6-methyl-1, 3, 5-triazine-2, 4-diamine;
capping with the triazine diamine;
the molar ratio of the diamine containing hydroxyl groups to the triazine diamine is 1: 0.4-0.8;
the molar ratio of the dianhydride to the diamine is 1: 1.01-1.025, wherein the diamine comprises the diamine containing hydroxyl and the triazine diamine.
2. The method of manufacturing according to claim 1, characterized in that: the dianhydride comprises flexible dianhydride and rigid dianhydride, and the molar content of the flexible dianhydride is more than or equal to 50 percent.
3. The preparation method according to claim 1 or 2, characterized in that: the flexible dianhydride is at least one selected from hexafluorodianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A dianhydride, 4 diphenyl ether dianhydride and diphenyl sulfide dianhydride;
the rigid dianhydride is at least one selected from the group consisting of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 2,3',3,4' -biphenyl tetracarboxylic dianhydride, pyromellitic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride and 1,2,3, 4-cyclopenta-tetracarboxylic dianhydride.
4. The preparation method according to claim 1 or 2, characterized in that: the alcohol compound containing unsaturated double bonds is selected from at least one of 2-hydroxy-3-phenoxypropyl methyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tertiary butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tertiary butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and 2-hydroxyethyl methacrylate;
the acyl chloride reagent is selected from thionyl chloride.
5. The polyamic acid ester resin prepared by the method of any one of claims 1 to 4;
the molecular weight of the polyamic acid ester resin is 15000-40000.
6. A photosensitive resin composition comprises the following components in parts by mass:
100 parts by mass of the polyamic acid ester resin according to claim 5, 30 to 60 parts by mass of a photocrosslinking agent, 0.1 to 15 parts by mass of a photoinitiator, 0.1 to 5 parts by mass of a polymerization inhibitor, 87 to 390 parts by mass of an inorganic filler, 1 to 5 parts by mass of a dispersing agent, and 100 to 300 parts by mass of a solvent.
7. The photosensitive resin composition according to claim 6, wherein: the photocrosslinker is at least one selected from the group consisting of 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl methacrylate, ethylene glycol diethyl ether acrylate and polyethylene glycol methacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tri (2-hydroxyethyl) isocyanurate triacrylate and tricyclic sunflower-alkane dimethanol diacrylate;
the photoinitiator is selected from at least one of benzophenone, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzil derivatives, benzoin derivatives, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime and 1, 3-diphenyl propanetrione-2- (O-ethoxycarbonyl) oxime;
The polymerization inhibitor is at least one selected from hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol;
the inorganic filler is at least one selected from silicon dioxide, mica powder, aluminum oxide and talcum powder;
the inorganic filler accounts for 50-70% of the total solid mass;
the dispersing agent is an adhesion promoter with an epoxy group;
the solvent is at least one selected from N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, ethyl lactate, propylene glycol methyl ether acetate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate.
8. An alkali aqueous developable photosensitive adhesive film resistant to mold pressing, which is made of the photosensitive resin composition of claim 6 or 7.
9. The method for preparing the anti-molding alkaline aqueous development photosensitive adhesive film according to claim 8, comprising the following steps:
s I, coating: coating the photosensitive resin composition according to claim 6 or 7 on the surface of a support film;
S II, pre-baking: baking the photosensitive resin composition on the surface of the support film to form a photosensitive solid adhesive film with the support film;
and S III, laminating a protective film: attaching the protective film to the photosensitive solid adhesive film to obtain an alkaline water-based developed negative photosensitive solid adhesive film;
the supporting film and the protecting film are made of PET or PP;
the thickness of the supporting film is 10-250 mu m, and the thickness of the protecting film is 5-250 mu m;
the baking conditions were as follows: baking in a hot plate, a baking oven or a baking channel at 60-120 ℃ for 1-60 min;
the bonding conditions are as follows: the temperature is 50-100 ℃, and the pressure is 0.1-0.5 MPa.
10. Use of the alkali aqueous developable photosensitive film of claim 8 for a cap of hollow structure as an electronic part.
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| CN115232017A (en) * | 2021-03-15 | 2022-10-25 | 华为技术有限公司 | Compound, resin, and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116577965A (en) * | 2023-07-13 | 2023-08-11 | 明士(北京)新材料开发有限公司 | Negative photosensitive solid adhesive film and preparation method thereof |
| CN116577965B (en) * | 2023-07-13 | 2023-10-03 | 明士(北京)新材料开发有限公司 | Negative photosensitive solid adhesive film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN116333303B (en) | 2023-08-04 |
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