CN117701233A

CN117701233A - Photosensitive polyimide glue solution suitable for coating and coating method thereof

Info

Publication number: CN117701233A
Application number: CN202311780786.9A
Authority: CN
Inventors: 唐新颖; 贾斌; 王敬波; 赵云云; 李响
Original assignee: Minseoa Beijing Advanced Materials Development Co Ltd
Current assignee: Minseoa Beijing Advanced Materials Development Co Ltd
Priority date: 2023-12-22
Filing date: 2023-12-22
Publication date: 2024-03-15
Anticipated expiration: 2043-12-22
Also published as: CN117701233B

Abstract

The invention discloses a photosensitive polyimide glue solution suitable for coating and a coating method thereof. The glue solution is prepared from the following raw materials in parts by weight: the viscosity of the glue solution is controlled between 800 cps and 1500cps, and the glue solution comprises alkali water-soluble resin, a photo-crosslinking agent, a photo-initiator, a polymerization inhibitor, an inorganic filler, a dispersing agent, a defoaming agent, a leveling agent, an anti-settling agent, a solvent and the like. The glue solution can reach normal temperature for 48 hours without sedimentation, the coated glue film can be baked to obtain the glue film with better thickness uniformity which is within +/-1 mu m deviation, and the surface has no defects of air holes, vertical bars, filler condensation points and the like.

Description

Photosensitive polyimide glue solution suitable for coating and coating method thereof

Technical Field

The invention belongs to the technical field of high polymer materials and semiconductor packaging, and particularly relates to a photosensitive polyimide glue solution suitable for coating and a coating method thereof.

Background

SAW surface filter devices in electronic products are currently a hollow structured electronic component. The hollow structure is divided into a roof and a wall. Because of the hollow structure, the hollow structure needs to be covered on a cavity formed by a wall body in a film mode, then photoetching and developing are carried out, finally, a stable cavity is obtained through heat curing, and other working procedures are carried out.

CN 113646882a, the photosensitive resin composition provided can improve the high sensitivity of the cap portion of the hollow structure and can be well patterned by photolithography. The photosensitive resin sheet using the photosensitive resin composition of the present invention is useful for the use of a hollow structure for covering an electronic component having a hollow structure. CN 115236938A provides and 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 that in filter manufacturing and needing photoetching development. The invention solves the problems that the size of the opening after photoetching development of the photosensitive solid adhesive film formed by the photosensitive adhesive is small and the size of the opening is large, and the electric performance reliability of the later process is affected. However, there is no mention of how glue is suitable for coating.

The photosensitive film for a filter is generally a thick film of 20 μm or more, and it is required to have good uniformity of film thickness and to control the film thickness deviation within + -1 μm. Meanwhile, the defects of air holes, orange peel, vertical bars, filler condensation points and the like cannot appear on the surface.

Disclosure of Invention

The invention aims to provide a photosensitive polyimide glue solution suitable for coating.

The photosensitive polyimide glue solution suitable for coating provided by the invention is prepared from the following raw materials: the coating comprises alkaline water-soluble resin, a photo-crosslinking agent, a photoinitiator, a polymerization inhibitor, an inorganic filler, a dispersing agent, a defoaming agent, a leveling agent, an anti-settling agent and a solvent.

The weight portions of the components are as follows: 100 parts by mass of an alkaline water-soluble resin, 40-100 parts by mass of a photo-crosslinking agent, 0.1-0.5 part by mass of a photoinitiator, 0.1-5 parts by mass of a polymerization inhibitor, 60-467 parts by mass of an inorganic filler, 1-5 parts by mass of a dispersing agent, 0.05-1 part by mass of a defoaming agent, 0.01-1 part by mass of a leveling agent, 0.01-2 parts by mass of an anti-settling agent and 100-300 parts by mass of a solvent.

For coating, the smaller the viscosity of the coating dope, the stronger the continuous coating property. However, too low a viscosity of the dope may result in uncontrollable fluidity of the dope during coating, and poor edge property after coating, and outflow of the dope may occur. Meanwhile, the viscosity of the glue solution is too low, which is unfavorable for the stability of the filler in the glue solution and easy sedimentation. In contrast, the higher the viscosity of the glue solution, the worse the coating property of the glue solution, and the film thickness uniformity is difficult to control, and the defects of vertical channels, filler condensation points and the like are easy to appear on the surface of the obtained glue film.

In order to achieve both the coatability of the dope, the surface defect after coating and the anti-settling property of the filler, the viscosity of the dope is controlled to be 800-1550cps, preferably 1000-1300cps.

Preferably, the molecular weight of the alkaline water-soluble resin is 15000-35000 in order to maintain the film forming property and the photolithography developing property of the adhesive film.

Preferably, in order to increase the universality of the glue solution to the additive, the alkaline water-soluble resin is an alkaline water-soluble PI resin. Because the PI resin does not contain esterified branched chains, the problem of unstable glue solution caused by the acid-base property of the additive is not easy to occur.

The alkaline water-soluble PI resin is prepared by the following steps:

(A) Adding diamine into an organic solvent, and stirring to dissolve the diamine to form a homogeneous diamine solution;

(B) Adding dianhydride and a molecular weight regulator into the homogeneous diamine solution formed in the step (A);

(C) Adding toluene into the reaction system of the step (B), and heating and refluxing to obtain a resin solution;

(D) Mixing the resin solution with a poor solvent to precipitate solid resin; the solid resin was washed and dried to obtain an alkaline water-soluble PI resin.

