CN117736541A - Composite resin composition and application thereof - Google Patents

Composite resin composition and application thereof Download PDF

Info

Publication number
CN117736541A
CN117736541A CN202311704156.3A CN202311704156A CN117736541A CN 117736541 A CN117736541 A CN 117736541A CN 202311704156 A CN202311704156 A CN 202311704156A CN 117736541 A CN117736541 A CN 117736541A
Authority
CN
China
Prior art keywords
parts
epoxy resin
resin
resin composition
benzoxazine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311704156.3A
Other languages
Chinese (zh)
Inventor
温文彦
沈永贤
郭永军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Ying Hua New Mstar Technology Ltd
Original Assignee
Guangdong Ying Hua New Mstar Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Ying Hua New Mstar Technology Ltd filed Critical Guangdong Ying Hua New Mstar Technology Ltd
Priority to CN202311704156.3A priority Critical patent/CN117736541A/en
Publication of CN117736541A publication Critical patent/CN117736541A/en
Pending legal-status Critical Current

Links

Abstract

The application provides a composite resin composition and application thereof, wherein the composite resin composition comprises the following components in parts by mass: 10-50 parts of epoxy resin, 10-30 parts of benzoxazine resin, 10-50 parts of curing agent, 5-30 parts of flame retardant and 10-60 parts of inorganic filler; wherein the curing agent contains a compound represented by the formula (1). The composite resin has high heat resistance, good cohesiveness, low water absorption, low dielectric constant and low dielectric loss value.

