阅读说明：本技术 一种具有uv遮蔽作用的树脂组合物及在覆铜板中的应用 (Resin composition with UV shielding effect and application thereof in copper-clad plate ) 是由 谢长乐 付艺伟 焦志慧 李广元 于 2021-08-28 设计创作，主要内容包括：本发明涉及一种具有UV遮蔽作用的树脂组合物及在覆铜板中的应用,其用于解决四官能基的环氧树脂的总产量不足,导致在覆铜板生产旺季时,此树脂货源紧张,此外,当下树脂组合物存在光学检测效率和准确性低且抗剥离强度低的问题。上述树脂组合物的重量份组成如下：酚醛环氧树脂80～120份、高溴环氧树脂30～50份、双酚A型环氧树脂5～15份、酚醛树脂20～100份、四酚基乙烷树脂3～10份、填料100～200份、界面结合剂0.01～0.5份、溶剂A40～80份、溶剂B60～100份。本发明的树脂组合物具有UV遮蔽作用,防重影效果优异,具有吸收氩激光的作用,可提高光学检测效率和准确性,玻璃化温度提高,树脂组合物应用于覆铜板时,抗剥离强度高。(The invention relates to a resin composition with a UV shielding effect and application thereof in a copper-clad plate, which is used for solving the problems that the total yield of epoxy resin with four functional groups is insufficient, so that the resin is in shortage in the busy production season of the copper-clad plate, and in addition, the optical detection efficiency and accuracy are low and the peel strength is low in the existing resin composition. The resin composition comprises the following components in parts by weight: 80-120 parts of phenolic epoxy resin, 30-50 parts of high-bromine epoxy resin, 5-15 parts of bisphenol A epoxy resin, 20-100 parts of phenolic resin, 3-10 parts of tetraphenylethane resin, 100-200 parts of filler, 0.01-0.5 part of interface bonding agent, 40-80 parts of solvent A and 60-100 parts of solvent B. The resin composition has the advantages of UV shielding effect, excellent anti-ghost effect, argon laser absorption effect, optical detection efficiency and accuracy improvement, glass transition temperature improvement, and high peel strength when the resin composition is applied to a copper-clad plate.)

1. The resin composition with the UV shielding effect is characterized by comprising the following components in parts by weight: 80-120 parts of phenolic epoxy resin, 30-50 parts of high-bromine epoxy resin, 5-15 parts of bisphenol A epoxy resin, 20-100 parts of phenolic resin, 3-10 parts of tetraphenylethane resin, 100-200 parts of filler, 0.01-0.5 part of interfacial bonding agent, 40-80 parts of solvent A and 60-100 parts of solvent B.

2. The resin composition with UV shielding effect according to claim 1, wherein the resin composition comprises the following components in parts by weight: 100-120 parts of phenolic epoxy resin, 35-50 parts of high-bromine epoxy resin, 10-15 parts of bisphenol A epoxy resin, 80-100 parts of phenolic resin, 3-6 parts of tetraphenylethane resin, 150-200 parts of filler, 0.2-0.5 part of interfacial bonding agent, 50-80 parts of solvent A and 90-100 parts of solvent B.

3. The resin composition with UV shielding effect according to claim 1, wherein the resin composition comprises the following components in parts by weight: 100 parts of novolac epoxy resin, 35 parts of high-bromine epoxy resin, 10 parts of bisphenol A epoxy resin, 80 parts of novolac resin, 3 parts of tetraphenylethane resin, 150 parts of filler, 0.2 part of interface bonding agent, 50 parts of solvent A and 90 parts of solvent B.

4. The resin composition with UV shielding effect according to claim 1, wherein the novolac epoxy resin is at least one of NPPN638A80, BNE200A80, NPPN438A80, KEB-3165M80S and CNE 202;

the high-bromine epoxy resin adopts BEB400T65 or BPEB400A 65;

the bisphenol A epoxy resin adopts at least one of NPEL-127E, BE188L, YD-128, YN-1828 and NPSN901A 80.

5. The resin composition with UV shielding effect according to claim 1, wherein the phenolic resin is selected from the group consisting of PF-8020 and Resicarre 3108; the tetraphenol ethane resin adopts KPE-F3110 or ZEH-8110;

the filler is at least one of magnesium hydroxide, aluminum hydroxide, spherical silica micropowder, fused silica micropowder, talcum powder, boehmite and barium sulfate.

