CN114163774A

CN114163774A - Resin composition, prepreg containing resin composition, laminated board and printed circuit board

Info

Publication number: CN114163774A
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: 2022-03-11
Anticipated expiration: 2041-12-20
Also published as: CN114163774B

Abstract

The present invention relates to a resin composition, a prepreg comprising the same, and a laminate and a printed circuit board, the resin composition comprising: (A) DCPD epoxy resin (B), active ester resin (C), phosphorus-containing phenolic resin (D) and inorganic filler; the DCPD epoxy resin at least contains a DCPD epoxy resin with the softening point of less than 95 ℃, and the mass percentage of the DCPD epoxy resin with the softening point of 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 bonding force.

Description

Resin composition, prepreg containing 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 the printed circuit board, and along with the wider application and higher application of the printed circuit board or the laminated board, the performance requirement on the printed circuit board or the laminated board is higher, and further, the components of the key resin composition playing a role of an insulating medium in the laminated board are more and more. The filler becomes an essential component in order to improve the thermal expansion coefficient, electrical properties, rigidity and the like, and multiphase and multicomponent components tend to cause multiphase compatibility problems. Resin enrichment means that in organic and inorganic fillers, which should be homogeneously distributed per se, no filler is present somewhere, all being resin components.

However, many of the resin compositions used in printed wiring boards at present have problems of resin which cannot be avoided, and the interlayer adhesion is generally exhibited.

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

Disclosure of Invention

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

In order 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 resin

(B) Active ester resin

(C) Phosphorus-containing phenolic resin

(D) An inorganic filler;

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

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

According to the resin composition, the softening point and the proportion of the DCPD epoxy resin are controlled, so that the flow matching window of the resin and the filler is effectively optimized, and the prepreg, the laminated board and the printed circuit board which are prepared from the resin composition have no resin enrichment problem; the DCPD epoxy is matched with other components and plays a mutual synergistic and promoting 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 in the DCPD epoxy resin, such as 60%, 80%, 100%, etc. The DCPD epoxy resin with the softening point less than 95 ℃ accounts for 60-100% by mass, and is more beneficial to the improvement of the interlayer adhesive force performance of a laminated board and a printed circuit board formed by the resin composition.

The softening point test method adopts a cup and ball method test, and a test instrument is a Mettler thermal analyzer, model FP 90.

Preferably, the component (B) is 36.8 to 51.6 parts by weight, such as 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, etc., 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, so that the interlayer bonding force is reduced; the active ester resin of component (B) is added in an amount too high to result in a glass transition temperature (T) of the composition_g) And is low.

Preferably, the component (C) is 42.8 to 66.8 parts by weight, such as 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, and the like. The phosphorus-containing phenolic resin as the component (C) is too little in addition amount, so that the sufficient flame retardant property of the resin composition cannot be guaranteed; when the phosphorus-containing phenol resin as component (C) is added in an excessive amount, the resin composition has a high water absorption rate, and the interlayer adhesion between the laminate and the printed wiring board formed therefrom is further lowered.

Preferably, the mass proportion of the component (D) is 30-50%, such as 35%, 40%, 45% and the like, calculated by taking the total of the component (a), the component (B), the component (C) and the component (D) as 100%, the filler proportion is too high, and the interlayer adhesion of the laminate and the printed circuit board formed by the filler proportion is deteriorated; too low a filler ratio results in a deterioration of Df and a deterioration of the thermal expansion coefficient.

The present invention utilizes the mutual coordination and mutual synergistic promotion effect among the above-mentioned four essential components in specific contents to obtain the above-mentioned 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 bonding force.

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

in the formula (I), x represents a phenyl group or a naphthyl group, j is 0 or 1, k is 0 or 1, and n is 0.25 to 1.25 (e.g., 0.5, 0.75, 1.0, etc.). The use of these active ester resins has the advantage of low interlayer adhesion;

in the formula (II), X is phenyl or naphthyl, Y in (Y) q is 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 of 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, wherein typical but non-limiting combinations include: a combination of a bisphenol a-type phosphorus-containing phenol resin and a bisphenol F-type phosphorus-containing phenol resin, a combination of a bisphenol F-type phosphorus-containing phenol resin, a dicyclopentadiene-type phosphorus-containing phenol resin, and a phenol-type phosphorus-containing phenol resin, a combination of a bisphenol a-type phosphorus-containing phenol resin, a bisphenol F-type phosphorus-containing phenol resin, a dicyclopentadiene-type phosphorus-containing phenol resin, and a phenol-type phosphorus-containing phenol resin, and the like. The phosphorus-containing phenolic resin has the advantage of good flame retardant property.