Description

Composite resin composition and application thereof
Technical Field
The invention relates to the technical field of resin, in particular to a composite resin composition and application thereof.
Background
With the high-speed development of high-frequency high-speed digital signal transmission technology and electronic installation technology, in order to ensure the durability and stability of the characteristic impedance of a transmission line on a printed circuit board (PCB board), the role of gradually converting a copper-clad laminate from circuit interconnection into a signal transmission line has become common in the art in the direction of high-frequency, high-speed, high-density and the like, and thus, higher requirements are put on heat resistance, dielectric properties and the like of the copper-clad laminate.
In the prior art, styrene-maleic anhydride copolymer is often used as a curing agent to react with resin for preparing a laminated board, and although the laminated board with lower dielectric constant, dielectric loss value and higher glass transition temperature can be obtained, the prepared laminated board still has the problems of higher water absorption, lower heat resistance, lower bonding performance with metal foil and the like.
Accordingly, the conventional technology has yet to be improved.
Disclosure of Invention
Based on this, the present application provides a composite resin composition which can combine high heat resistance, good adhesion, low water absorption, low dielectric constant and dielectric loss value, and its use.
The technical scheme of the application is as follows.
In a first aspect of the present application, there is provided a composite resin composition comprising, in parts by mass:
10-50 parts of epoxy resin,
10 to 30 parts of benzoxazine resin,
10-50 parts of curing agent,
5-30 parts of flame retardant,
10-60 parts of inorganic filler;
wherein the curing agent contains a compound represented by the formula (1):
r is selected from oxygen atom, carbonyl or any structure in the following formulas (a) - (e):
wherein R is 1 And R is 2 Each independently selected from any one of a single bond, an alkane subunit having 1 to 5 carbon atoms, an oxygen atom and a sulfone group; r is R 3 ~R 6 Each independently selected from a single bond or an alkane subunit having 1 to 3 carbon atoms; * Representing the ligation site.
The composite resin composition contains epoxy resin, benzoxazine resin, curing agent, flame retardant and inorganic filler in a specific weight ratio, and the components are synergistic, so that the composite resin composition has high heat resistance, good cohesiveness, low water absorption and low dielectric constant and dielectric loss value. Wherein the curing agent contains a compound shown in a formula (1), is a polybasic acid anhydride curing agent with a specific structure, and the compound shown in the formula (1) contains a plurality of benzene ring structures and a plurality of acid anhydride groups, and improves the adhesive property of the composite resin composition while maintaining excellent heat resistance, low water absorption and excellent dielectric property after being cooperated with other components by a specific proportion.
In some embodiments, the composite resin composition satisfies any one of the following conditions (1) to (2):
(1)R 1 any one selected from single bond, oxygen atom and sulfonyl;
(2)R 2 any one selected from alkane subunit with 1-3 carbon atoms, oxygen atoms and sulfonyl;
(3)R 3 ~R 6 independently selected from a single bond and an alkane subunit having 1 to 3 carbon atoms.
In some embodiments, R is selected from formula (d).
The structure of R is further regulated, so that the bonding performance can be further improved.
In some embodiments, R is selected from any one of the structures (1-1) - (1-9) below:
。
in some of these embodiments, the composite resin composition includes, in parts by mass:
20-40 parts of epoxy resin,
20 to 30 parts of benzoxazine resin,
30-50 parts of curing agent,
10-20 parts of flame retardant,
20-40 parts of inorganic filler.
The mass parts of each component in the composite resin composition are further regulated, the heat resistance, dielectric property and adhesive property of the composite resin are further improved, and meanwhile, the lower water absorption rate is maintained.
In some of these embodiments, the composite resin composition satisfies at least one of the following conditions (1) to (4):
(1) The epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A phenolic epoxy resin, phenol phenolic epoxy resin, trifunctional phenol epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type phenolic epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin;
(2) The benzoxazine resin comprises at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diamine type benzoxazine resin, MDA type benzoxazine, ODA type benzoxazine, DCPD type benzoxazine, phenol type benzoxazine and DOPO type benzoxazine;
(3) The inorganic filler comprises at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass ceramics, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talcum powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin;
(4) The flame retardant comprises at least one of decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate compound and phosphorus-containing cyanate.
In some of these embodiments, the composite resin composition further includes other adjuvants including at least one of a curing accelerator, a coupling agent, and a toughening agent.
In a second aspect of the present application, there is also provided a cured resin produced using the raw material of the composite resin composition of the first aspect.
