CN114163774B

CN114163774B - Resin composition, prepreg comprising resin composition, laminated board and printed circuit board

Info

Publication number: CN114163774B
Application number: CN202111564351.1A
Authority: CN
Inventors: 何烈相; 吴彦兵
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2021-12-20
Filing date: 2021-12-20
Publication date: 2023-09-12
Anticipated expiration: 2041-12-20
Also published as: CN114163774A

Abstract

The present invention relates to a resin composition, a prepreg comprising the same, and a laminate and a printed circuit board, wherein the resin composition comprises: (A) DCPD epoxy resin (B) active ester resin (C) phosphorus-containing phenolic resin (D) inorganic filler; the DCPD epoxy resin at least contains one DCPD epoxy resin with a softening point less than 95 ℃, and the mass percentage of the DCPD epoxy resin with the softening point less than 95 ℃ in the DCPD epoxy resin is more than 40%. The prepreg, the laminated board and the printed circuit board prepared from the resin composition have no resin enrichment problem and have excellent interlayer adhesion.

Description

Resin composition, prepreg comprising resin composition, laminated board and printed circuit board

Technical Field

The invention relates to the technical field of printed circuit boards, in particular to a resin composition, a prepreg containing the resin composition, a laminated board and a printed circuit board.

Background

The laminated board is a substrate material of a printed circuit board, and as the printed circuit board or the laminated board is more widely applied and more highly applied, the performance requirement on the printed circuit board or the laminated board is also more and more high, and further, the components of the key resin composition which plays a role of an insulating medium in the laminated board are more and more high. In order to improve the thermal expansion coefficient and improve the electrical properties, rigidity and other properties, the filler becomes an essential component, and multiphase multicomponent tends to cause multiphase compatibility problems. Resin enrichment refers to the fact that, among organic and inorganic fillers which should be homogeneously distributed, no filler appears somewhere, all resin components.

However, many resin compositions are currently used for printed wiring boards, resin problems are unavoidable, and interlayer adhesion is generally exhibited.

In view of the above, it is important to develop a resin composition for laminates and printed circuit boards which can solve the problem of resin enrichment and have excellent interlayer adhesion.

Disclosure of Invention

In view of the shortcomings of the prior art, the invention aims to provide a resin composition, a prepreg, a laminated board and a printed circuit board containing the resin composition, and the prepreg, the laminated board and the printed circuit board prepared from the resin composition have no resin enrichment problem and have excellent interlayer adhesion.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a resin composition comprising:

(A) Dicyclopentadiene (DCPD) epoxy resins

(B) Active ester resins

(C) Phenolic resin containing phosphorus

(D) An inorganic filler;

the DCPD epoxy resin at least contains one DCPD epoxy resin (such as 2, 3, 4 and the like) with softening point less than 95 ℃ (such as 90 ℃, 85 ℃, 80 ℃ and the like),

the DCPD epoxy resin with the softening point of less than 95 ℃ comprises more than 40 percent (such as 50 percent, 60 percent, 70 percent, 80 percent and the like) of the mass of the DCPD epoxy resin.

According to the resin composition, the softening point and the proportion of DCPD epoxy resin are controlled, so that the flow matching window of resin and filler is effectively optimized, and prepregs, laminated boards and printed circuit boards manufactured by the resin composition have no resin enrichment problem; the DCPD epoxy is matched with other components and plays a synergistic promotion role, so that the bonding force between layers in the laminated board and the printed circuit board is effectively improved, and the laminated board and the printed circuit board prepared from the resin composition have excellent interlayer bonding force.

Preferably, the DCPD epoxy resin having a softening point of less than 95 ℃ is 60% to 100% by mass, such as 60%, 80%, 100% or the like, in the DCPD epoxy resin. The DCPD epoxy resin with the softening point less than 95 ℃ is more beneficial to the improvement of interlayer adhesive force performance of a laminated board and a printed circuit board further formed by the resin composition when the mass percentage of the DCPD epoxy resin is in the range of 60-100%.

