Star-shaped alicyclic structure photosensitive base developing resin, preparation method and application thereof

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a star aliphatic ring structure photosensitive alkali developing resin and a preparation method and application thereof. The raw material composition of the star aliphatic ring structure photosensitive alkali developing resin includes cyclohexene acid 10-30 parts, polyhydric alcohol 5-20 parts, unsaturated monobasic acid 8-20 parts, dicarboxylic acid anhydride 20-40 parts, solvent 20-40 parts, first catalyst 0.04-0.08 parts, second catalyst 0.02-0.08 parts, polymerization inhibitor 0.01-0.03 parts, hydrogen peroxide 5-10 parts, saturated sodium bicarbonate solution 5-10 parts, diethyl ether 5-10 parts, and formic acid 10-25 parts, all in terms of weight. The cyclohexene acid is esterified with the polyhydric alcohol to form a star oligomer, the star ends of which are all aliphatic ring double bond structures, then the double bond is epoxidized by hydrogen peroxide, then ring-opening esterification is carried out by using the unsaturated monobasic acid, then modification is carried out by using the acid anhydride to introduce carboxyl groups, and finally the photosensitive developing main body resin with internal polyester bond structure is obtained. The resin has excellent photosensitivity, etching resistance, electroplating resistance, film stripping resistance and other performances, and is suitable for application in preparation of IC carrier boards.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a star-shaped alicyclic structure photosensitive alkali developing resin and a preparation method and application thereof. BACKGROUND

[0002] IC carrier board technology originated in Japan in the 1980s, and has a history of more than 30 years. In the early stage, it coexisted with IC integrated packaging technology. At present, high-end ICs basically adopt carrier board packaging technology as a precise connecting device of core chips and conventional printed circuit boards (PCBs). The IC carrier board is made of a copper-clad board through processes such as photoetching, solder resist photosensitive developing, and gold plating, and is different from the traditional copper-clad board of the PCB in the following aspects. First, the base material of the copper-clad board of the IC carrier board is different from the epoxy / glass fiber composite material of the traditional copper-clad board, and mainly adopts BT resin, ABF insulating film (Ajinomoto Build-up Film of Ajinomoto Co., Inc.) and MIS polymer as the base material of the copper-clad board (film). The three types of baseboard materials are monopolized by foreign enterprises and often become a choke point for chip manufacturing. Second, the IC carrier board is made of a special copper-clad board (film), and the line etching and solder resist photosensitive developing processes experienced require more precise technical requirements than the conventional PCB manufacturing, that is, the etching and solder resist developing resolution is higher, and the line width is usually controlled within tens of microns. Third, the solder resist photosensitive developing ink as a permanent fine protective thin layer material is required to have strict heat resistance, thermal expansion resistance, hardness, scratch resistance, impact resistance, and even lower dielectric constant in some application scenarios to meet the requirements of high-frequency communication. Fourth, the post-processing of the IC carrier board mostly adopts chemical gold plating (industrial abbreviation: gold plating), rather than electroplating. The gold plating solution generally has strong acidity or alkalinity, which requires the solder resist layer of the IC carrier board to have high gold plating resistance (that is, corrosion resistance) to avoid defects such as discoloration, denaturation and easy peeling of the solder resist layer. In summary, the IC carrier board directly participates in IC die packaging, and high requirements are placed on the performance reliability and size precision of various materials (especially solder resist materials) on the carrier board to ensure the working reliability of the packaged chip. There is still a lack of an IC carrier board solder resist material with excellent photosensitivity, etch resistance, electroplating resistance and film fading resistance in the prior art. SUMMARY

[0003] A first object of the present application is to provide a star-shaped alicyclic structure photosensitive alkali developing resin, a second object of the present application is to provide a preparation method of the photosensitive alkali developing resin, and a third object of the present application is to provide an application of the photosensitive alkali developing resin.