Preferably, the inorganic filler includes any one or a combination of at least two of fused silica, crystalline silica, spherical silica, angle silica, chemical spherical silica, hollow glass microspheres, aluminum hydroxide, alumina, 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: fused silica, a combination of crystalline silica and spherical silica, a combination of alumina, talc, aluminum nitride and boron nitride, a combination of barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder, etc., and silica is more preferable. The inorganic filler is mainly used for adjusting some physical property effects of the epoxy resin composition, such as further reducing the Coefficient of Thermal Expansion (CTE), reducing water absorption, improving thermal conductivity and the like.

Preferably, the inorganic filler is silica, and the filler has a particle size median value of 0.1 to 15 μm, for example, 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, and the like, and more preferably, the filler has a particle size median value of 0.1 to 10 μm.

The particle size of the filler herein was tested by laser diffraction method with a test instrument, malvern laser granulometer, model MS 3000.

Preferably, the resin composition further comprises diamino diphenyl sulfone. Diaminodiphenyl sulfone further increases the glass transition temperature of the resin composition.

Preferably, the resin composition further includes a curing accelerator.

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

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

For example, the resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a tackifier, a pigment, a colorant, a lubricant, and the like. These various additives may be used alone or in combination of two or more.

Illustratively, the preparation method of the resin composition of the present invention comprises the steps of: taking a container, firstly putting solid components needing to be dissolved, 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 a glue solution.

In a second aspect, the present invention provides a resin film or a resin-coated copper foil obtained 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 of the first aspect attached thereto by impregnation drying.

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 sheet (e.g. 2, 3, 4, etc.) of prepreg according to 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.) prepreg as described in the second aspect, or at least one (e.g. 2, 3, 4, etc.) 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 bonding force.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

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

KES-7695M 75: epoxy resin with softening point more than or equal to 95 ℃ and DCPD structure is purchased from KOLON.

KES-7680M 75: epoxy resins having a softening point of < 95 ℃ and containing DCPD structures are available from KOLON.

HPC-8000-65T: activated ester resin, available from DIC.

HPC-8000L-65 MT: activated ester resin, available from DIC.

JFH-Z3101P 60: bisphenol a type phosphorus containing phenolic resin, available from suzhou Kyoho.

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

DS 2032A: silica filler, available from biseri, Jiangsu.

NQ 1028L: silica filler, available from biseri, Jiangsu.

DMAP: curing accelerator, 4-dimethylaminopyridine, available from Guangrong Chemicals.

Diamino diphenyl sulfone: purchased from atlas, designation DDS.

Example 1

This example provides an epoxy resin-clad copper foil laminate prepared from a resin composition as a raw material, the resin composition comprising: (A) DCPD epoxy resin with the softening point of less than 95 ℃, (B) active ester resin, (C) phosphorus-containing phenolic resin and (D) inorganic filler.

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

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, 30 wt% (85.2 parts by weight, accounting for 30 wt% of the total of the epoxy resin, the active ester resin, the phosphorus-containing phenolic resin and the inorganic filler) of inorganic filler DS2032A, dissolving a curing accelerator DMAP in advance, continuously stirring uniformly, and finally adjusting the solid content of the liquid to 65% by using a solvent to prepare the glue solution.

And (3) dipping the glue solution by 2116 glass fiber cloth, and then drying to remove the solvent to obtain the prepreg. And (3) overlapping 6 prepared prepregs, respectively laminating a 35-micron copper foil on two sides of the prepregs, and curing in a hot press at 190 ℃ for over 120 minutes to prepare the epoxy resin copper-clad laminate.

Examples 2 to 11

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

Comparative examples 1 to 4

Comparative examples 1 to 4 were prepared by the same process as in example 1, and the formulation compositions and physical property indexes thereof are shown in Table 3.