The softening point test method is a cup and ball method test, and a testing instrument is a mertler thermal analyzer, model FP90.

Preferably, the component (B) is 36.8 to 51.6 parts by weight, for example, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, or the like, based on 100 parts by weight of the component (a). The addition amount of the active ester resin of the component (B) is too low, which can lead to the reduction of interlayer adhesion; the addition of too high an amount of the active ester resin of component (B) results in a composition having a glass transition temperature (T) _g ) And lower.

Preferably, the component (C) is 42.8 to 66.8 parts by weight, for example 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, etc. The addition amount of the component (C) phosphorus-containing phenolic resin is too small to ensure the enough flame retardant property of the resin composition; when the phosphorus-containing phenolic resin of the component (C) is added in an excessive amount, the water absorption of the resin composition becomes large, and the interlayer adhesion between the laminate and the printed wiring board formed by the resin composition is further lowered.

Preferably, the mass ratio of the component (D) is 30 to 50%, for example 35%, 40%, 45%, etc., calculated on 100% of the sum of the component (a), the component (B), the component (C) and the component (D), and the filler ratio is too high, and the interlayer adhesion of the laminate and the printed wiring board which are further formed is deteriorated; too low a filler ratio results in deterioration of Df and deterioration of thermal expansion coefficient.

The present invention utilizes the mutual cooperation and mutual synergistic promotion effect between the four essential components with the specific content to obtain the resin composition. The prepreg, the laminated board and the printed circuit board prepared from the resin composition have no resin enrichment problem and have excellent interlayer adhesion.

Preferably, the structure of the active ester resin is selected from one or two of the formulas (I) - (II):

in formula (I), x represents phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n is 0.25-1.25 (e.g., 0.5, 0.75, 1.0, etc.). The active ester resins are selected to have low interlayer adhesion;

in the formula (II), X is phenyl or naphthyl, Y in (Y) q is each independently methyl, hydrogen atom or ester group, q is an integer of 1 to 3, n is an integer of 1 to 10, and m is an integer of 1 to 10.

Preferably, the phosphorus-containing phenolic resin comprises any one or a combination of at least two of bisphenol a-type phosphorus-containing phenolic resin, bisphenol F-type phosphorus-containing phenolic resin, dicyclopentadiene-type phosphorus-containing phenolic resin, or phenol-type phosphorus-containing phenolic resin, wherein typical but non-limiting combinations include: bisphenol a type phosphorus-containing phenolic resin and bisphenol F type phosphorus-containing phenolic resin, dicyclopentadiene type phosphorus-containing phenolic resin and phenol type phosphorus-containing phenolic resin, bisphenol a type phosphorus-containing phenolic resin, bisphenol F type phosphorus-containing phenolic resin, dicyclopentadiene type phosphorus-containing phenolic resin and phenol type phosphorus-containing phenolic resin, and the like. The phosphorus-containing phenolic resin has the advantage of good flame retardant property.

Preferably, the inorganic filler comprises any one or a combination of at least two of fused silica, crystalline silica, spherical silica, angular silica, chemical process spherical silica, hollow glass microspheres, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, or glass fiber powder, wherein typical but non-limiting combinations include: combinations of fused silica, crystalline silica and spherical silica, combinations of alumina, talc, aluminum nitride and boron nitride, combinations of barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder, and the like, and silica is further preferred. The inorganic filler is mainly used for adjusting some physical effects of the epoxy resin composition, such as further lowering of Coefficient of Thermal Expansion (CTE), lowering of water absorption, and improving of thermal conductivity.

Preferably, the inorganic filler is silica, and the particle diameter median of the filler is 0.1 to 15. Mu.m, for example, 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, etc., and more preferably, the particle diameter median of the filler is 0.1 to 10. Mu.m.

The particle size of the filler is tested by a laser diffraction method, and the test instrument is a Markov laser particle sizer, model MS3000.