6. The resin composition with UV shielding effect according to claim 1, wherein the interfacial bonding agent is at least one of silane, titanate and aluminate coupling agent;

the solvent A and the solvent B respectively adopt cyclohexanone, butanone, acetone, propylene glycol methyl ether or N, N-dimethylformamide.

7. A method for producing a resin composition having UV screening effect for obtaining the resin composition having UV screening effect according to any one of claims 1 to 6, characterized by comprising the steps of:

s1, cleaning a glue mixing tank by using acetone, and then sequentially adding a solvent A, a solvent B and an interface bonding agent into the glue mixing tank to obtain a mixed solution;

s2, adding the solid raw materials into the mixed solution, adding the rest raw materials, and stirring to obtain a glue solution, namely the resin composition.

8. An application of a resin composition with a UV shielding effect in a copper-clad plate.

9. The use of the resin composition with UV screening effect in copper clad laminate according to claim 8, wherein the operation of the use is as follows:

providing the resin composition according to any one of claims 1 to 6, which is prepared by the preparation method according to claim 7;

carrying out impregnation and baking treatment on the resin composition to obtain a plurality of groups of prepregs for later use;

taking six prepregs, stacking the prepregs in order to obtain a stacked object, and covering copper foils on the upper part and the lower part of the stacked object respectively to obtain a stacked body;

and carrying out pressing treatment on the laminated structure to obtain a composite laminated board, namely the copper-clad board.

10. The use of the resin composition with UV shielding effect in copper-clad plate according to claim 9, wherein the copper foil has a thickness of 1 OZ.

Technical Field

The invention relates to a resin composition, in particular to a resin composition with a UV shielding effect and application thereof in a copper-clad plate.

Background

With the development of the manufacturing process of the printed circuit board, the photosensitive solder resist is popularized, so as to avoid double images generated by mutual influence of two surfaces of a substrate of the printed circuit board during exposure, therefore, the substrate is required to have the function of shielding ultraviolet rays, meanwhile, Automatic Optical Inspection (AOI) equipment is popularized for quality inspection in the printing process, an automatic optical inspection instrument uses argon laser as an irradiation light source, substrate resin must absorb the argon laser and excite fluorescence with lower energy, and the automatic inspection of the printed circuit board is realized by measuring the fluorescence of the substrate, so that the inspection efficiency and the accuracy are improved.

At present, tetrafunctional epoxy resin is generally used for shielding ultraviolet rays when a copper-clad plate is manufactured, but the total yield of tetrafunctional epoxy resin is insufficient, so that the supply of the resin is tense when the copper-clad plate is produced in a busy season, and in addition, the problems of low optical detection efficiency and accuracy and low peeling strength exist in the current resin composition.

Disclosure of Invention

Therefore, it is necessary to provide a resin composition with a UV shielding effect and an application thereof in the copper clad laminate, aiming at the problem that the prior art generally uses a tetrafunctional epoxy resin as an ultraviolet shielding effect, but the total yield of the tetrafunctional epoxy resin is insufficient, so that the resin is in shortage in the production season of the copper clad laminate, and the problem that the prior resin composition has low optical detection efficiency and accuracy and low peel strength is solved.

A resin composition with a UV shielding effect comprises the following components in parts by weight: 80-120 parts of phenolic epoxy resin, 30-50 parts of high-bromine epoxy resin, 5-15 parts of bisphenol A epoxy resin, 20-100 parts of phenolic resin, 3-10 parts of tetraphenylethane resin, 100-200 parts of filler, 0.01-0.5 part of interfacial bonding agent, 40-80 parts of solvent A and 60-100 parts of solvent B.

The resin composition has the advantages of UV shielding effect, excellent anti-ghost effect, argon laser absorption effect, capability of improving optical detection efficiency and accuracy, and high glass transition temperature, and when the resin composition is applied to a copper-clad plate, the peel strength is high.