The cured resin has high heat resistance, good cohesiveness, low water absorption, low dielectric constant and low dielectric loss value.
In a third aspect of the present application, there is provided a prepreg comprising a reinforcing material and a resin material supported by the reinforcing material, the resin material comprising the cured resin of the second aspect.
In a fourth aspect of the present application, there is also provided a laminate, the laminate being prepared from a starting material comprising the prepreg of the first aspect.
In a fifth aspect of the present application, there is also provided a printed circuit board comprising the laminate of the fourth aspect.
Detailed Description
In order to facilitate an understanding of the present application, a more complete description of the present application will be provided below, along with preferred embodiments of the present application. This application may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, the term "alkane subunit" refers to a group formed by the alkane losing two hydrogens, e.g. methane losing two hydrogens to form a methylene group.
The term "alkane subunit" refers to a group formed by the loss of two hydrogens from an alkane in which the carbon atoms are all singly linked and not in a ring, and the remaining valences are all hydrogen bonded, including straight chain alkane subunits and branched alkane subunits.
In this application, "×" indicates a ligation site.
In this application, where no attachment site is indicated in a group, an optionally attachable site in the group is meant as an attachment site.
In the present application, a single bond to a substituent extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.gR in (C) is connected with any substitutable site of benzene ring.
Styrene-maleic anhydride copolymers are often used as curing agents in the traditional technology for preparing laminated boards by curing reaction with resins, however, the prepared laminated boards have poor bonding performance with metal foils.
In the conventional technology, the resin is modified to improve the adhesive property, for example, other functional resins are added into an epoxy resin system to prepare a prepreg and a copper clad laminate, and although the laminate with lower dielectric constant, dielectric loss value and higher glass transition temperature can be obtained, the prepared laminate still has the defects of higher water absorption rate, lower heat resistance and the like, and is difficult to apply in the high-frequency and high-speed field.
The technical personnel of styrene-maleic anhydride copolymer curing agent (SMA for short below) have conducted intensive studies to find that: the nonpolar styrene structure of SMA reduces the polarity of the resin system, thereby weakening the interaction force between the resin and the copper foil. Thus, after a great deal of creative investigation, a composite resin composition having high heat resistance, good adhesion, low water absorption, low dielectric constant and dielectric loss value is obtained.
An embodiment of the present application provides a composite resin composition, which includes, in parts by mass:
10-50 parts of epoxy resin,
10 to 30 parts of benzoxazine resin,
10-50 parts of curing agent,
5-30 parts of flame retardant,
10-60 parts of inorganic filler;
wherein the curing agent contains a compound represented by the formula (1):
r is selected from oxygen atom, carbonyl or any structure in the following formulas (a) - (e):
wherein R is 1 And R is 2 Each independently selected from any one of a single bond, an alkane subunit having 1 to 5 carbon atoms, an oxygen atom and a sulfone group; r is R 3 ~R 6 Each independently selected from a single bond or an alkane subunit having 1 to 3 carbon atoms; * Representing the ligation site.
The composite resin composition contains epoxy resin, benzoxazine resin, curing agent, flame retardant and inorganic filler in a specific weight ratio, and the components are synergistic, so that the composite resin composition has high heat resistance, good cohesiveness, low water absorption and low dielectric constant and dielectric loss value. Wherein the curing agent contains a compound shown in a formula (1), is a polybasic acid anhydride curing agent with a specific structure, and the compound shown in the formula (1) contains a plurality of benzene ring structures and a plurality of acid anhydride groups, and improves the adhesive property of the composite resin composition while maintaining excellent heat resistance, low water absorption and excellent dielectric property after being cooperated with other components by a specific proportion.
In some embodiments, the curing agent comprises a compound of formula (1A);
。
in some of these embodiments, R 1 Selected from any one of a single bond, an oxygen atom and a sulfone group.
In some of these embodiments, R 2 Selected from any one of alkane subunit with 1-3 carbon atoms, oxygen atom and sulfonyl.
In some of these embodiments, R 2 Selected from one of a paraffinic subunit having 1 to 3 carbon atoms, an oxygen atom and a sulfone group.
In some of these embodiments, R 2 Selected from any one of methylene, ethylene, butylene, oxygen atom and sulfone group.
In some of these embodiments, R 3 And R is 4 Independently selected from a single bond and an alkane subunit having 1 to 3 carbon atoms.
In some of these embodiments, R 3 And R is 4 Independently selected from a single bond and a paraffinic subunit having 1 to 3 carbon atoms.
In some of these embodiments, R 3 And R is 4 Each independently selected from any one of single bond methylene, ethylene and butylene.
In some of these embodiments, R 3 And R is 4 The same applies.
In some of these embodiments, R 5 And R is 6 Independently selected from a single bond and an alkane subunit having 1 to 3 carbon atoms.