Further:

in the step (A), the diamine is diamine containing hydroxyl;

The diamine containing hydroxyl groups may be selected from: at least one of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 2-bis (3-amino-4-hydroxyphenyl) propane, 3' -dihydroxybenzidine, and an aromatic diamine having the structural formula shown below:

the organic solvent is NMP (N-methyl pyrrolidone);

in step (B), the dianhydride may be selected from: at least one of hexafluorodianhydride (6 FDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), bisphenol A dianhydride (BPADA), 4' -biphenyl ether dianhydride (ODPA), diphenyl sulfide dianhydride (TDPA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 2,3',3,4' -biphenyl tetracarboxylic dianhydride (alpha-BPDA), pyromellitic dianhydride (PMDA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, and 1,2,3, 4-cyclopentanetetracarboxylic dianhydride.

The molecular weight regulator is phthalic anhydride;

the molar ratio of the diamine in the step (A) to the dianhydride and the molecular weight modifier in the step (B) may be as follows: 1:0.999-0.98:0.002-0.04;

in the step (C), the temperature of the heating reflux can be 180 ℃ and the time can be 4-6h;

in step (D), the poor solvent may be selected from: at least one of water, ethanol and isopropanol.

Preferably, the photocrosslinking agent may be 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, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate and tricyclic sunflower dimethanol diacrylate.

Preferably, the photoinitiator may be selected from: at least one of IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE 03.

Preferably, the polymerization inhibitor may be 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 may be selected from: at least one of silica, mica powder, alumina, yttria, and the like.

Among them, the silica is preferably angular silica (commercially available) having a size of 0.2 to 3. Mu.m.

The mica powder is preferably a dry-produced mica powder (commercially available) having a size of 0.2 to 6. Mu.m, preferably 0.5 to 3. Mu.m.

The alumina (commercially available) has a size of 0.2-3 μm.

The yttrium oxide (commercially available) has a size of 0.2 to 3. Mu.m, preferably 0.5 to 1.5. Mu.m.

In order to maintain the anti-molding performance and film forming property of the photosensitive adhesive film after coating and film forming, the inorganic filler accounts for 30-70% of the total solid matter;

Preferably, the dispersant is a silane coupling agent free of free amine groups and mercapto groups, preferably, the dispersant is KH570 (γ - (methacryloyloxy) propyl trimethoxysilane) having a double bond.

Preferably, the defoamer is organosilicon and cannot contain free amine groups and mercapto groups; KS-603 defoamer and KS-66 defoamer are preferred.

Preferably, the leveling agent cannot contain free amine groups and mercapto groups and is selected from acrylic esters; BYK-354, BYK-361N are preferred.

Preferably, the anti-settling agent does not contain free amine and mercapto groups, preferably fumed silica.

Preferably, the solvent consists of a high boiling point solvent and a low boiling point solvent.

The mass ratio of the high-boiling point solvent to the low-boiling point solvent is 3:2-1:2 (preferably 3:2-1:1) for adjusting the coating speed and the drying speed.

The high boiling point solvent may be selected from: one or two of N-methyl pyrrolidone and gamma-butyrolactone.

The low boiling point solvent may be selected from: one or a mixture of several of N, N' -dimethylformamide, ethyl lactate, propylene glycol methyl ether acetate, cyclopentanone, tetrahydrofuran, ethyl acetate and butyl acetate.

According to one embodiment of the invention, the solvent consists of N-methyl pyrrolidone, gamma-butyrolactone and ethyl lactate according to a mass ratio of 2:1:2, and mixing the materials in proportion.

According to another embodiment of the invention, the solvent is prepared from N-methyl pyrrolidone and ethyl lactate according to a mass ratio of 1:1, and mixing the materials in proportion.

According to a further embodiment of the invention, the solvent consists of N-methyl pyrrolidone and ethyl lactate according to a mass ratio of 1:2, and mixing the materials in proportion.

According to one embodiment of the invention, the solvent is prepared from N-methyl pyrrolidone, gamma-butyrolactone and propylene glycol methyl ether acetate according to a mass ratio of 2:1:2, and mixing the materials in proportion.

The preparation method of the photosensitive polyimide glue solution suitable for coating comprises the following steps:

(a) Mixing and stirring alkaline water-soluble resin, a photo-crosslinking agent, a photo-initiator, a polymerization inhibitor and part of solvent, and keeping the resin for later use after the resin is dissolved;

(b) Mixing and stirring inorganic filler, dispersing agent and part of solvent, and forming flowable slurry for later use;

(c) Mixing and stirring the defoaming agent and the residual solvent, and standing by after a uniform solution is formed;

(d) Dispersing the clear resin liquid in the step (a) into the slurry formed in the step (b) at a high speed, and respectively adding an anti-settling agent, a defoaming agent diluted in the step (c) and a leveling agent to obtain uniformly dispersed slurry;

(f) And carrying out vacuum defoaming on the slurry to obtain the photosensitive polyimide glue solution suitable for coating.