In one embodiment, the resin composition comprises the following components in parts by weight: 100-120 parts of phenolic epoxy resin, 35-50 parts of high-bromine epoxy resin, 10-15 parts of bisphenol A epoxy resin, 80-100 parts of phenolic resin, 3-6 parts of tetraphenylethane resin, 150-200 parts of filler, 0.2-0.5 part of interfacial bonding agent, 50-80 parts of solvent A and 90-100 parts of solvent B.

In one embodiment, the resin composition comprises the following components in parts by weight: 100 parts of novolac epoxy resin, 35 parts of high-bromine epoxy resin, 10 parts of bisphenol A epoxy resin, 80 parts of novolac resin, 3 parts of tetraphenylethane resin, 150 parts of filler, 0.2 part of interface bonding agent, 50 parts of solvent A and 90 parts of solvent B.

In one embodiment, the novolac epoxy resin is at least one of NPPN638A80, BNE200A80, NPPN438A80, KEB-3165M80S and CNE 202; the high-bromine epoxy resin adopts BEB400T65 or BPEB400A 65; the bisphenol A epoxy resin adopts at least one of NPEL-127E, BE188L, YD-128, YN-1828 and NPSN901A 80.

In one embodiment, the phenolic resin is PF-8020 or Resicarre 3108; the tetraphenol ethane resin adopts KPE-F3110 or ZEH-8110; the filler is at least one of magnesium hydroxide, aluminum hydroxide, spherical silica micropowder, fused silica micropowder, talcum powder, boehmite and barium sulfate.

In one embodiment, the interface bonding agent is at least one of silane, titanate and aluminate coupling agent; the solvent A and the solvent B respectively adopt cyclohexanone, butanone, acetone, propylene glycol methyl ether or N, N-dimethylformamide.

A method for producing a resin composition having UV-screening effect, which is used for producing the resin composition having UV-screening effect, the production method comprising the steps of:

s1, cleaning a glue mixing tank by using acetone, and then sequentially adding a solvent A, a solvent B and an interface bonding agent into the glue mixing tank to obtain a mixed solution;

s2, adding the solid raw materials into the mixed solution, adding the rest raw materials, and stirring to obtain a glue solution, namely the resin composition.

An application of a resin composition with a UV shielding effect in a copper-clad plate.

In one embodiment, the application operates as follows:

providing the resin composition using the resin composition having a UV-screening effect;

carrying out impregnation and baking treatment on the resin composition to obtain a plurality of groups of prepregs for later use;

taking six prepregs, stacking the prepregs in order to obtain a stacked object, and covering copper foils on the upper part and the lower part of the stacked object respectively to obtain a stacked body;

and carrying out pressing treatment on the laminated structure to obtain a composite laminated board, namely the copper-clad board.

Further, the thickness of the copper foil is 1 OZ.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, the resin composition is prepared by doping the tetraphenolethane resin, and the molecular structure of the tetraphenolethane resin contains delocalized pi bonds, so that the energy is low and stable, and most of the energy is absorbed when the tetraphenolethane resin is irradiated by Ultraviolet (UV), so that the prepared resin composition has a UV shielding function, and the condition of double images can be avoided.

When the argon laser is used for irradiation, because the argon laser is higher than ultraviolet light, electrons in molecules at a low energy level absorb energy, the electrons are transited from a low energy level to a high energy level, and then the electrons are transited from the high energy level to the low energy level, the absorbed energy is partially released to generate fluorescence, so that the resin composition prepared by doping the tetraphenolethane resin has the function of absorbing the argon laser, is suitable for the process of automatic optical detection, can replace tetrafunctional epoxy resin, realizes the automatic detection of a printed board by measuring the fluorescence of a substrate, and improves the detection efficiency and accuracy.

According to the invention, the glass transition temperature of the prepared resin composition is increased, and the resin composition has high peel strength when being applied to a copper-clad plate.

In conclusion, the resin composition has the UV shielding effect, the anti-ghost effect is excellent, the argon laser absorption effect is realized, the optical detection efficiency and accuracy can be improved, the glass transition temperature is improved, and the peel strength is high when the resin composition is applied to a copper-clad plate.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a flow chart showing a method for preparing a resin composition having UV screening effect according to example 1 of the present invention.

FIG. 2 is a flow chart showing the application of the resin composition with UV shielding effect in the copper-clad plate in embodiment 2 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "or/and" includes any and all combinations of one or more of the associated listed items.