[0004] According to a first aspect of the present application, there is provided a star-shaped alicyclic structure photosensitive alkali developing resin, the raw material composition of which comprises, by weight:

[0005] Cyclohexene acid 10-30 parts, polyol 5-20 parts, unsaturated monobasic acid 8-20 parts, dicarboxylic anhydride 20-40 parts, solvent 20-40 parts, first catalyst 0.04-0.08 parts, second catalyst 0.02-0.08 parts, polymerization inhibitor 0.01-0.03 parts, hydrogen peroxide 5-10 parts, saturated sodium bicarbonate solution 5-10 parts, diethyl ether 5-10 parts, formic acid 10-25 parts.

[0006] In some embodiments, the cyclohexene acid is selected from 3-cyclohexene-1-carboxylic acid or 4-methyl-3-cyclohexene-1-carboxylic acid.

[0007] In some embodiments, the polyol is selected from one or more of oligomeric propylene glycol, polyether triol, polycaprolactone triol (cas number 37625-56-2), ditrimethylolpropane, dipentaerythritol, trimethylolpropane, pentaerythritol, hydrogenated bisphenol A, tricyclodecane dimethanol.

[0008] In some embodiments, the oligomeric propylene glycol is polypropylene glycol 500 and the polyether triol is trihydroxy polyether 1000.

[0009] In some embodiments, the unsaturated monobasic acid is selected from one or more of acrylic acid, methacrylic acid, butenoic acid.

[0010] In some embodiments, the dicarboxylic anhydride is selected from one or more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride.

[0011] In some embodiments, the solvent is selected from xylene.

[0012] In some embodiments, the xylene is selected from one or more of p-xylene, m-xylene, o-xylene.

[0013] In some embodiments, the first catalyst is selected from p-toluenesulfonic acid or chlorosulfoxide.

[0014] In some embodiments, the second catalyst is selected from one or more of benzyltriethylammonium chloride, benzyl diamine, triethylamine, diethylamine, triphenylphosphine.

[0015] In some embodiments, the polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butyl hydroquinone, catechol.

[0016] According to a second aspect of the present application, there is provided a method for preparing the star-shaped alicyclic structure photosensitive alkali developing resin as described above, comprising the following steps:

[0017] S1, mix cyclohexene acid, polyol, first catalyst and solvent, heat the system to 100-130°C under nitrogen protection, stir for 4-5h, remove water in the system;

[0018] S2, cooling the system temperature to 50-60℃, adding formic acid, stirring for 1-2h, then adding hydrogen peroxide, continuing to react for 3-5h, after the reaction is completed, pouring the reaction product into a separatory funnel, then adding saturated sodium bicarbonate solution and diethyl ether to the reaction product, shaking uniformly and then standing to separate the layers, separating the organic layer, then washing the organic layer with deionized water for 2-3 times, then removing diethyl ether from the washed organic layer by rotary evaporation, adding anhydrous magnesium sulfate overnight for drying, then filtering to remove the magnesium sulfate, to obtain an intermediate product;

[0019] S3, adding a polymerization inhibitor and a second catalyst to the intermediate product obtained in S2, heating to 90-100℃, then adding an unsaturated monobasic acid, after adding, heating to 110-120℃, continuing to react for 2-3h, after the reaction is completed, cooling the reaction system temperature to 70-90℃, then adding a dicarboxylic anhydride, reacting for 6-8h, to obtain.

[0020] The cyclohexene acid contains an alicyclic structure, an oxidizable double bond, and a reactable carboxyl group. In the present application, the cyclohexene acid is esterified with a polyol to form a star-shaped oligomer, the star-shaped ends of which are all alicyclic double bond structures. Then, the double bond is epoxidized by hydrogen peroxide, and then ring-opening esterification is performed by an unsaturated monobasic acid, and then a carboxyl group is introduced by anhydride modification, to finally obtain a photosensitive developing main body resin with an internal multi-ester bond structure. The resin adopts an internal ester bond design, avoiding serious inter-chain entanglement and strong interaction of straight-chain polymers, so that the developing boundary can be clearer and more vertical, and the developing resolution, thermal expansion resistance, and resistance to gold can be effectively improved.

[0021] When the cyclohexene acid is 3-cyclohexene-1-carboxylic acid, the polyol is trimethylolpropane, the unsaturated monobasic acid is acrylic acid, and the dicarboxylic anhydride is tetrahydrophthalic anhydride, the synthesis route of the present application is as shown in Figure 1 .