In the step (a), the stirring speed is 100-300r/min, and the stirring time is more than or equal to 12h.

In the step (b), the stirring speed is 100-300r/min, and the stirring time is more than or equal to 12h.

In the step (c), the stirring speed is 100-300r/min, and the stirring time is more than or equal to 2h.

In the step (d), the high-speed dispersion speed is 1000-3000r/min, and the dispersion time is 1-3h.

In the step (f), the vacuum degree of the vacuum defoaming is 0.1MPa, and the defoaming time is 0.5-1h.

The invention also provides a coating method of the photosensitive polyimide glue solution suitable for the preparation.

The coating method of the photosensitive polyimide glue solution provided by the invention comprises the following steps:

(1) Coating: coating the photosensitive polyimide glue solution suitable for coating on the surface of a support film;

(2) Pre-baking: baking the photosensitive polyimide glue solution coated on the surface of the support film to form a photosensitive solid glue film with the support film;

(3) And (3) laminating a protective film: and bonding the protective film and the photosensitive solid adhesive film with the support film to obtain the negative photosensitive solid adhesive film subjected to alkaline water development.

In the step (1) of the method, the material of the support film comprises PET, TPX, PP plasma film; the thickness of the support film may be 25 to 100. Mu.m, preferably 30 to 50. Mu.m.

The coating method is selected from knife coating, slot coating, micro-gravure coating, screen printing, etc.

The coating speed of the coating may be 1-100mm/s.

In the method step (2), the baking conditions are as follows: baking for 1-60 min at 80-100 deg.C with hot plate or hot air. The photosensitive performance of the glue solution after forming the glue film can be destroyed when the temperature exceeds 100 ℃, the solvent is volatilized slower and the baking time is long when the temperature is lower than 80 ℃, and the baking efficiency is reduced.

In the step (3), the protective film is made of PE, PP or PET;

the thickness of the protective film is 25-50 μm, preferably 30-50 μm; the protective film is not easy to be too thin, and the too thin is easy to deform in the attaching process. Too thick is not beneficial to winding.

The attaching of the protective film is carried out at 70-90 ℃;

the laminating pressure of the protective film is 0.1-0.5 MPa.

The laminating needs to have certain temperature and pressure, and the protection film just can be better with the glued membrane laminating. But the bonding temperature is lower than the baking temperature, so that the secondary volatilization of the solvent during bonding is avoided.

The negative photosensitive solid adhesive film prepared by the method and developed by the alkaline water system also belongs to the protection scope of the invention.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention is based on the problem of coating in the research and development process, and the invention is a photosensitive polyimide solution and coating method for coating. The photosensitive polyimide glue solution obtained by the invention is coated, and the surface of the obtained glue film has no defects and better uniformity of the film thickness. The photosensitive polyimide solution and the coating method can effectively consider the coating efficiency and the retention of photoetching properties, and the film thickness uniformity and the defect-free film surface play a decisive role in the process operability repeatability and the yield of the photosensitive polyimide film formed by the photosensitive polyimide glue solution in the film pasting process.

Drawings

FIG. 1 is a schematic illustration of measuring film thickness at selected edge and center locations according to the 9-point method;

FIG. 2 is a photograph showing the surface state of the adhesive film prepared in example 1;

FIG. 3 is a photograph of the dope prepared in example 1 stored for 96 hours without precipitation;

FIG. 4 is a photograph showing the precipitation of the dope prepared in example 1 after 120 hours of storage;

FIG. 5 is a microscope photograph of the photosensitive polyimide film obtained in example 1 subjected to photolithography to obtain a pattern;

FIG. 6 is a microscopic photograph of the pattern obtained by photolithography of the photosensitive polyimide film obtained in example 4;

FIG. 7 is a photograph of a vertical bar defect of the adhesive film prepared in comparative example 2;

FIG. 8 is a photograph showing the surface state of the adhesive film prepared in comparative example 3;

FIG. 9 is a microscopic photograph of the photo-sensitive polyimide film obtained in comparative example 3 by photolithography to obtain a pattern;

FIG. 10 is a graph showing defects in bubble and filler condensation points of the adhesive film prepared in comparative example 5.

Detailed Description

The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.

The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.

The method for detecting the adhesive film in the following embodiment comprises the following steps:

Selecting square blocks with the size of 10cm from the middle of the adhesive film; according to the 9-point method, the film thickness is measured at the edge and the middle (shown in figure 1), the square is placed in a strong light detection table, and the defect phenomena such as bubbles, filler condensation points, vertical bars and the like are observed.

And (3) observing the stability of the glue solution: 5ml of the glue solution was placed in a 10ml transparent colorless sample bottle, and the presence or absence of sedimentation was observed every 24 hours.

The alumina used in the examples below was purchased from Hangzhou Hengna, model alpha; the silicon dioxide is purchased from Anhuixin Jintong material, model XY-01.

Example 1

40.29g of 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 250g of NMP, and stirred at room temperature until dissolved. 44.42g of 6FDA is added after the diamine is completely dissolved, 2.96g of phthalic anhydride is added after 20 hours of reaction, and the reaction is continued for 5 hours. 100ml of toluene was added to the reaction system, and the temperature was raised to 180℃and the mixture was refluxed for 5 hours to obtain a polyimide resin solution.