TABLE 1 formulation compositions of examples 1-6 and physical property data thereof

Substance(s)

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 resin enrichment is present or not

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(s)	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 resin enrichment is present or not	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: the dimensionless components in the table are all in parts by weight, and the weight percent 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 separation method): a small knife is used for peeling 2 layers of bonding sheets at one end of a copper-clad laminate sample (the width is 3mm, the length is 150mm), the length is about 20mm, the sample is clamped on a test fixture, and the upper end and the lower end of the sample are fixed, so that the sample is kept in a vertical state. The test strip is peeled to one end to cross over 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 pulling force is applied in the vertical direction at the speed of 50mm/min, the test sample is separated by the axe blade, the separation is at least 50mm, and the interlayer bonding force is the average separation force of the test sample/the width of the test sample.

(2) Resin enrichment: by making sample sizes 10mm long and 10mm wide, and observing with SEM (electron microscope) at magnification of 100 times after making slices, it is judged whether resin enrichment exists in the substrate region. If the phenomenon that the resin is separated from the filler in the observation area or the resin is obviously only not filled in the specific area is generated, the resin is enriched. If no resin phase separation with the filler occurs in the observation area, no resin without filler is observed, i.e. no resin enrichment is observed.

Physical Property analysis

As is clear from the data in tables 1-2, the resin compositions of the present invention in each example did not produce resin enrichment and had excellent interlayer adhesion, and laminates formed from the resin compositions of examples 1-11 had interlayer adhesion between 0.65 and 1.25.

As can be seen from the data in Table 3, the resin polymers produced resin enrichment and exhibited poor interlayer adhesion in each comparative example.

Specifically, as can be seen from the analysis of comparative examples 2 and 2, comparative examples 4, and 7 and 8, the interlayer adhesion performance of comparative examples 2 and 4 is worse, and resin enrichment occurs, and it is proved that the DCPD epoxy resin with a softening point of less than 95 ℃ in the invention has a mass percentage of more than 40%, more preferably 60% -100%, in the DCPD epoxy resin, and the performance of the formed resin composition is better.

The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A resin composition, characterized in that the resin composition comprises:

(A) DCPD epoxy resin

(B) Active ester resin

(C) Phosphorus-containing phenolic resin

(D) An inorganic filler;

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

the DCPD epoxy resin with the softening point less than 95 ℃ accounts for more than 40% of the DCPD epoxy resin by mass.

2. The resin polymer according to claim 1, wherein the DCPD epoxy resin having a softening point of less than 95 ℃ is 60 to 100% by mass in the DCPD epoxy resin.

3. The resin composition according to claim 1 or 2, characterized in that the component (B) is 36.8 to 51.6 parts by weight based on 100 parts by weight of the component (a);

preferably, the component (C) is 42.8 to 66.8 parts by weight;

preferably, the mass proportion of the component (D) is 30-50% calculated by taking the total of the component (A), the component (B), the component (C) and the component (D) as 100%.

4. The resin composition according to any one of claims 1 to 3, wherein the structure of the active ester resin is selected from one or two of formula (I) to formula (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;

5. The resin composition according to any one of claims 1 to 4, wherein the phosphorus-containing phenol resin comprises any one of or a combination of at least two of bisphenol A type phosphorus-containing phenol resin, bisphenol F type phosphorus-containing phenol resin, dicyclopentadiene type phosphorus-containing phenol resin, or phenol resin;

preferably, the inorganic filler includes any one or a combination of at least two of fused silica, crystalline silica, spherical silica, angle silica, chemical process silica, hollow glass microspheres, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, or glass fiber powder.

6. Resin composition according to any one of claims 1-5, characterized in that the resin composition further comprises diaminodiphenyl sulfone. Preferably, the resin composition further includes a curing accelerator;

preferably, the curing accelerator is selected from the group consisting of: any one or combination of at least two of zinc isooctanoate, 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole.

7. 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 6 on a release material or a copper foil.

8. A prepreg comprising a reinforcing material and the resin composition according to any one of claims 1 to 6 attached thereto by impregnation drying.

9. A laminate comprising at least one prepreg according to claim 8.

10. A printed circuit board, comprising: at least one prepreg according to claim 8, or at least one laminate according to claim 9.