Preferably, the resin composition further comprises diaminodiphenyl sulfone. Diamino diphenyl sulfone further increases the glass transition temperature of the resin composition.

Preferably, the resin composition further comprises a curing accelerator.

Preferably, the curing accelerator is selected from the group consisting of: any one or a combination of at least two of zinc iso-octoate, 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole, wherein typical but non-limiting combinations include: zinc isooctanoate in combination with 4-dimethylaminopyridine, 2-methylimidazole in combination with 2-ethyl-4-methylimidazole in combination with 2-phenylimidazole, and the like.

Preferably, the curing accelerator is 0.05 to 1 part by weight, for example, 0.08 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, 0.5 part by weight, 0.55 part by weight, 0.60 part by weight, 0.65 part by weight, 0.7 part by weight, 0.75 part by weight, 0.8 part by weight, 0.85 part by weight, 0.9 part by weight, or 0.95 part by weight, based on 100 parts by weight of the total amount of the DCPD epoxy resin, the active ester resin, and the phosphorus-containing phenolic resin.

The term "comprising" as used herein means that it may contain, in addition to the components, other components which impart different properties to the resin composition. In addition, the "comprising" described in this disclosure may be replaced with closed "being" or "consisting of … …".

For example, the resin composition may further contain various additives, and specific examples thereof include antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, adhesives, pigments, colorants, lubricants, and the like. These various additives may be used alone or in combination of two or more.

Illustratively, the method of preparing the resin composition of the present invention comprises the steps of: taking a container, firstly putting solid components to be dissolved into the container, then adding a solvent, stirring until the solid components are completely dissolved, then adding liquid resin, a filler flame retardant and a curing accelerator, continuously stirring uniformly, and finally adjusting the solid content of the liquid to 65% by using the solvent to prepare the glue solution.

In a second aspect, the present invention provides a resin film or a resin-coated copper foil, which is produced by coating the resin composition according to the first aspect on a release material or a copper foil.

In a third aspect, the present invention provides a prepreg comprising a reinforcing material and the resin composition according to the first aspect attached thereto after drying by impregnation.

The reinforcing material can be organic fiber cloth, inorganic fiber woven cloth or non-woven cloth; wherein the organic fiber is aramid non-woven fabric; the inorganic fiber woven cloth is E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or Q quartz cloth.

In a fourth aspect, the present invention provides a laminate comprising at least one (e.g. 2, 3, 4, etc.) sheet of prepreg as described in the first aspect.

In a fifth aspect, the present invention provides a printed circuit board comprising: at least one (e.g. 2, 3, 4, etc.) sheet of prepreg as described in the second aspect, or at least one (e.g. 2, 3, 4, etc.) sheet of laminate as described in the third aspect.

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

the prepreg, the laminated board and the printed circuit board prepared from the resin composition have no resin enrichment problem and have excellent interlayer adhesion.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

The materials listed in the examples of the present invention are as follows:

KES-7695M75: epoxy resins with softening points of more than or equal to 95 ℃ and DCPD structures are purchased from KOLON.

KES-7680M75: epoxy resins with a softening point of < 95 ℃ and containing DCPD structures are available from KOLON.

HPC-8000-65T: active ester resins, available from DIC.

HPC-8000L-65MT: active ester resins, available from DIC.

JFH-Z3101P60: bisphenol A type phosphorus-containing phenolic resin is purchased from Kyoho.

NRS-480A: phosphorus-containing phenolic resins available from Nanokor.

DS2032A: silica filler, available from Jiangsu-niruri.

NQ1028L: silica filler, available from Jiangsu-niruri.

DMAP: curing accelerator, 4-dimethylaminopyridine, purchased from Yu Anrong chemistry.

Diamino diphenyl sulfone: purchased from Armadillidium, brand DDS.

Example 1

The embodiment provides an epoxy resin copper clad laminate, which is prepared by taking a resin composition as a raw material, wherein the resin composition comprises the following components: (A) a DCPD epoxy resin having a softening point of less than 95 ℃, a (B) an active ester resin, a (C) a phosphorus-containing phenolic resin, and (D) an inorganic filler.