Pouring the polyimide resin solution into 5L of deionized water, precipitating solid, filtering, and drying in vacuum to obtain polyimide resin. The molecular weight of the polyimide resin was 30000.

In a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 50g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

In a thousands of ultra clean room equipped with yellow light, 50g of alumina (size 1 μm), 100g of silica (size 1 μm), 2g of KH570, 150g of solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

0.5g KS-66 was mixed with 20g solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:2, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3 hours.

The high-speed dispersing machine is started, the high-speed dispersing speed is 2000r/min, resin clear liquid, flowable slurry, dilution defoamer, 1g of fumed silica and 1.0g of BYK-361N are poured into the high-speed dispersing tank, and the high-speed dispersing time is 1.5h, so that the slurry which is uniformly dispersed is obtained.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1005cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

The coating was performed using a doctor blade at a coating speed of 50mm/s and a coating thickness of 100. Mu.m, and baked in a hot air oven at 80℃for 10 minutes.

And (3) attaching a 36-mu m PET protective film on the baked adhesive film by using the pressure of 0.2MPa to obtain the photosensitive adhesive film with a three-layer structure.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 1.

TABLE 1

0.039	0.040	0.039
			0.040	0.041	0.040
0.040	0.041	0.039

Defective results are presented: defect free (as shown in fig. 2).

5mL of the glue solution was placed in a 10mL sample bottle, and no sedimentation was observed for 24h, 48h,72h and 96h (as shown in FIG. 3). Delamination occurred after 120h (as shown in FIG. 4).

After the photosensitive polyimide glue solution is used for forming a photosensitive polyimide glue film through the method, film pasting and photoetching are carried out to obtain a microscopic picture of a pattern, and the photoetching is normal (as shown in figure 5).

Example 2

The overall viscosity of the dope was reduced to 856cps by adding the solvent to 60g of the resin clear solution as compared with example 1.

The preparation method of the resin clear liquid comprises the following steps: in a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 60g (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

The coating was performed using a doctor blade at a coating speed of 100mm/s and a coating thickness of 100. Mu.m, and baked in a hot air oven at 80℃for 10 minutes.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 2.

TABLE 2

0.038	0.038	0.038
			0.038	0.039	0.039
0.038	0.038	0.038

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h and 72 h. Layering sedimentation occurs after 96 hours. Photolithography is normal.

Example 3

The solvent of the resin clear solution was reduced to 42g and the overall viscosity of the dope increased to 1527cps as compared to example 1.

The preparation method of the resin clear liquid comprises the following steps: in a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 42g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 10mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 10min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 3.

TABLE 3 Table 3

0.041	0.041	0.040
			0.039	0.039	0.041
0.039	0.040	0.040

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h, 72h and 96 h. Layering sedimentation occurs after 120 h. Photolithography is normal.

Example 4

In contrast to example 1, the dianhydride in the resin was replaced with ODPA.

40.29g of 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 250g of NMP, and stirred at room temperature until dissolved. 31.02g of ODPA is added after the diamine is completely dissolved, 2.96g of phthalic anhydride is added after 20 hours of reaction, and the reaction is continued for 5 hours. 100ml of toluene was added to the reaction system, and the temperature was raised to 180℃and the mixture was refluxed to obtain a polyimide resin solution.

Pouring the polyimide resin solution into 5L of deionized water, precipitating solid, filtering, and drying in vacuum to obtain polyimide resin. The molecular weight of the polyimide resin was 25000.

In a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 40g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 977cps.

The obtained photosensitive polyimide glue solution is subjected to coating test.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 50mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 10min.

And (3) attaching a 50 mu m PP protective film on the baked adhesive film by using the pressure of 0.2MPa to obtain the photosensitive adhesive film with the three-layer structure.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 4.

TABLE 4 Table 4

0.040	0.041	0.040
			0.039	0.039	0.040
0.040	0.041	0.041

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h,72h and 96 h. Delamination occurred after 120 h. Photolithography is normal (as shown in fig. 6).

From the comparison of examples 1, 2, 3 and 4, the viscosity of the photosensitive polyimide glue solution is between 800 and 1550cps, and the glue film with good film thickness uniformity and no defect on the surface of the film can be obtained after coating. Meanwhile, the maximum storage at normal temperature reaches 96 hours without sedimentation, which is greater than the index of 48 hours without sedimentation in normal temperature storage. When the resin structures are different, the formula can also enable the coating glue solution to reach a better coating state, and the photoetching is normal.

Example 5

The ratio of high boiling point and low boiling point solvents compared to example 1 was from 3:2 to 1:1.

in a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 53g of solvent (N-methylpyrrolidone: ethyl lactate=1:1, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

In a thousands of ultra clean room equipped with yellow light, 50g of alumina (size 1 μm), 100g of silica (size 1 μm), 2g of KH570, 150g of solvent (N-methylpyrrolidone: ethyl lactate=1:1, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

0.5g KS-66 was mixed with 20g solvent (N-methylpyrrolidone: ethyl lactate=1:1, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3h.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1103cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

The coating was performed using a doctor blade at a coating speed of 55mm/s and a coating thickness of 100. Mu.m, and baked in a hot air oven at 80℃for 9 minutes.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 5.