In some of these embodiments, R 5 And R is 6 Independently selected from a single bond and a paraffinic subunit having 1 to 3 carbon atoms.
In some of these embodiments, R 5 And R is 6 Each independently selected from any one of single bond methylene, ethylene and butylene.
In some of these embodiments, R 5 And R is 6 The same applies.
In some embodiments, R is selected from formula (a) or formula (d).
In some embodiments, R is selected from any one of the structures (1-1) - (1-9) below:
。
in some embodiments, R is selected from structures represented by formulas (1-4).
In some of these embodiments, the curing agent comprises a compound of formula (1B):
。
in some of these embodiments, the composite resin composition includes, in parts by mass:
20-40 parts of epoxy resin,
20 to 30 parts of benzoxazine resin,
30-50 parts of curing agent,
10-20 parts of flame retardant,
20-40 parts of inorganic filler.
The mass parts of each component in the composite resin composition are further regulated, the heat resistance, dielectric property and adhesive property of the composite resin are further improved, and meanwhile, the lower water absorption rate is maintained.
In the above-mentioned "10 parts to 50 parts", the values of the epoxy resin in parts by mass include the minimum value and the maximum value of the range, and each value between such minimum value and maximum value, and specific examples include, but are not limited to, the point values in the examples and the point values below: 10 parts, 13 parts, 15 parts, 17 parts, 20 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, 30 parts, 31 parts, 33 parts, 35 parts, 37 parts, 39 parts, 40 parts, 41 parts, 43 parts, 45 parts, 47 parts, 49 parts, 50 parts; or any two values, for example, may be: 10 to 50 parts, 10 to 45 parts, 10 to 40 parts, 10 to 35 parts, 10 to 30 parts, 10 to 25 parts, 10 to 20 parts, 20 to 45 parts, 20 to 40 parts, 20 to 35 parts, 20 to 30 parts, and 20 to 25 parts.
In the above-mentioned "10 parts to 30 parts", the values of the benzoxazine resin in parts by mass include the minimum value and the maximum value of the range, and each value between such minimum value and maximum value, and specific examples include, but are not limited to, the point values in the examples and the following point values: 10 parts, 13 parts, 15 parts, 17 parts, 20 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, 30 parts; or any two values, for example, may be: 10-30 parts, 10-25 parts, 10-20 parts, 20-30 parts, and 20-25 parts.
In the above-mentioned "10 parts to 50 parts", the mass part values of the curing agent include the minimum value and the maximum value of the range, and each value between the minimum value and the maximum value, and specific examples include, but are not limited to, the point values in the examples and the following point values: 10 parts, 13 parts, 15 parts, 17 parts, 20 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, 30 parts, 31 parts, 33 parts, 35 parts, 37 parts, 39 parts, 40 parts, 41 parts, 43 parts, 45 parts, 47 parts, 49 parts, 50 parts; or any two values, for example, may be: 10 to 50 parts, 10 to 45 parts, 10 to 40 parts, 10 to 35 parts, 10 to 30 parts, 10 to 25 parts, 10 to 20 parts, 20 to 45 parts, 20 to 40 parts, 20 to 35 parts, 20 to 30 parts, and 20 to 25 parts.
In the above "5 parts to 30 parts", the mass part values of the flame retardant include the minimum value and the maximum value of the range, and each value between the minimum value and the maximum value, and specific examples include, but are not limited to, the point values in the examples and the point values below: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts; or a range of any two values.
In the above-mentioned "10 parts to 60 parts", the values of the inorganic filler in parts by mass include the minimum value and the maximum value of the range, and each value between such minimum value and maximum value, and specific examples include, but are not limited to, the point values in the examples and the point values below: 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts; or a range of any two values.
In some of these embodiments, the mass fraction of the curing agent is greater than the mass fraction of the epoxy resin.
In some of these embodiments, the ratio of the mass of the curing agent to the mass of the epoxy resin is T: t is more than or equal to 1.2.
In some of these embodiments, T is 1.3 or greater.
In some of these embodiments, 1.2.ltoreq.T.ltoreq.3.
In some embodiments, 1.2.ltoreq.T.ltoreq.2.5.
In some of these embodiments, the benzoxazine resin is less than or equal to the mass fraction of the curing agent. In other words, the mass ratio of the benzoxazine resin to the curing agent is less than or equal to 1.
In some of these embodiments, the inorganic filler is less than or equal to the mass fraction of the curing agent. In other words, the mass ratio of the inorganic filler to the curing agent is 1 or less.
In some of these embodiments, the epoxy resin includes at least one of a saturated epoxy resin and an unsaturated epoxy resin; further, the saturated epoxy resin includes at least one of an alicyclic epoxy resin and an aliphatic epoxy resin, and the unsaturated epoxy resin includes at least one of an olefin epoxy resin, an aromatic epoxy resin, and a heteroaromatic epoxy resin.
In some of these embodiments, the epoxy resin includes at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, phosphorous-containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, aralkyl novolac epoxy resin, glycidylamine epoxy resin, and glycidylester epoxy resin.