The invention provides a resin composition with a UV shielding effect, which comprises the following components in parts by weight: 80-120 parts of phenolic epoxy resin, 30-50 parts of high-bromine epoxy resin, 5-15 parts of bisphenol A epoxy resin, 20-100 parts of phenolic resin, 3-10 parts of tetraphenylethane resin, 100-200 parts of filler, 0.01-0.5 part of interfacial bonding agent, 40-80 parts of solvent A and 60-100 parts of solvent B.

The novolac epoxy resin adopts at least one of NPPN638A80, BNE200A80, NPPN438A80, KEB-3165M80S and CNE 202. The high bromine epoxy resin adopts BEB400T65 or BPEB400A 65. The bisphenol A epoxy resin adopts at least one of NPEL-127E, BE188L, YD-128, YN-1828 and NPSN901A 80. The phenolic resin adopts PF-8020 or Resicarre 3108. The tetraphenol ethane resin adopts KPE-F3110 or ZEH-8110; the filler is at least one of magnesium hydroxide, aluminum hydroxide, spherical silica micropowder, fused silica micropowder, talcum powder, boehmite and barium sulfate. The interface bonding agent adopts at least one of silane, titanate and aluminate coupling agent. The solvent A and the solvent B respectively adopt cyclohexanone (CYC), butanone (MEK), acetone, propylene glycol methyl ether or N, N-dimethylformamide.

According to the invention, the resin composition is prepared by doping the tetraphenolethane resin, and the molecular structure of the tetraphenolethane resin contains delocalized pi bonds, so that the energy is low and stable, and most of the energy is absorbed when the tetraphenolethane resin is irradiated by Ultraviolet (UV), so that the prepared resin composition has a UV shielding function, and the condition of double images can be avoided. When the argon laser is used for irradiation, because the argon laser is higher than ultraviolet light, electrons in molecules at a low energy level absorb energy, the electrons are transited from a low energy level to a high energy level, and then the electrons are transited from the high energy level to the low energy level, the absorbed energy is partially released to generate fluorescence, so that the resin composition prepared by doping the tetraphenolethane resin has the function of absorbing the argon laser, is suitable for the process of automatic optical detection, can replace tetrafunctional epoxy resin, realizes the automatic detection of a printed board by measuring the fluorescence of a substrate, and improves the detection efficiency and accuracy. The glass transition temperature of the resin composition prepared by the invention is increased, and the resin composition has high peel strength when being applied to a copper-clad plate.

In summary, the resin composition of the present invention has the following advantages compared to the following resin compositions: the resin composition has the advantages of UV shielding effect, excellent anti-ghost effect, argon laser absorption effect, capability of improving optical detection efficiency and accuracy, and high glass transition temperature, and is high in peel strength when applied to a copper-clad plate.

Example 1

Referring to fig. 1, this embodiment provides a method for preparing a resin composition with UV-screening effect, which is used to prepare the resin composition with UV-screening effect according to any one of claims 1 to 6. The preparation method comprises the following steps:

s1, cleaning the glue mixing tank by using acetone, and then sequentially adding the solvent A, the solvent B and the interface bonding agent into the glue mixing tank to obtain a mixed solution.

S2, adding the solid raw materials into the mixed solution, then adding the rest raw materials, and stirring to obtain a glue solution, namely a resin composition;

adding the solid raw materials into the mixed solution, stirring to completely dissolve the solid raw materials, then adding the rest raw materials, stirring for 3h at the rotating speed of 1000rpm, stirring for 2h at the rotating speed of 600rpm to obtain glue solution, and carrying out SGS test on the glue solution to obtain the qualified glue solution, namely the resin composition. Obtaining the glue solution for the copper-clad plate.

Example 2

This example provides a resin composition having a UV-screening effect. The resin composition comprises the following components in parts by weight: 100 parts of novolac epoxy resin, 35 parts of high-bromine epoxy resin, 10 parts of bisphenol A epoxy resin, 80 parts of novolac resin, 3 parts of tetraphenylethane resin, 150 parts of filler, 0.2 part of interfacial bonding agent, 50 parts of butanone and 90 parts of cyclohexanone.