TABLE 5

0.041	0.040	0.039
			0.040	0.041	0.040
0.040	0.041	0.039

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h and 72 h. Delamination occurred after 96 hours.

Example 6

The ratio of high boiling point and low boiling point solvents compared to example 1 was from 3:2 to 1:2.

in a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 62g of solvent (N-methylpyrrolidone: ethyl lactate=1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

In a thousands of ultra clean room equipped with yellow light, 50g of alumina (size 1 μm), 100g of silica (size 1 μm), 2g of KH570, 150g of solvent (N-methylpyrrolidone: ethyl lactate=1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

0.5g KS-66 was mixed with 20g solvent (N-methylpyrrolidone: ethyl lactate=1:2, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3h.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1092cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 55mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 7min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 6.

TABLE 6

0.038	0.040	0.039
			0.039	0.039	0.38
0.039	0.039	0.038

Defective results are presented: defect-free.

5mL of the glue solution is taken and placed in a 10mL sample bottle, and no sedimentation is caused after 24h and 48h observation. Delamination occurred after 72 h.

Example 7

In contrast to example 1, the low boiling solvent "ethyl lactate" was replaced with "propylene glycol methyl ether acetate".

In a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 50g of solvent (N-methylpyrrolidone: gamma-butyrolactone: propylene glycol methyl ether acetate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

In a thousand-level ultra clean room equipped with yellow light, 50g of alumina, 100g of silica, 2g of KH570, 150g of solvent (N-methylpyrrolidone: γ -butyrolactone: propylene glycol methyl ether acetate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

0.5g KS-66 was mixed with 20g solvent (N-methylpyrrolidone: gamma-butyrolactone: propylene glycol methyl ether acetate=2:1:2, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3 hours.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1088cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 7.

TABLE 7

0.039	0.040	0.039
			0.041	0.040	0.040
0.040	0.041	0.040

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h,72h and 96 h. Delamination occurred after 120 h. Photolithography is normal.

From examples 1, 5, 6 and 7, the ratio of the solvent high boiling point and low boiling point solvents of the photosensitive polyimide dope was from 3: 2-1: 2, to obtain the film with good uniformity and no defect on the film surface. However, changing the ratio of the solvent to the high and low boiling point solvents affects the coating speed and baking time of the adhesive film. Meanwhile, the low boiling point solvent may be replaced with other low boiling point solvents. The high boiling point solvent may also be a single high boiling point solvent. The maximum storage at normal temperature reaches 96 hours without sedimentation, which is greater than the index of 48 hours without sedimentation in normal temperature storage. Photolithography is normal.

Example 8

Compared to example 1, 0.5g of defoamer was replaced with 0.3g of KS-603.

0.3g KS-603 was mixed with 20g solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:2, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3 hours.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 996cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 8.

TABLE 8

0.040	0.041	0.040
			0.040	0.040	0.039
0.040	0.040	0.039

Defective results are presented: defect-free.

Example 9

1.0g of BYK-361N leveling agent was replaced by 0.8g of BYK-354 in comparison with example 1.

The high-speed dispersing machine is started, the high-speed dispersing speed is 2000r/min, resin clear liquid, flowable slurry, dilution defoamer, 1g of fumed silica and 0.8g of BYK-354N are poured into the high-speed dispersing tank, and the high-speed dispersing time is 1.5h, so that the slurry which is uniformly dispersed is obtained.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1028cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 9.

TABLE 9

0.041	0.040	0.040
			0.040	0.040	0.040
0.039	0.039	0.039

Defective results are presented: defect-free.

From examples 1, 8 and 9, the defoamer and leveling agent of the photosensitive polyimide dope can be replaced with each other in the preferred material, but the amount to be used needs to be adjusted. Replacement of the defoamer and leveling agent does not cause an influence on the normal-temperature storability. The maximum storage at normal temperature reaches 96 hours without sedimentation, which is greater than the index of 48 hours without sedimentation in normal temperature storage.

Example 10

The filler content was increased from 50% to 70% compared to example 1.

In a thousand-level ultra clean room equipped with yellow light, 117g of alumina, 233g of silica, 4.5g of KH570, 200g of solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 823cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 100mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 5min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 10.

Table 10

0.037	0.038	0.038
			0.037	0.038	0.037
0.036	0.038	0.037

Defective results are presented: defect-free.

5mL of the glue solution is taken and placed in a 10mL sample bottle, and no sedimentation is caused after 24h and 48h observation. Delamination occurred after 72 h. Photolithography is normal.

Example 11

Compared with example 1, the filler content was reduced from 50% to 30%.

21g of alumina (size 1 μm), 43g of silica (size 1 μm), 4.5g of KH570, 100g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16h in a thousands of ultra clean room equipped with yellow light, to form a flowable slurry.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1378cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 50mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 13min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 11.

TABLE 11

0.042	0.042	0.042
			0.043	0.042	0.041
0.042	0.041	0.041

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h, 72h, 96h, 120h and 144 h. Delamination occurred after 168 h. Photolithography is normal.