The preparation method of the laminated board comprises the following steps:

taking a container, adding 100 parts by weight of epoxy resin KES-7680M75, 22.3 parts by weight of active ester resin HPC-8000-65T, 22.3 parts by weight of active ester resin HPC-8000L-65MT, 54.2 parts by weight of phosphorus-containing phenolic resin JFH-Z3101P60 and 30wt% (85.2 parts by weight, accounting for 30wt% of the sum of epoxy resin, active ester resin, phosphorus-containing phenolic resin and inorganic filler) of inorganic filler DS2032A, dissolving a curing accelerator DMAP in advance, continuing stirring uniformly, and finally regulating the solid content of liquid to 65% by using a solvent, thereby preparing a glue solution.

The glue solution was impregnated with 2116 glass fiber cloth, and then dried to remove the solvent, thereby obtaining a prepreg. The prepared 6 prepregs are mutually overlapped, two 35 mu m copper foils are respectively pressed on the two sides of the prepreg, and the prepreg is put into a hot press to be cured for more than 120 minutes at the temperature of 190 ℃ to prepare the epoxy resin copper foil-clad laminate.

Examples 2 to 11

The production process of examples 2 to 11 was the same as that of example 1, and the formulation composition and physical properties thereof are shown in tables 1 to 2.

Comparative examples 1 to 4

Comparative examples 1 to 4 were prepared in the same manner as in example 1, and the formulation composition and physical properties thereof are shown in Table 3.

TABLE 1 formulation compositions and physical Property data for examples 1-6

Substance (B)

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

KES-7695M75

KES-7680M75

100

HPC-8000-65T

22.3

HPC-8000L-65MT

22.3

36.8

51.6

JFH-Z3101P60

54.2

66.8

42.8

NRS-480A

DS2032A

30％

40％

50％

55％

40％

DQ1028L

/

DDS

/

DMAP

Proper amount of

2E4MI

Proper amount of

Whether or not to enrich the resin

Whether or not

Interlayer adhesion (N/mm)

0.80-1.20

0.74-1.13

0.65-0.95

0.60-0.90

0.68-0.98

0.85-1.25

TABLE 2 formulation compositions and physical Property data for examples 7-11

Substance (B)	Example 7	Example 8	Example 9	Example 10	Example 11
						KES-7695M75	60	20
KES-7680M75	40	80	100	100	100
						HPC-8000-65T	22.3	22.3	22.3	22.3	/
HPC-8000L-65MT	22.3	22.3	22.3	22.3	11.9
						JFH-Z3101P60	54.2	54.2	/	54.2	11.9
NRS-480A			54.2		49.1
						DS2032A	40％	40％	/	/
DQ1028L	/	/	40％	40％	40％
						DDS	/	/	/	/	7.0
DMAP	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of
						2E4MI	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of
Whether or not to enrich the resin	Whether or not	Whether or not	Whether or not	Whether or not	Whether or not
						Interlayer adhesion (N/mm)	0.66-0.97	0.68-1.01	0.75-1.16	0.72-1.10	0.65-0.96

TABLE 3 formulation composition and physical Property data of each comparative example

Note that: the non-dimensional components in the table are all in parts by weight, and the weight percentage of the filler of component (D) is 100% based on the total mass of component (A), component (B), component (C) and component (D).

The test method of the above characteristics is as follows:

(1) Interlayer adhesion (axe blade separation method): and (3) peeling one end of a test sample (with the width of 3mm and the length of 150 mm) of the copper-clad laminate by using a knife to form 2 layers of bonding sheets, peeling the bonding sheets to the length of about 20mm, clamping the test sample on a test fixture, and fixing the upper end and the lower end of the test sample to keep the test sample in a vertical state. One end of the test strip is peeled off to cross the blade of the axe-shaped test head, the separated surface of the test sample and the axe blade are kept on the same axis, a peeling strength tester is started, a tensile force is applied in the vertical direction at a speed of 50mm/min, the test sample is separated by the axe blade, at least 50mm is separated, and the interlayer cohesive force is the average separation force of the test sample/the width of the test sample.