In some of these embodiments, the benzoxazine resin is not limited to a particular type, including but not limited to: at least one of bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, diamine type benzoxazine resin, MDA type benzoxazine, ODA type benzoxazine, DCPD type benzoxazine, phenol type benzoxazine, DOPO type benzoxazine.
In some of these embodiments, the inorganic filler comprises at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass-ceramic, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay, and kaolin.
The silica may be any one of spherical, composite, and fused.
In some of these embodiments, the inorganic filler comprises at least one of spherical silica and modified spherical alumina.
In some of these embodiments, the inorganic filler comprises at least one of epoxy-modified spherical silica, anilino-modified spherical silica, vinyl-modified spherical silica, hollow spherical silica, acrylic-modified spherical silica, fluoroalkyl-modified spherical silica, molybdate-modified spherical silica, epoxy-modified spherical alumina, anilino-modified spherical alumina, vinyl-modified spherical alumina, hollow spherical alumina, acrylic-modified spherical alumina, fluoroalkyl-modified spherical alumina, and molybdate-modified spherical alumina.
In some of these embodiments, the composite resin composition further includes other adjuvants.
In some of these embodiments, the other adjuvants include at least one of a cure accelerator, a coupling agent, a toughening agent.
The curing accelerator, coupling agent, toughening agent may be one commonly used in the art.
For example, the curing accelerator may be selected from imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and may be selected from at least one of organic metal salts such as zinc octoate, zinc iso-octoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate, copper acetylacetonate.
In some embodiments, the mass portion of the other auxiliary agent is 1-10.
Further, the composite resin composition comprises, in parts by mass:
10-50 parts of epoxy resin,
10 to 30 parts of benzoxazine resin,
10-50 parts of curing agent,
5-30 parts of flame retardant,
10-60 parts of inorganic filler;
1-10 parts of other auxiliary agents.
Further, the composite resin composition may further include an organic solvent to uniformly mix the components for easy processing into a film.
The organic solvent can be added during construction application, the dosage is not particularly limited, and the components can be uniformly mixed.
In one embodiment of the present application, there is also provided a cured resin prepared from the raw materials including the above-described composite resin composition.
The cured resin has high heat resistance, good cohesiveness, low water absorption, low dielectric constant and low dielectric loss value.
An embodiment of the present application further provides a prepreg, which includes a reinforcing material and a resin material supported by the reinforcing material, wherein the resin material is a cured resin as described above.
In some of these embodiments, the reinforcing material is selected from inorganic fibrous materials or organic fibrous materials.
Inorganic fiber materials include, but are not limited to, glass fibers, carbon fibers, silicon carbide fibers, asbestos fibers, and the like. The machine fiber material includes, but is not limited to, nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, cotton fiber, and the like.
Wherein the glass fibers comprise E, NE, D, S, T and other different types of glass fibers.
Further, the preparation of the prepreg comprises the following steps S20-S30.
Step S20, mixing the composite resin composition and an organic solvent to prepare a prepreg.
In some embodiments, the organic solvent is selected from at least one of butanone and cyclohexanone. Further, the organic solvent includes butanone and cyclohexanone.
In some embodiments, the mass ratio of butanone to cyclohexanone is (1-5): 1-5.
And step S30, placing the reinforcing material into the resin glue solution obtained in the step S20, and heating to obtain the prepreg.
In some of these embodiments, in step S30, the heating conditions are: heating at 130-250 ℃ for 2-10 min.
During the heating, the organic solvent volatilizes and a slight curing reaction accompanies, and a prepreg is obtained.
An embodiment of the present application also provides a laminate, wherein the raw materials for preparing the laminate include the prepreg as described above.
It can be understood that the amount of the prepreg used in the raw materials for preparing the laminated board can be adjusted according to practical application; further, the preparation raw material comprises a plurality of prepregs which are arranged in a stacked manner.
In one embodiment, the laminate is coated on one or both sides with a metal foil. At this time, the metal foil laminate is obtained.
It will be appreciated that the metal foils may be copper foils or aluminum foils, and their thickness is not particularly limited and may be adaptively adjusted according to practical applications. Specifically, the metal foil is copper foil, and the laminated board is copper-clad plate.
In some embodiments, the thickness of the metal foil is 3 μm to 105 μm.
Further, the preparation of the laminate includes the following step S40.
And step S40, hot-pressing the prepreg under a vacuum condition to obtain the laminated board.
In some of these embodiments, the process parameters of the hot press are: vacuum degree is less than 2kPa, temperature is 150-300 ℃, and pressure is 10 kgf/cm 2 ~30kgf/cm 2 And the time is 180-400 min.
It is understood that when the laminate is prepared from a starting material comprising two or more prepregs, the prepregs are laminated and hot pressed.
Further, an embodiment of the present invention also provides a printed circuit board including the laminate as described above.