According to the embodiment 1, 10 and 11, the filler content of the photosensitive polyimide glue solution is from 30% to 70%, so that the photosensitive polyimide glue solution can be stored for more than 48 hours at normal temperature without sedimentation, and can be maximally 144 hours without sedimentation. The photosensitive polyimide glue solution has good film thickness uniformity after coating and no defect on the surface. Photolithography is normal. It should be noted that as the filler content changes, the solvent content of the flowable slurry will also change.

Comparative example 1

The overall viscosity of the dope was reduced to 655cps by adding the solvent to 70g of the resin clear solution as compared to example 1.

In a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 70g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 120mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 10min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 12.

Table 12

0.035	0.036	0.035
			0.035	0.036	0.035
0.036	0.035	0.035

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24 hours. Delamination subsides after 48 h.

Comparative example 2

The solvent of the resin clear solution was reduced to 37g and the overall viscosity of the dope was increased to 1921cps as compared to example 1.

In a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 37g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 13.

TABLE 13

0.042	0.044	0.040
			0.045	0.042	0.043
0.045	0.045	0.040

Defective results are presented: there are vertical stripes. (as shown in FIG. 7)

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h, 72h, 96h, 120h, 144h and 168 h. Layering sedimentation occurs after 192 h.

From the comparison of example 1, comparative examples 1 and 2, it is apparent that the uniformity of the coated dope and the surface defect are not problematic when the viscosity of the dope is < 800cps, but only 24g of normal temperature storage without sedimentation can be maintained, and storage without sedimentation cannot be achieved for 48 hours at normal temperature. When the viscosity is more than 1500cps, the storage property at normal temperature is better, and no sedimentation is achieved for 168 hours. However, the thickness uniformity of the adhesive film was poor, and the deviation was more than + -1 μm. Meanwhile, vertical stripes appear after coating, resulting in surface defects.

Comparative example 3

The ratio of high boiling point and low boiling point solvents compared to example 1 was from 3:2 to 3:1.

in a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane trimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 50g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:1, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

In a thousand-level ultra clean room equipped with yellow light, 50g of alumina, 100g of silica, 2g of KH570, 150g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:1, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

0.5g KS-66 was mixed with 20g solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:1, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3 hours.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 877cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 10mm/s and a coating thickness of 100. Mu.m. The phenomenon of sticking hands still occurs when the glass is baked for 30min in hot air baking at 80 ℃, and the solvent volatility is poor.

Changing the coating conditions: blade coating was used at a coating speed of 10mm/s and a coating thickness of 100. Mu.m. Baking in hot air at 105deg.C for 10min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 14.

TABLE 14

0.041	0.040	0.040
			0.041	0.039	0.041
0.040	0.041	0.040

Defective results are presented: the phenomenon of filler condensation point occurs. (as shown in FIG. 8)

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h, 72h and 96 h. Delamination occurred after 120 h. And (3) baking the film in hot air at 105 ℃ for 10 minutes to obtain a photosensitive film with abnormal photoetching, failure of the photosensitive polyimide film and no optical etching performance. (as in FIG. 9)

Comparative example 4

The ratio of high boiling point and low boiling point solvents compared to example 1 was from 3:2 to 1:3.

in a thousands of ultra clean room equipped with yellow light, 100g of polyimide resin, 50g of trimethylolpropane dimethacrylate (photo-crosslinking agent), 0.2g IRGACURE OXE03 (photo-initiator), 0.2g of hydroquinone (polymerization inhibitor), 70g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:9, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours, and the resin was completely dissolved.

In a thousand-level ultra clean room equipped with yellow light, 50g of alumina, 100g of silica, 2g of KH570, 150g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:9, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

0.5g KS-66 was mixed with 20g solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:9, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3 hours.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1338cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 50mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 5min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 15.

TABLE 15

0.039	0.040	0.040
			0.040	0.039	0.041
0.040	0.041	0.040

Defective results are presented: defect-free. But the phenomenon of surface dryness occurs. The anti-sticking problem can occur after the adhesive film is placed at normal temperature.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h, 72h and 96 h. Delamination occurred after 120 h.

From the comparison of example 1, comparative examples 3, 4, it is seen that when the high boiling point solvent: the ratio of low boiling point solvent is greater than 3:2, after the baking temperature is increased, the solvent causes the failure of the photosensitive adhesive film, and meanwhile, the phenomenon that the surface of the adhesive film also has a filler condensation point appears. When a high boiling point solvent: the ratio of low boiling point solvents is less than 1:2, the surface dry phenomenon is easy to occur, and the adhesive film is easy to have the anti-adhesion phenomenon at normal temperature. This is because the low boiling point solvent is easily volatilized, and the surface of the adhesive film is easily skinned, so that the solvent inside the adhesive film is not easily volatilized.

Comparative example 5

In contrast to example 1, the defoamer was replaced with BYK-054 which was free of silicon.

0.5g of BYK-054 was mixed with 20g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio), and stirred in a beaker at a stirring speed of 180r/min for 3h.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1097cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 16.

Table 16

0.039	0.040	0.039
			0.040	0.041	0.040
0.040	0.041	0.039

Defective results are presented: there are bubbles and filler condensation points. (as shown in FIG. 10)

5mL of the glue solution is placed in a 10mL sample bottle, and the solution is observed for 24h, 48h,72h and 96h without sedimentation. Delamination occurred after 120 h.