[0022] In some embodiments, in step S2, the hydrogen peroxide needs to be slowly added dropwise, and the dropwise adding time is controlled to be 2-4h.

[0023] In some embodiments, in steps S1 and S2, the stirring speed is 600-800rpm.

[0024] According to a third aspect of the present application, the application provides a use of the above-mentioned star-shaped alicyclic structure photosensitive alkali developing resin in the preparation of an IC carrier plate.

[0025] According to a fourth aspect of the present application, a dry film obtained by photocuring or thermocuring the above-mentioned photosensitive alkali developing resin is provided.

[0026] In some embodiments, the photosensitive alkali developing resin is printed on a carrier, and baked at 70-80°C for 20-30 minutes to obtain a dry film.

[0027] According to a fifth aspect of the present application, the dry film described above is used in the preparation of an IC carrier.

[0028] The advantages of the present application include:

[0029] The star-shaped alicyclic structure photosensitive alkali developing resin of the present application has high photosensitive curing activity, strong adhesion, high glass transition temperature (Tg), fine developing characteristics, and low thermal expansion coefficient, and has excellent photosensitivity, etching resistance, plating resistance, and film stripping performance, and is suitable for use in the preparation of an IC carrier. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The following is a synthetic route of Example 1 of the present application. DETAILED DESCRIPTION

[0031] The present application will be further described in detail below, and it should be noted that the following examples are only used to better explain the content of the present application, and do not limit the scope of protection of the present application. The process steps not disclosed in the examples are prior art. Unless otherwise specified, the following raw materials are commercially available.

[0032] In the following examples, the stirring speed is 600 rpm.

[0033] Example 1

[0034] The preparation method of the star-shaped alicyclic structure photosensitive alkali developing resin of the present embodiment includes the following steps:

[0035] (1) 50.00 g of 3-cyclohexen-1-carboxylic acid, 18.61 g of trimethylolpropane, 2.05 g of p-toluenesulfonic acid, and 68.61 g of p-xylene are added to a three-necked flask, a water separator is installed, and the system is connected to nitrogen. The system is heated to 130°C and stirred vigorously for about 4 h until no more water is generated in the water separator, and then cooled to 50°C.

[0036] (2) 75.17 g of formic acid is added to the three-necked flask, stirred vigorously for 1 h, and then 24.26 g of hydrogen peroxide is slowly added dropwise over a period of about 4 h. After the addition is completed, the reaction is continued for 4 h. After the reaction is completed, the reaction product is poured into a separatory funnel, then 50 g of saturated sodium bicarbonate solution and 25 g of diethyl ether are added, shaken uniformly, and then allowed to stand to separate the layers. The organic layer is separated, then washed with distilled water 3 times, then poured into a beaker after washing, and the diethyl ether is removed by rotary evaporation. Then 30 g of anhydrous magnesium sulfate is added and dried overnight, then the magnesium sulfate is removed by filtration to obtain an intermediate product.

[0037] (3) The intermediate product obtained in step (2) is added to a new three-necked flask, 0.48 g of hydroquinone and 0.32 g of benzyltriethylammonium chloride are added, the system is warmed to 90°C, then 28.53 g of acrylic acid is added dropwise to the three-necked flask, after the dropwise addition is completed, the temperature is raised to 110°C, the reaction is continued for 2.5 h, after the reaction is completed, the temperature of the reaction system is reduced to 80°C, then 60.41 g of tetrahydrophthalic anhydride is added, and the reaction is carried out for 6 h, and then the reaction is completed.

[0038] Example 2

[0039] The preparation method of the star-shaped alicyclic structure photosensitive alkali developing resin of the present example comprises the following steps:

[0040] (1) 50.00 g of 3-cyclohexen-1-carboxylic acid, 66.05 g of polycaprolactone triol, 2.05 g of p-toluenesulfonic acid and 68.61 g of p-xylene are added to a three-necked flask, a water separator is installed, nitrogen is connected, the system is warmed to 130°C, and is stirred vigorously for about 4 h until no water is generated in the water separator, and then the temperature is reduced to 50°C.