The printed circuit board has high heat resistance, good cohesiveness, low water absorption, low dielectric constant and low dielectric loss value, and is beneficial to expanding the application in the fields of integrated circuit packaging, high-frequency high-speed and other high-performance printed circuit boards.
The present application will be described in connection with specific embodiments, but is not limited thereto, and it is to be understood that the appended claims outline the scope of the application, and those skilled in the art, guided by the concepts herein provided, will recognize certain changes made to the embodiments of the application that will be covered by the spirit and scope of the claims of the application.
The following are specific examples.
Example 1
(1) According to the mass portion, 30 portions of biphthalic anhydride curing agent BisDA, 30 portions of bisphenol A epoxy resin and 20 portions of bisphenol A benzoxazine resin are sequentially dissolved in 70 portions of mixed solvent, wherein the mixed solvent comprises butanone and cyclohexanone with the mass ratio of 1:1, 30 portions of spherical silicon dioxide, 10 portions of flame retardant and 6 portions of curing accelerator 2-methylimidazole are added under the stirring condition, and stirring is continued to obtain a uniform composite resin composition. The specific components and mass fractions are shown in Table 1.
The 2116 glass fiber cloth (basis weight 105 g/m) is immersed in the resin composition, and baked for 3min at 180 ℃ in a hot air circulation oven, so as to obtain the prepreg with 50% of resin content.
8 prepregs are laminated, an electrolytic copper foil with the thickness of 18 mu m is respectively covered on the upper surface and the lower surface of the laminated body, the laminated body is placed in a vacuum press with programmable temperature control and pressure control, and under the vacuum state and the pressure of 30kgf/cm, the laminated body is cured for 3 hours at 220 ℃ to prepare the copper foil-clad laminated board with the thickness of 0.6 mm.
(2) The performance test is specifically as follows:
peel strength: the test method is carried out according to IPC-TM-650-2.4.8;
glass transition temperature (Tg): according to IPC-TM650 2.4.25D test;
thermal decomposition temperature (Td): according to the IPC-TM650 2.4.24.6 test electrical properties, higher thermal decomposition temperature (Td) indicates better heat resistance;
flame retardant rating: according to IPC-TM650 2.3.10 test;
Dk/Df: the dielectric constant (Dk) and dielectric loss angle (Df) were tested according to IPC-TM 650-2.5.5.2;
water absorption rate: according to IPC-TM 650-2.6.2.1.
The specific results are shown in Table 1.
Examples 2 to 7
Examples 2 to 7 are basically the same as example 1, except that: the mass parts of the components of the composite resin composition are different from those of example 1. The mass parts of the specific components are shown in Table 1.
The other steps were the same as in example 1.
Examples 8 to 10
Examples 8 to 10 are basically the same as example 1, except that: the type of the curing agent in the composite resin composition was different from example 1. Wherein, the curing agent adopted in the example 8 is 4,4 '-diphenyl ether dianhydride (ODPA, CAS: 1823-59-2), the curing agent adopted in the example 9 is 3,3',4 '-benzophenone tetracarboxylic dianhydride (BTDA, CAS: 2421-28-5), and the curing agent adopted in the example 10 is 4,4' -terephthaloyl diphthalic anhydride (HQDA, CAS: 17828-53-4).
The other steps were the same as in example 1.
Comparative examples 1 to 2
Comparative examples 1 to 2 are basically the same as example 1 except that: the component types and parts by mass of the composite resin composition were different from those of example 1. The specific components and mass fractions are shown in Table 1.
The other steps were the same as in example 1.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the curing agent is replaced with an equal mass of phthalic anhydride in comparative example 3: 85-44-9 parts of CAS.
The other steps were the same as in example 1.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: the mass parts of the components of the composite resin composition are different from those of example 1. See Table 1 for details.
The other steps were the same as in example 1.
The raw materials and the test results in each example and each comparative example are shown in table 1.
TABLE 1
Wherein, the raw materials are all available from commercial products: for example, bisDA is 4,4' - [ propane-2, 2-diylbis (1, 4-phenylene oxy) ] diphthalic dianhydride, commercially available from Saint Foundation Industrial, model BisDA-1000, having the structure:
styrene-maleic anhydride copolymer is available from gram Lei Weili under the model number EF-60.
Bisphenol A type epoxy resin is commercially available from Japanese chemical, model XD-1000.
Bisphenol A type benzoxazine resin is available from Henschel under the model LZ 8290H 62.
Flame retardants are commercially available from Daba chemistry, model number PX200.
Spherical silica is available from jacobian under the model number SC6500-SXD.
The curing accelerator 2-methylimidazole is commercially available from four nations.
Analysis of the data in table 1 shows that: the laminated board prepared by the composite resin composition has high heat resistance, good cohesiveness, low water absorption rate, low dielectric constant and low dielectric loss value.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples represent only a few embodiments of the present application, which are described in more detail and are not thereby to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the protection scope of this patent shall be subject to the appended claims.