Comparative example 6

In contrast to example 1, the leveling agent was replaced with BYK-399.

The high-speed dispersing machine is started, the high-speed dispersing speed is 2000r/min, resin clear liquid, flowable slurry, dilution defoamer, 1g of fumed silica and 1.0g of BYK-399 are poured into the high-speed dispersing tank, and the high-speed dispersing time is 1.5h, so that the slurry which is uniformly dispersed is obtained.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1045cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 17.

TABLE 17

0.039	0.040	0.038
			0.043	0.032	0.041
0.040	0.040	0.037

Defective results are presented: has vertical stripe defect.

From a comparison of example 1, comparative examples 6 and 7, it is evident that other defoamers and leveling agents cause defects to the coated film surface.

Comparative example 7

In contrast to example 1, the filler content was increased to 80%.

200g of alumina, 400g of silica, 2.5g of KH570, 270g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16h in a thousands of ultra clean room equipped with yellow light, to form a flowable slurry.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 819cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 18.

TABLE 18

0.040	0.040	0.039
			0.039	0.038	0.038
0.040	0.039	0.039

Defective results are presented: the filler condensation point occurs.

Comparative example 8

In contrast to example 1, the filler content was reduced to 20%.

In a thousand-level ultra clean room equipped with yellow light, 12g of alumina, 25g of silica, 1.5g of KH570, and 100g of solvent (N-methylpyrrolidone: γ -butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

The high-speed dispersing machine is started, the high-speed dispersing speed is 2000r/min, resin clear liquid, flowable slurry, diluting defoamer, 0.5g fumed silica and 1.0g BYK-361N are poured into the high-speed dispersing tank, and the high-speed dispersing time is 1.5h, so that the slurry which is uniformly dispersed is obtained.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1067cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

Blade coating was used at a coating speed of 50mm/s and a coating thickness of 100. Mu.m. Baking in 80deg.C hot air for 15min.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 19.

TABLE 19

0.040	0.040	0.039
			0.039	0.038	0.038
0.040	0.039	0.039

Defective results are presented: defect-free.

5mL of the glue solution is placed in a 10mL sample bottle, and no sedimentation is observed for 24h, 48h, 72h, 96h, 120h and 144 h. Delamination occurred after 168 h.

However, the filler content of less than 30% affects other properties of the photosensitive paste after forming the adhesive film, and is not included in the scope of the present patent.

From comparison of comparative examples 8 and 9 in example 1, it is evident that when the filler content is more than 70%, the dispersibility of the filler is poor, resulting in defects of the condensation point of the filler after coating.

Comparative example 9

In contrast to example 1, no anti-settling agent was present.

The high-speed dispersing machine is started, the high-speed dispersing speed is 2000r/min, resin clear liquid, flowable slurry, dilution defoamer and 1.0g BYK-361N are poured into the high-speed dispersing tank, and the high-speed dispersing time is 1.5h, so that slurry with uniform dispersion is obtained.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1085cps.

And coating and testing the obtained photosensitive polyimide glue solution.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 1. Mu.m. The results are shown in Table 20.

Table 20

0.039	0.040	0.039
			0.040	0.041	0.040
0.040	0.041	0.039

Defective results are presented: defect-free.

5mL of the glue solution is put into a 10mL sample bottle, and layering occurs after 24 hours.

Comparative example 10

In contrast to example 1, no defoamer or leveling agent was added

In a thousand-level ultra clean room equipped with yellow light, 50g of alumina, 100g of silica, 2g of KH570, 150g of solvent (N-methylpyrrolidone: gamma-butyrolactone: ethyl lactate=2:1:2, mass ratio) were placed in a three-necked flask and stirred at a stirring speed of 100r/min for 16 hours to form a flowable slurry.

And (3) starting the high-speed dispersing machine, wherein the high-speed dispersing speed is 2000r/min, pouring resin clear liquid, flowable slurry and 1g of fumed silica into the high-speed dispersing tank, and the high-speed dispersing time is 1.5h, so as to obtain uniformly dispersed slurry.

And (3) carrying out vacuum defoaming on the slurry, wherein the vacuum degree is 0.1MPa, and the defoaming time is 0.5h, so as to obtain the photosensitive polyimide glue solution suitable for coating, and the viscosity of the test glue solution is 1207cps.

A PET release film was used as a support film, with a thickness of 50. Mu.m.

And (3) performing glue film detection: as a result, the thickness was found to be (. Mu.m), and the film thickness deviation was found to be within.+ -. 2. Mu.m. The results are shown in Table 21.

Table 21

0.038	0.040	0.039
			0.040	0.042	0.040
0.040	0.041	0.039

Defective results are presented: has bubbles and vertical stripe defects.

From the comparison of comparative examples 10 and 11 in example 1, it is understood that an antifoaming agent and a leveling agent are required to help reduce or avoid defects on the surface of the adhesive film and to improve the uniformity of the film thickness.

The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. The application of some of the basic features may be done in accordance with the scope of the claims that follow.