(2) Enriching resin: and (3) judging whether the resin is enriched in the substrate region or not by making a sample size with the length of 10mm and the width of 10mm and observing with an SEM (electron microscope) at a magnification of 100 times after making a slice. If the resin phase and the filler phase are separated in the observation area or the resin is obviously only free of the filler in the specific area, the resin enrichment is realized. If no resin phase separation from the filler occurs in the observation area, no filler is observed, i.e. no enrichment of the resin is observed.

Analysis of physical Properties

As is clear from the data in tables 1 to 2, in each example, the resin composition of the present invention does not give rise to resin enrichment and has excellent interlayer adhesion, and as exemplified in examples 1 to 11, the resin composition forms a laminate having an interlayer adhesion of 0.65 to 1.25.

As can be seen from the data in table 3, in each comparative example, the resin polymer resulted in resin enrichment and poor interlayer adhesion.

Specifically, analysis of comparative example 2 and example 2, comparative example 4 and examples 7 and 8 shows that the interlayer adhesion properties of comparative example 2 and comparative example 4 are worse and resin enrichment occurs, which proves that the DCPD epoxy resin with softening point less than 95 ℃ according to the present invention has a mass percentage of more than 40%, more preferably 60% -100% in the DCPD epoxy resin, and the resulting resin composition has better properties.

The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. A resin composition for prepregs, laminates and printed circuit boards free of resin enrichment problems, characterized in that the resin composition comprises:

(A) DCPD epoxy resin

(B) Active ester resins

(C) Phenolic resin containing phosphorus

(D) An inorganic filler;

the DCPD epoxy resin at least contains one DCPD epoxy resin with a softening point less than 95 ℃;

the mass percentage of the DCPD epoxy resin with the softening point less than 95 ℃ in the DCPD epoxy resin is 60-100%;

based on 100 parts by weight of the component (A), the component (B) is 42-51.6 parts by weight; the component (C) is 42.8-55 parts by weight;

the mass ratio of the component (D) is 30-45 percent calculated by taking the sum of the component (A), the component (B), the component (C) and the component (D) as 100 percent.

2. The resin composition of claim 1, wherein the structure of the active ester resin is selected from one or two of the formulas (I) - (II):

in the formula (I), x represents phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n is 0.25-1.25;

3. The resin composition of claim 1, wherein the phosphorus-containing phenolic resin comprises any one or a combination of at least two of bisphenol a-type phosphorus-containing phenolic resin, bisphenol F-type phosphorus-containing phenolic resin, dicyclopentadiene-type phosphorus-containing phenolic resin, or phenol-phenolic-type phosphorus-containing phenolic resin.

4. The resin composition of claim 1, wherein the inorganic filler comprises any one or a combination of at least two of fused silica, crystalline silica, spherical silica, angular silica, chemical silica, hollow glass microspheres, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, or glass fiber powder.

5. The resin composition of claim 1, wherein the resin composition further comprises diamino diphenyl sulfone.

6. The resin composition of claim 1, wherein the resin composition further comprises a cure accelerator.

7. The resin composition of claim 6, wherein the cure accelerator is selected from the group consisting of: any one or a combination of at least two of zinc isooctanoate, 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole.

8. A resin film or a resin-coated copper foil, which is obtained by coating the resin composition according to any one of claims 1 to 7 on a release material or a copper foil.

9. A prepreg comprising a reinforcing material and the resin composition according to any one of claims 1 to 7 attached thereto after drying by impregnation.

10. A laminate comprising at least one prepreg according to claim 9.

11. A printed circuit board, the printed circuit board comprising: at least one prepreg according to claim 9, or at least one laminate according to claim 10.