Claims (11)

1. A composite resin composition characterized by comprising, in parts by mass:
10-50 parts of epoxy resin,
10 to 30 parts of benzoxazine resin,
10-50 parts of curing agent,
5-30 parts of flame retardant,
10-60 parts of inorganic filler;
wherein the curing agent contains a compound represented by the formula (1):
r is selected from oxygen atom, carbonyl or any structure in the following formulas (a) - (e):
wherein R is 1 And R is 2 Each independently selected from any one of a single bond, an alkane subunit having 1 to 5 carbon atoms, an oxygen atom and a sulfone group; r is R 3 ~R 6 Each independently selected from a single bond or an alkane subunit having 1 to 3 carbon atoms; * Representing the ligation site.
2. The composite resin composition according to claim 1, wherein the composite resin composition satisfies any one of the following conditions (1) to (2):
(1)R 1 any one selected from single bond, oxygen atom and sulfonyl;
(2)R 2 any one selected from alkane subunit with 1-3 carbon atoms, oxygen atoms and sulfonyl;
(3)R 3 ~R 6 independently selected from a single bond and an alkane subunit having 1 to 3 carbon atoms.
3. The composite resin composition of claim 1, wherein R is selected from formula (d).
4. The composite resin composition according to claim 1, wherein R is selected from an oxygen atom, a carbonyl group or any one of the structures of the following formulae (1-1) to (1-9):
。
5. the composite resin composition according to any one of claims 1 to 4, wherein the composite resin composition comprises, in parts by mass:
20-40 parts of epoxy resin,
20 to 30 parts of benzoxazine resin,
30-50 parts of curing agent,
10-20 parts of flame retardant,
20-40 parts of inorganic filler.
6. The composite resin composition according to any one of claims 1 to 4, wherein the composite resin composition satisfies at least one of the following conditions (1) to (4):
(1) The epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A phenolic epoxy resin, phenol phenolic epoxy resin, trifunctional phenol epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type phenolic epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin;
(2) The benzoxazine resin comprises at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diamine type benzoxazine resin, MDA type benzoxazine, ODA type benzoxazine, DCPD type benzoxazine, phenol type benzoxazine and DOPO type benzoxazine;
(3) The inorganic filler comprises at least one of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass ceramics, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talcum powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin;
(4) The flame retardant comprises at least one of decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate compound and phosphorus-containing cyanate.
7. The composite resin composition according to any one of claims 1 to 4, further comprising other auxiliary agents including at least one of a curing accelerator, a coupling agent and a toughening agent.
8. A cured resin prepared from the raw material comprising the composite resin composition according to any one of claims 1 to 7.
9. A prepreg comprising a reinforcing material and a resin material supported by the reinforcing material, the resin material comprising the cured resin of claim 8.
10. A laminate, characterized in that the raw material for the preparation of the laminate comprises the prepreg according to claim 9.
11. A printed circuit board comprising the laminate of claim 10.
CN202311704156.3A 2023-12-13 2023-12-13 Composite resin composition and application thereof Pending CN117736541A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311704156.3A CN117736541A (en) 2023-12-13 2023-12-13 Composite resin composition and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311704156.3A CN117736541A (en) 2023-12-13 2023-12-13 Composite resin composition and application thereof