Claims

1. A photosensitive polyimide gum solution suitable for coating, characterized in that: the photosensitive polyimide glue solution is prepared from the following raw materials in parts by weight: the coating comprises alkaline water-soluble resin, a photo-crosslinking agent, a photoinitiator, a polymerization inhibitor, an inorganic filler, a dispersing agent, a defoaming agent, a leveling agent, an anti-settling agent and a solvent;

The weight portions of the components are as follows: 100 parts by mass of an alkaline water-soluble resin, 40-100 parts by mass of a photo-crosslinking agent, 0.1-0.5 part by mass of a photoinitiator, 0.1-5 parts by mass of a polymerization inhibitor, 60-467 parts by mass of an inorganic filler, 1-5 parts by mass of a dispersing agent, 0.05-1 part by mass of a defoaming agent, 0.01-1 part by mass of a leveling agent, 0.01-2 parts by mass of an anti-settling agent and 100-300 parts by mass of a solvent;

the alkaline water-soluble resin is alkaline water-soluble polyimide resin, and the molecular weight is 15000-35000.

2. The photosensitive polyimide dope suitable for coating according to claim 1, wherein: the viscosity of the photosensitive polyimide glue solution is controlled between 800 and 1550 cps.

3. The photosensitive polyimide dope suitable for coating according to claim 1 or 2, wherein: the alkaline water-soluble polyimide resin is prepared by the following steps:

(D) Mixing the resin solution with a poor solvent to precipitate solid resin; washing and drying the solid resin to obtain alkaline water-soluble polyimide resin;

in the step (A), the diamine is diamine containing hydroxyl;

in the step (B), the dianhydride may be selected from: at least one of hexafluorodianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol a dianhydride, 4' -biphenyl ether dianhydride, diphenyl sulfide dianhydride, 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, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride;

in the step (B), the molecular weight regulator is phthalic anhydride.

4. A photosensitive polyimide gum solution suitable for coating according to claim 3, characterized in that:

the diamine containing hydroxyl groups is selected from: at least one of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 2-bis (3-amino-4-hydroxyphenyl) propane, 3' -dihydroxybenzidine, and an aromatic diamine having the structural formula shown below:

5. the photosensitive polyimide dope suitable for coating according to claim 1 or 2, wherein: the photocrosslinking agent 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, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate and tricyclic sunflower dimethanol diacrylate;

Or, the photoinitiator is selected from: at least one of IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE 03;

or, the polymerization inhibitor is selected from: at least one of hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-t-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2, 6-di-t-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol;

or, the inorganic filler is selected from: at least one of silica, mica powder, alumina and yttria;

or the dispersing agent is a silane coupling agent which does not contain free amino and sulfhydryl groups;

or, the defoamer: an organosilicon defoamer which cannot contain free amine groups and mercapto groups;

or, the leveling agent: the acrylic leveling agent cannot contain free amino and mercapto;

or, the anti-settling agent: free amine and thiol groups cannot be contained.

6. The photosensitive polyimide gum solution suitable for coating according to claim 5, wherein:

the dispersing agent is KH570 with double bond;

or, the defoaming agent is at least one of KS-603 defoaming agent and KS-66 defoaming agent;

Or, the leveling agent is at least one of BYK-354 and BYK-361N;

or, the anti-settling agent is fumed silica.

7. The photosensitive polyimide dope suitable for coating according to claim 1 or 2, wherein: the inorganic filler accounts for 30-70% of the mass of the total solids in the photosensitive polyimide glue solution.

8. The photosensitive polyimide dope suitable for coating according to claim 1 or 2, wherein: the solvent consists of a high boiling point solvent and a low boiling point solvent; the mass ratio of the high-boiling point solvent to the low-boiling point solvent is 3:2-1: 2.

9. The photosensitive polyimide glue solution suitable for coating according to claim 8, wherein: the high boiling point solvent is selected from: one or two of N-methyl pyrrolidone and gamma-butyrolactone;

the low boiling point solvent is selected from: one or a mixture of several of N, N' -dimethylformamide, ethyl lactate, propylene glycol methyl ether acetate, cyclopentanone, tetrahydrofuran, ethyl acetate and butyl acetate.

10. A process for preparing a photosensitive polyimide gum solution suitable for coating as claimed in any one of claims 1 to 9, comprising the steps of:

11. A method of coating a photosensitive polyimide gum solution suitable for coating as claimed in any one of claims 1 to 9, comprising the steps of:

(1) Coating: applying the photosensitive polyimide dope suitable for coating as claimed in any one of claims 1 to 9 to a surface of a support film;

(3) And (3) laminating a protective film: and (3) attaching the protective film to the photosensitive solid film with the support film to obtain the negative photosensitive solid film subjected to alkaline water development.

12. The coating method according to claim 11, characterized in that: in the step (1), the thickness of the support film is 25-100 μm;

or, in the step (1), the coating method is selected from at least one of the following: blade coating, slot coating, gravure coating, screen printing;

or, in the step (1), the coating speed of the coating is 1-100mm/s;

or, in the step (2), the baking conditions are as follows: baking for 1-60 min at 80-100 ℃ by hot plate or hot air;

or, in the step (3), the protective film is selected from PE, PP or PET materials;

or the thickness of the protective film is 25-50 mu m,

or, the attaching of the protective film is carried out at 70-90 ℃; the laminating pressure of the protective film is 0.1-0.5 MPa.

13. The negative photosensitive solid adhesive film of alkaline aqueous development prepared by the coating method of claim 11 or 12.