[0041] (2) 75.17 g of formic acid is added to the three-necked flask, stirred vigorously for 1 h, then 24.26 g of hydrogen peroxide is slowly added dropwise, the dropwise addition is carried out for about 4 h, after the dropwise addition is completed, the reaction is continued for 4 h, after the reaction is completed, the reaction product is poured into a separatory funnel, then 50 g of saturated sodium bicarbonate solution and 25 g of ethyl ether are added, after shaking uniformly, the layers are separated, the organic layer is separated out, then the organic layer is washed with distilled water for 3 times, then the washed organic layer is poured into a beaker, the ethyl ether is removed by rotary evaporation, 30 g of anhydrous magnesium sulfate is added and dried overnight, then the magnesium sulfate is removed by filtration, and the intermediate product is obtained.

[0042] (3) The intermediate product obtained in step (2) is added to a new three-necked flask, 0.48 g of hydroquinone and 0.32 g of benzyltriethylammonium chloride are added, the system is warmed to 90°C, then 28.53 g of acrylic acid is added dropwise to the three-necked flask, after the dropwise addition is completed, the temperature is raised to 110°C, the reaction is continued for 2.5 h, after the reaction is completed, the temperature of the reaction system is reduced to 80°C, then 60.41 g of tetrahydrophthalic anhydride is added, and the reaction is carried out for 6 h, and then the reaction is completed.

[0043] Example 3

[0044] The preparation method of the star-shaped alicyclic structure photosensitive alkali developing resin of the present example comprises the following steps:

[0045] (1) 50.00 g of 3-cyclohexen-1-carboxylic acid, 132.11 g of trihydroxy polyether 1000, 2.05 g of p-toluenesulfonic acid and 68.61 g of p-xylene are added to a three-necked flask, a water separator is installed, nitrogen is connected, the system is warmed to 130°C, and is stirred vigorously for about 4 h until no water is generated in the water separator, and then the temperature is reduced to 50°C.

[0046] (2) In a three-necked flask, 75.17 g of formic acid was added, and stirred vigorously for 1 h, then 24.26 g of hydrogen peroxide was added dropwise slowly, the dropwise addition took about 4 h, after the dropwise addition was completed, the reaction was continued for 4 h, after the reaction was completed, the reaction product was poured into a separatory funnel, then 50 g of saturated sodium bicarbonate solution and 25 g of diethyl ether were added, after shaking uniformly, it was allowed to stand to separate into layers, the organic layer was separated, then the organic layer was washed with distilled water for 3 times, then the washed organic layer was poured into a beaker, diethyl ether was removed by rotary evaporation, then 30 g of anhydrous magnesium sulfate was added and dried overnight, then the magnesium sulfate was removed by filtration, to obtain an intermediate product.

[0047] (3) The intermediate product obtained in step (2) was added to a new three-necked flask, then 0.48 g of hydroquinone and 0.32 g of benzyltriethylammonium chloride were added, the system was warmed to 90 °C, then 28.53 g of acrylic acid was added dropwise to the three-necked flask, after the dropwise addition was completed, the temperature was raised to 110 °C, and the reaction was continued for 2.5 h, after the reaction was completed, the temperature of the reaction system was reduced to 80 °C, then 60.41 g of tetrahydrophthalic anhydride was added, and the reaction was continued for 6 h, to obtain the product.

[0048] Example 4

[0049] The preparation method of the star-shaped alicyclic structure photosensitive alkali developing resin of the present embodiment comprises the following steps:

[0050] (1) 50.00 g of 3-cyclohexen-1-carboxylic acid, 18.61 g of trimethylolpropane, 2.05 g of p-toluenesulfonic acid and 68.61 g of o-xylene were added to a three-necked flask, a water separator was installed, and nitrogen was connected, the system was warmed to 130 °C, and stirred vigorously for about 4 h, until no water was generated in the water separator, then the temperature was reduced to 50 °C.

[0051] (2) In a three-necked flask, 75.17 g of formic acid was added, and stirred vigorously for 1 h, then 24.26 g of hydrogen peroxide was added dropwise slowly, the dropwise addition took about 4 h, after the dropwise addition was completed, the reaction was continued for 4 h, after the reaction was completed, the reaction product was poured into a separatory funnel, then 50 g of saturated sodium bicarbonate solution and 25 g of diethyl ether were added, after shaking uniformly, it was allowed to stand to separate into layers, the organic layer was separated, then the organic layer was washed with distilled water for 3 times, then the washed organic layer was poured into a beaker, diethyl ether was removed by rotary evaporation, then 30 g of anhydrous magnesium sulfate was added and dried overnight, then the magnesium sulfate was removed by filtration, to obtain an intermediate product.

[0052] (3) The intermediate product obtained in step (2) was added to a new flask, 0.48 g of hydroquinone and 0.32 g of benzyltriethylammonium chloride were added, the system was warmed to 90°C, then 28.53 g of acrylic acid was added dropwise to the flask, after the dropwise addition was completed, the temperature was raised to 110°C, and the reaction was continued for 2.5 h, after the reaction was completed, the temperature of the reaction system was reduced to 80°C, then 60.41 g of tetrahydrophthalic anhydride was added, and the reaction was continued for 6 h to obtain the product.

[0053] Example 5

[0054] The preparation method of the star-shaped alicyclic structure photosensitive alkali developing resin of the present example comprises the following steps:

[0055] (1) 50.00 g of 3-cyclohexen-1-carboxylic acid, 18.61 g of trimethylolpropane, 2.05 g of p-toluenesulfonic acid and 68.61 g of p-xylene were added to a flask, a water separator was installed, and nitrogen was connected. The system was warmed to 130°C, and stirred vigorously for about 4 h until no more water was generated in the water separator, and then cooled to 50°C.

[0056] (2) 75.17 g of formic acid was added to the flask, stirred vigorously for 1 h, then 24.26 g of hydrogen peroxide was slowly added dropwise, the dropwise addition took about 4 h, after the dropwise addition was completed, the reaction was continued for 4 h, after the reaction was completed, the reaction product was poured into a separatory funnel, then 50 g of saturated sodium bicarbonate solution and 25 g of ethyl ether were added, after shaking and uniform distribution, the layers were allowed to stand, the organic layer was separated, then the organic layer was washed with distilled water for 3 times, then the washed organic layer was poured into a beaker, the ethyl ether was removed by rotary evaporation, 30 g of anhydrous magnesium sulfate was added and dried overnight, then the magnesium sulfate was removed by filtration to obtain an intermediate product.

[0057] (3) The intermediate product obtained in step (2) was added to a new flask, 0.48 g of hydroquinone and 0.32 g of benzyltriethylammonium chloride were added, the system was warmed to 90°C, then 28.53 g of acrylic acid was added dropwise to the flask, after the dropwise addition was completed, the temperature was raised to 110°C, and the reaction was continued for 2.5 h, after the reaction was completed, the temperature of the reaction system was reduced to 80°C, then 69.81 g of methyl tetrahydrophthalic anhydride was added, and the reaction was continued for 6 h to obtain the product.

[0058] Next, the star-shaped alicyclic structure photosensitive alkali developing resin prepared in Examples 1-5 was tested for performance, and the testing method was as follows:

[0059] (1) Photosensitivity: The photosensitive alkali developing resin was printed on a copper-clad plate, baked at 75°C for 20 minutes, and exposed and developed under an LED light source exposure machine with a 21-level light gradient ruler placed above the film layer, with the time for the film layer to remain 7 grades as the standard.

[0060] (2) Minimum line / space: tested according to GB / T 29846-2013 Method for printed boards - photoimagable resist for dry film resist - electroplating resistance.

[0061] (3) Etch resistance: tested according to GB / T 29846-2013 Method for printed boards - photoimagable resist for dry film resist - electroplating resistance, the pattern is complete, the line edge is neat, no wrinkles, no shedding or dog-tooth shape after etching, which is excellent, no shedding with wrinkles is good, and shedding is poor.

[0062] (4) Electroplating resistance: tested according to GB / T 29846-2013 Method for printed boards - photoimagable resist for dry film resist - electroplating resistance, the pattern is complete, no plating, no bubbles, no shedding after electroplating, which is excellent, plating with no shedding is good, and shedding is poor.

[0063] (5) Stripping resistance: the test sample is placed in a 50℃, 3wt% NaOH aqueous solution, and the stripping performance is observed, and the sample is completely stripped without residue within 60s, which is excellent, the sample is completely stripped without residue within 60-120s, which is good, and the sample is completely stripped without residue after 120s, which is poor.

[0064] The test results are shown in Table 1.

[0065] Table 1 Performance test results of the photosensitive alkali developing resin of Examples 1-5

[0066]

[0067] As shown in Table 1, the photosensitive alkali developing resin of the present application has excellent photosensitivity, etch resistance, electroplating resistance, and stripping resistance, and is suitable for preparing IC carrier boards.

[0068] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods, and are all included in the protection scope of the present application.

Claims

1. A star-shaped alicyclic-structure photosensitive base developing resin, characterized by comprising: The preparation method of the star-shaped alicyclic structure photosensitive alkali developing resin comprises the following steps: S1, mixing cyclohexene acid, polyol, first catalyst and solvent, heating the system to 100-130 DEG C under nitrogen protection, stirring for 4-5 h, removing water in the system; S2, cooling the system temperature to 50-60 DEG C, adding formic acid, stirring for 1-2 h, then adding hydrogen peroxide, continuing to react for 3-5 h, after the reaction is completed, adding saturated sodium bicarbonate solution and diethyl ether into the reaction product, shaking uniformly, then standing and separating, separating the organic layer, then cleaning the organic layer, then removing diethyl ether by rotary evaporation, then adding anhydrous magnesium sulfate overnight for drying, then filtering to remove magnesium sulfate, obtaining an intermediate product; S3, adding polymerization inhibitor and second catalyst into the intermediate product obtained in S2, heating to 90-100 DEG C, then adding unsaturated monobasic acid, heating to 110-120 DEG C after adding, continuing to react for 2-3 h, after the reaction is completed, cooling the reaction system temperature to 70-90 DEG C, then adding dicarboxylic anhydride, reacting for 6-8 h, obtaining the star-shaped alicyclic structure photosensitive alkali developing resin. The raw material composition is as follows in terms of weight parts: cyclohexene acid 10-30 parts, polyol 5-20 parts, unsaturated monobasic acid 8-20 parts, dicarboxylic anhydride 20-40 parts, solvent 20-40 parts, first catalyst 0.04-0.08 parts, second catalyst 0.02-0.08 parts, polymerization inhibitor 0.01-0.03 parts, hydrogen peroxide 5-10 parts, saturated sodium bicarbonate solution 5-10 parts, diethyl ether 5-10 parts, formic acid 10-25 parts; The first catalyst is selected from p-toluenesulfonic acid or chlorosulfoxide; The second catalyst is selected from one or more of benzyltriethylammonium chloride, benzyl diamine, triethylamine, diethylamine and triphenylphosphine; The cyclohexene acid is selected from 3-cyclohexene-1-carboxylic acid; The polyol is selected from one or more of polyether triol, polycaprolactone triol and trimethylolpropane, and the polyether triol is trihydroxy polyether 1000; The unsaturated monobasic acid is selected from acrylic acid; The dicarboxylic anhydride is selected from tetrahydrophthalic anhydride and / or methyl tetrahydrophthalic anhydride; The solvent is one or more of p-xylene, m-xylene and o-xylene.

2. The star-like alicyclic-structure photosensitive base developing resin according to claim 1, characterized by comprising: The polymerization inhibitor is at least one of hydroquinone, p-tert-butyl hydroquinone and catechol.

3. The star-like alicyclic-structure photosensitive base developing resin according to claim 1, wherein In step S2, the hydrogen peroxide needs to be slowly added dropwise, and the dropwise adding time is controlled to be 2-4 h.

4. Application of the star-shaped alicyclic structure photosensitive alkali developing resin in any one of claims 1-3 in the preparation of IC carrier plate.

5. A dry film, characterized by, It is obtained by photo-curing or thermal curing of the star-shaped alicyclic structure photosensitive alkali developing resin in any one of claims 1-3.

6. Application of the dry film in claim 5 in the preparation of IC carrier plate.

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