Referring to fig. 2, the embodiment further provides an application of the resin composition with UV shielding effect in the copper clad laminate. The operation of the application is as follows:

the resin composition is provided, which is prepared by the preparation method as described in example 1.

Carrying out impregnation and baking treatment on the resin composition to obtain a plurality of groups of prepregs for later use;

and (3) placing the resin composition in a vertical gluing machine for dipping treatment, and then baking to obtain a prepreg. In the process of dipping and baking treatment, the content of glue in the resin composition is controlled to be 40-78%, the fluidity is controlled to be 10-50%, and the volatile matter is less than 0.5%.

And taking six prepregs, stacking the prepregs together in order to obtain a stacked object, and covering one copper foil (with the thickness of 1 OZ) on each of the upper part and the lower part of the stacked object to obtain a stacked body.

Carrying out pressing treatment on the stacked structure to obtain a composite laminated board, namely a copper-clad plate;

and putting the stacked body into a hot press, and pressing after a certain time, temperature and pressure to obtain the composite laminated board.

Example 3

The difference between this example and example 2 is that the resin composition comprises, in parts by weight: 5 parts of tetraphenol ethane resin and 0.035 part of interface bonding agent.

Example 4

The difference between this example and example 2 is that the resin composition comprises, in parts by weight: 7 parts of tetraphenol ethane resin and 0.035 part of interface bonding agent.

Example 5

The difference between this example and example 2 is that the resin composition comprises, in parts by weight: 10 parts of tetraphenol ethane resin and 0.035 part of interface bonding agent.

Comparative example 1

This comparative example provides a resin composition having a UV-screening effect. The resin composition comprises the following components in parts by weight: 100 parts of phenolic epoxy resin, 35 parts of high-bromine epoxy resin, 10 parts of bisphenol A type epoxy resin, 80 parts of phenolic resin, 150 parts of filler, 0.035 part of interface bonding agent, 50 parts of butanone and 90 parts of cyclohexanone.

The comparative example differs from example 1 in that, in the composition of the resin composition in parts by weight: 0.035 parts of interfacial bonding agent, and tetraphenylethane was not added.

Comparative example 2

The comparative example differs from comparative example 1 in that the resin composition comprises, in parts by weight: 1 part of tetraphenylethane resin.

Comparative example 3

The comparative example differs from comparative example 1 in that the resin composition comprises, in parts by weight: and 2 parts of tetraphenylethane resin.

Comparative examples 1, 2 and 3 were used as control groups to conduct control experiments to analyze properties of the resin compositions prepared in examples 2, 3, 4 and 5. Table 1 shows a comparative table of the compositions in parts by weight of the resin compositions in examples 2 to 5 and comparative examples 1 to 3.

Table 1:

the glass transition temperature (Tg) of the resin compositions in the above examples and comparative examples was measured according to Differential Scanning Calorimetry (DSC) by the DSC method specified by IPC-TM-6502.4.25. The thermal delamination time T-288 of the resin compositions of the above examples and comparative examples was measured in accordance with the method specified by IPC-TM-6502.4.24.1. The thermal cracking temperature (Td) of the resin compositions in the above examples and comparative examples was measured in accordance with the method specified by IPC-TM-6502.4.25.6. The flame retardancy of the resin compositions of the above examples and comparative examples was measured according to the vertical flame method specified in UL 94. The copper clad laminates in the above examples and comparative examples were tested for white spots, delamination and blistering by autoclaving for 2 hours in a tin furnace at 288 ℃. The coating adhesion of the copper clad laminates in the above examples and comparative examples was tested according to the method specified in IPC-650.

The detection results are shown in table 2, and table 2 is a comparison table of performance test results of the resin composition/copper-clad plate in examples 2-5 and comparative examples 1-3;

table 2:

by carrying out comparative analysis on the test results of table 2, it is known that the resin composition of the present invention has high UV absorption rate, excellent anti-ghost effect, argon laser absorption effect, improved optical detection efficiency and accuracy, improved glass transition temperature, and high peel strength. The performance test results prove that the resin composition prepared by the invention has the advantages of UV shielding effect, excellent anti-ghost effect, argon laser absorption effect, optical detection efficiency and accuracy improvement, and high glass transition temperature, and when the resin composition is applied to a copper-clad plate, the peel strength is high.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above examples are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.