Polyimide oligomer and liquid photoimagable solder resist ink

A technology of polyimide and oligomer, which is applied in ink, optics, optomechanical equipment, etc., can solve the problems of decreased adhesion, decreased adhesion and physical and mechanical properties, and low cross-linking density, and meets the requirements of Bending resistance, excellent adhesion fastness, high reflective whiteness effect

Active Publication Date: 2013-06-12
东莞德芳油墨科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the implementation of the lead restriction order, the use of lead-free solder is required in the manufacture of circuit boards, which puts forward higher requirements for the heat resistance of solder mask inks (280 ° C, 10s three times), novolak epoxy resin is soldered with pure tin Or when it is tinned, it will appear powerless, resulting in an increase in the scrap rate, and the heat resistance still needs to be improved
Because it contains benzene rings, it is prone to yellowing at high temperature. In some occasions where white solder resist ink is required (such as photosensitive solder resist ink for LED), the whiteness cannot meet the requirements.
In addition, novolac epoxy resin shrinks greatly after curing, and the solder mask layer tends to become brittle, resulting in a high scrap rate in the production process
And it is not resistant to bending, it is difficult to meet the folding resistance requirements of flexible boards
[0005] Use bisphenol A type epoxy resin or bisphenol F type epoxy resin or hydroxymethyl bisphenol A type epoxy resin to partially or completely replace the novolac epoxy resin as the photosensitive resin, which has a great impact on bending resistance. Improved but still not good enough, only suitable for low-end flexible boards
The shrinkage after curing has indeed been greatly improved, but unfortunately its heat resistance is always difficult to meet the requirements of users. When soldering pure tin or tin, there are more attacks on solder resistance, and the scrap rate is higher.
Compared with novolac epoxy resin, bisphenol A epoxy resin has a lower epoxy group content in the molecular structure and a lower crosslinking density, resulting in a lower heat resistance, chemical resistance and dimensional stability of the product. Limited improvement in flexibility while sacrificing other properties
[0006] CN1390898A discloses a "dilute alkali developing photosensitive imaging solder resist ink". The photosensitive resin of this invention is a mo

Method used

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  • Polyimide oligomer and liquid photoimagable solder resist ink

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0075] 1) Add 16.8 grams (0.08 moles) of 4,4'-diaminodicyclohexylmethane, 20 grams (0.01 moles) of polyetheramine D-2000 (x=33) and 17.52 grams (0.12 moles) of lysine In 295 grams of m-cresol, keep the temperature at 50°C for 10 minutes to completely dissolve it;

[0076] 2) Under nitrogen protection, add 42 grams (0.2 moles) of 1,2,3,4-cyclopentane tetracarboxylic dianhydride, and react at 50°C for 30 minutes;

[0077] 3) Add 1.96 g (0.02 mol) of maleic anhydride, first react at 50°C for 30 minutes, and then react at 120°C for 2 hours;

[0078] 4) Then heat up to 200°C and react for 5 hours;

[0079] 5) After the reaction, pour the reaction solution into anhydrous methanol to obtain a light yellow solid, wash the light yellow solid with anhydrous methanol, and then dry it at 50°C to obtain a white solid, namely polyimide Oligomer.

[0080] The polyimide oligomer after above-mentioned purification is carried out thermogravimetric analysis, the result is as follows figure 1...

Embodiment 2

[0095] 1) Add 8.5 grams (0.05 moles) of isophorone diamine, 20 grams (0.02 moles) of polyetheramine D-1000 (x=16) and 13.14 grams (0.09 moles) of lysine to 232 grams of N- In methylpyrrolidone, keep the temperature at 70°C for 10 minutes to completely dissolve;

[0096] 2) Under nitrogen protection, add 33.6 g (0.15 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and react at 70°C for 30 minutes;

[0097] 3) Add 1.96 g (0.02 mol) of maleic anhydride, first react at 70°C for 30 minutes, and then react at 140°C for 2 hours;

[0098] 4) Then heat up to 220°C and react for 5 hours;

[0099] After the reaction, pour the reaction solution into anhydrous methanol to obtain a light yellow solid, wash the light yellow solid with anhydrous methanol, and then dry it at 50°C to obtain a white solid, which is polyimide oligomerization thing.

[0100] Liquid photosensitive alkali developing solder resist ink:

[0101] Weight percentage ratio: photosensitive resin (polyimide ol...

Embodiment 3

[0115] 1) 8.40 g (0.04 mol) of 4,4'-diaminodicyclohexylmethane, 9.52 g (0.04 mol) of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, polyether Amine D-400 (x=5) 16 g (0.04 mol) and lysine 20.44 g (0.14 mol) were successively added to 335 g of N-methylpyrrolidone, and kept at 60°C for 10 minutes to completely dissolve;

[0116] 2) Under nitrogen protection, add 25.48 grams (0.13 moles) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and bicyclo[2.2.2]oct-7-ene-2,3,5,6 - 29.76 grams (0.12 moles) of tetracarboxylic dianhydride, reacted for 30 minutes at 60°C;

[0117] 3) Add 1.96 g (0.02 mol) of maleic anhydride, first react at 60°C for 30 minutes, and then react at 130°C for 2 hours;

[0118] 4) Then heat up to 180°C and react for 5 hours;

[0119] 5) After the reaction, pour the reaction solution into anhydrous methanol to obtain a light yellow solid, wash the light yellow solid with anhydrous methanol, and then dry it at 50°C to obtain a white solid, namely polyimide Oligo...

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Abstract

The invention discloses a polyimide oligomer and a liquid photoimagable solder resist ink. A structural formula of the polyimide oligomer is as follows: R1 is alicyclic, R2 is alkyl with at least one carbon ring structure, n is not less than 1 and not more than 30, m is not less than 1 and not more than 30, p is not less than 1 and not more than 30, and (n+1-m-p) is more than 0, x is not less than 5 and not more than 50. The photoimagable polyimide oligomer has the advantages of excellent heat resistance, soldering resistance, golden resistance, chemical resistance, and yellowing resistance. The liquid photoimagable solder resist ink prepared from the oligomer has excellent heat resistance, soldering resistance, golden resistance, chemical resistance, yellowing resistance, insulativity, high resolution, high flexibility and high adhesion, can be used for effectively solving the problem that the liquid photoimagable solder resist ink is easy to yellow at high temperature under the processes of thermocuring, solder coating and reflow soldering, and is especially suitable for preparing white solder resist ink so as to achieve high reflecting whiteness.

Description

technical field [0001] The invention relates to a photosensitive polymer and a liquid photosensitive solder resist ink and a flexible circuit board using the photosensitive polymer. Background technique [0002] In recent years, our PCB industry has developed at a high speed of more than 15% every year, and has entered the ranks of the world's largest PCB countries. In recent years, electronic information and communication products continue to introduce new ones, and their volume keeps shrinking, but their functions keep increasing. Therefore, flexible circuit boards have to be used instead, resulting in a substantial increase in their usage. Flexible circuit board (FPC for short) provides excellent electrical performance, can meet the design needs of smaller and higher density installation, and also helps to reduce assembly processes and enhance reliability. Flexible circuit boards are the only solution to meet the miniaturization and mobility requirements of electronic pr...

Claims

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Application Information

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IPC IPC(8): C08G73/12C07D519/00C07D487/04C09D11/10G03F7/004G03F7/027C09D11/50
Inventor 杨翰王小妹马志平
Owner 东莞德芳油墨科技有限公司
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