Publications (1)

Publication Number Publication Date
CN117736541A true CN117736541A (en) 2024-03-22

Family

ID=90280420

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311704156.3A Pending CN117736541A (en) 2023-12-13 2023-12-13 Composite resin composition and application thereof

Country Status (1)

Country Link
CN (1) CN117736541A (en)

Similar Documents

Publication Publication Date Title
TWI678390B (en) Resin composition, and prepreg, metal-clad laminate, and printed circuit board using the same
US8258216B2 (en) Thermosetting resin compositions and articles
TWI541288B (en) A resin composition and a prepreg and laminate using the same
CN106810820B (en) Thermosetting alkyl polyol glycidyl ether resin composition and application thereof
TWI745627B (en) Thermal-curable resin composition, and pre-preg, metal-clad laminate and printed circuit board manufactured using the same
JP6195650B2 (en) Resin composition and copper-clad laminate and printed circuit board using the same
KR101819949B1 (en) Ultra low loss dielectric thermosetting resin compositions and high preformance laminates manufactured therefrom
TWI654243B (en) Resin composition, and prepreg, metal foil laminate, and printed circuit board prepared using the same
EP4253480A1 (en) Modified bismaleimide prepolymer, preparation method therefor, and application thereof
EP2799493B1 (en) Thermoset resin composition, and prepreg and laminate for printed circuit board manufactured therefrom
TWI671355B (en) Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same
CN108440901B (en) High-frequency resin composition, and prepreg, interlayer insulating film and laminated board prepared from high-frequency resin composition
WO2014036712A1 (en) Composite material, high frequency circuit substrate made from the same, and production method thereof
WO2017152602A1 (en) Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using same
WO2013083062A1 (en) Epoxy-modified polyphenylene oxide resin, resin composition and applications thereof
CN108117723B (en) Thermosetting resin composition, prepreg using same and laminated board for printed circuit
CN113088039A (en) Insulating adhesive film and preparation method and application thereof
JP2003231762A (en) Prepreg and laminated sheet
WO2021172317A1 (en) Resin composition, cured product, prepreg, metal foil-clad laminate board, resin sheet, and printed circuit board
CN115181395B (en) Thermosetting resin composition and application thereof
CN117736541A (en) Composite resin composition and application thereof
JPS6356548A (en) Thermosetting resin composition, laminated sheet produced by using same and production thereof
CN111961193A (en) Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same
CN114133748B (en) Low dielectric resin composition and application thereof
CN114292492B (en) Resin composition and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination