阅读说明：本技术 一种碳氢覆铜板用树脂组合物 (Resin composition for carbon-hydrogen copper-clad plate ) 是由 陈功田 李海林 邓万能 桂鹏 刘俊琨 贺杨海 吴娟英 于 2020-07-27 设计创作，主要内容包括：本发明公开了一种碳氢覆铜板用树脂组合物,包括以下重量份原料：聚丁二烯20-40份,腈基树脂/改性马来酰亚胺树脂的混合物10-20份,陶瓷粉和火山灰的混合物25-45份,聚二烯烃-苯乙烯-乙烯三元共聚物15-40份,交联剂8-12份,固化剂4-6份。本发明提供的碳氢覆铜板用树脂组合物,其制成的覆铜板具有介电常数可控、低介电损耗、抗剥离强度高、耐热性好以及良好的加工性等优点。(The invention discloses a resin composition for a carbon-hydrogen copper-clad plate, which comprises the following raw materials in parts by weight: 20-40 parts of polybutadiene, 10-20 parts of a nitrile resin/modified maleimide resin mixture, 25-45 parts of a ceramic powder and volcanic ash mixture, 15-40 parts of polydiene-styrene-ethylene terpolymer, 8-12 parts of a cross-linking agent and 4-6 parts of a curing agent. The resin composition for the carbon-hydrogen copper-clad plate provided by the invention has the advantages of controllable dielectric constant, low dielectric loss, high peel strength resistance, good heat resistance, good processability and the like.)

1. The resin composition for the carbon-hydrogen copper-clad plate is characterized by comprising the following raw materials in parts by weight: 20-40 parts of polybutadiene, 10-20 parts of a nitrile resin/modified maleimide resin mixture, 25-45 parts of a ceramic powder and volcanic ash mixture, 15-40 parts of polydiene-styrene-ethylene terpolymer, 8-12 parts of a cross-linking agent and 4-6 parts of a curing agent.

2. The resin composition for the carbon-hydrogen copper-clad plate as claimed in claim 1, wherein the polybutadiene has a molecular weight of 400-.

3. The resin composition for the carbon-hydrogen copper-clad plate according to claim 1, wherein the mass ratio of the nitrile-based resin to the modified maleimide resin in the mixture of the nitrile-based resin and the modified maleimide resin is 1 (3-5).

4. The resin composition for the carbon-hydrogen copper-clad plate according to claim 1, wherein the nitrile-based resin comprises at least one of a classical nitrile-based resin, an amino-type nitrile-based resin, a hydroxyl-type nitrile-based resin and a benzoxazine-type nitrile-based resin.

5. The resin composition for the carbon-hydrogen copper-clad plate according to claim 3, wherein the preparation method of the modified maleimide resin comprises the following steps: the barbituric acid, the allyl compound and the bismaleimide resin are mixed evenly and reacted for 2 to 3 hours at the temperature of 110-120 ℃.

6. The resin composition for the carbon-hydrogen copper-clad plate according to claim 5, wherein the mass ratio of the barbituric acid, the allyl compound and the bismaleimide resin is 1 (2-5) to (3-4).

7. The resin composition for the carbon-hydrogen copper-clad plate according to claim 1, wherein in the mixture of the ceramic powder and the volcanic ash, the mass ratio of the ceramic powder to the volcanic ash is (5-7): (1-2).

8. The resin composition for the carbon-hydrogen copper-clad plate according to claim 1, wherein the mass ratio of the polydiene block, the polystyrene block and the ethylene block is (1-5): (2-4): (1-3); a single pendant group of said polydiene block contains at least one reactive carbon-carbon double bond.

9. The resin composition for the carbon-hydrogen copper-clad plate according to claim 1, wherein the crosslinking agent comprises any one or two of triallyl isocyanurate, ethylene propylene diene monomer and divinylbenzene.

10. The resin composition for the carbon-hydrogen copper-clad plate according to claim 1, wherein the curing agent is any one or two of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, dicumyl peroxide and benzoyl peroxide.

Technical Field

The invention belongs to the technical field of communication materials, and particularly relates to a resin composition for a carbon-hydrogen copper-clad plate.

Background

The copper-clad plate is widely applied to the fields of mobile phones, computers, wearable equipment, communication base stations, satellites, unmanned automobiles, unmanned aerial vehicles, intelligent robots and the like, and is one of key materials in electronic communication and information industries. The progress of modern information technology makes digital circuits enter the stages of high speed information processing and high frequency signal transmission, and higher requirements are put on the dielectric constant and dielectric loss of the microwave dielectric circuit substrate.

Since the polarity of C-H in the molecular chain of hydrocarbon resin is small (the electronegativity of C and H is 2.5 and 2.1 respectively), the resin has excellent dielectric properties (volume resistivity of 10 Ω. m; dielectric constant (1MHz) of 2.4-2.8; tan0.0002-0.0006), and has been gaining more and more attention in recent years. However, the hydrocarbon resin has problems of insufficient rigidity, low strength, poor heat resistance, low glass transition temperature (Tg), low peel strength, and the like in the cured product due to its flexibility and nonpolar carbon chain structure, and thus its use is limited. In the prior art, a lot of research and improvement are carried out by those skilled in the art, but they all achieve the purpose of improving heat resistance by means of forming a composition by a hydrocarbon resin and a heat-resistant resin and then crosslinking the composition by an initiator initiating system to form a polymer, for example: JP19770061619 (application date: 1977.5.26, publication number: JP53145891A, publication number: 1978.12.19) discloses a high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but the graft ratio of MA functional groups on the molecular chain after modification is not given, and if the graft ratio is too large, the polarity of the composite material is increased, and the dielectric constant and the dielectric loss are increased. If the grafting ratio of the functional group is too small, the peeling strength between the resin system and the copper foil is too small; the patent with application number of JP19800183423 (application date: 1980.12.24, publication number: JP57105347A, publication number: 1982.6.30) discloses a high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but the grafting ratio of the modified polymer maleic anhydride is too high, which leads to the increase of polarity of the composite material and the increase of dielectric constant and dielectric loss, and in addition, the MA modified polybutadiene disclosed in the patent has the molecular weight of 5-20 ten thousand, is difficult to dissolve in a solvent, and has poor subsequent manufacturability. .

Therefore, the resin composition for the carbon-hydrogen copper clad laminate, which integrates excellent heat resistance, high toughness, high strength, high peel strength and good dielectric property, is a problem to be solved by the technical personnel in the field.

Disclosure of Invention

In view of the above, the invention provides a resin composition for a carbon-hydrogen copper-clad plate, and the copper-clad plate prepared from the resin composition has the advantages of controllable dielectric constant, low dielectric loss, high peel strength, good heat resistance, good processability and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

the resin composition for the carbon-hydrogen copper-clad plate comprises the following raw materials in parts by weight: 20-40 parts of polybutadiene, 10-20 parts of a nitrile resin/modified maleimide resin mixture, 25-45 parts of a ceramic powder and volcanic ash mixture, 15-40 parts of polydiene-styrene-ethylene terpolymer, 8-12 parts of a cross-linking agent and 4-6 parts of a curing agent.

The resin composition for the carbon-hydrogen copper-clad plate is prepared by taking polybutadiene matrix resin, polydiene-styrene-ethylene terpolymer as a compatilizer, a mixture of nitrile resin/modified maleimide resin as composite modified resin and ceramic powder, volcanic ash, a cross-linking agent, a curing agent and a solvent as auxiliary materials.

The polydiene-styrene-ethylene terpolymer effectively increases the compatibility between the polybutadiene and the composite modified resin; according to the invention, the nitrile-based resin and the modified maleimide resin are combined, and have synergistic effect, and the nitrile-based resin and the modified maleimide resin are combined with the polybutadiene matrix resin, so that the properties of heat resistance, rigidity, strength, peeling strength and the like of the polybutadiene matrix resin can be obviously improved, meanwhile, the interaction among the filler, the matrix resin and the compatilizer is further enhanced, the dispersibility of the filler in the composition is improved, and the nitrile-based resin and the modified maleimide resin have outstanding substantive characteristics and obvious progress. In addition, the mixture of the ceramic powder and the volcanic ash is adopted, so that the thermal conductivity of the composition is improved under the synergistic effect, the rigidity, the flame retardance and the strength of the composition are obviously improved, and the composition has outstanding substantive characteristics.

Preferably, the polybutadiene molecular weight is 400-.

The molecular weight polybutadiene has excellent dielectric property, can be well combined with a compatilizer, composite modified resin, filler and the like, and solves the problems of insufficient rigidity, low strength, poor heat resistance and the like.

Preferably, in the mixture of the nitrile-based resin/the modified maleimide resin, the mass ratio of the nitrile-based resin to the modified maleimide resin is 1 (3-5).

Preferably, the nitrile-based resin comprises at least one of a classical nitrile-based resin, an amino-type nitrile-based resin, and a hydroxyl-type nitrile-based resin.

The nitrile resin is a high-temperature resistant resin containing a nitrile structure, and the resin and the composite material thereof have the characteristics of high strength, high modulus, high temperature resistance, corrosion resistance, self-flame retardance and the like, do not release small molecules in the curing process, have low porosity of products and nearly zero shrinkage, and have the characteristics of low thermal expansion coefficient, stable size, low water absorption and the like. Meanwhile, the nitrile resin has strong molecular designability, and different monomers can be selected according to different purposes to introduce groups with different functional structures, so that the requirements of different use occasions are met.

Preferably, the preparation method of the modified maleimide resin is as follows: the barbituric acid, the allyl compound and the bismaleimide resin are mixed evenly and reacted for 2 to 3 hours at the temperature of 110-120 ℃.

Preferably, the mass ratio of the barbituric acid to the allyl compound to the bismaleimide resin is 1 (2-5) to (3-4).

Preferably, the allyl compound is a 3, 4-diacetoxyallyl compound.

Preferably, the modified maleimide resin comprises: 4,4' -diphenylmethane bismaleimide, and allyl-modified diphenylmethane bismaleimide.

The composite modified resin adopts the mixture of the nitrile-based resin and the modified maleimide resin, the nitrile-based resin and the modified maleimide resin are synergistic, and the composite modified resin is combined with the polybutadiene matrix resin, so that the problems of rigidity, strength, peeling strength and the like of the polybutadiene matrix resin can be obviously improved, meanwhile, the interaction among the filler, the matrix resin and the compatilizer is further enhanced, the dispersibility of the filler in the composition is improved, and the composite modified resin has outstanding substantive characteristics and obvious progress. In addition, the matrix resin is combined with the composite modified resin, so that the problems of stress cracking and crazing caused by the fact that a large number of internally dense uneven states in a product are easy to damage in daily use due to uneven molecular weight distribution of the polymer are solved.

Preferably, in the mixture of the ceramic powder and the volcanic ash, the mass ratio of the ceramic powder to the volcanic ash is (5-7): (1-2), wherein the ceramic powder consists of low dielectric ceramic powder and high dielectric ceramic powder.

The ceramic powder of the invention is composed of low dielectric and high dielectric ceramic powder according to a proportion, such as fused silica, strontium titanate, barium titanate, titanium dioxide and the like, so that the dielectric constant of the product can be controlled within 3.0-10.5, and the ceramic powder can be produced according to actual needs.

Preferably, the mass ratio of the polydiene block, the polystyrene block, and the ethylene block is (1-5): (2-4): (1-3); a single pendant group of said polydiene block contains at least one reactive carbon-carbon double bond.

The polybutadiene and polydiene-styrene-ethylene terpolymer with excellent dielectric property is taken as a material, so that the dielectric constant and the dielectric loss can be reduced, and the compatibility between the polybutadiene and the composite modified resin as two matrix resins is effectively increased.

Preferably, the crosslinking agent comprises one or both of triallyl isocyanurate (TAIC), ethylene propylene diene monomer, and divinylbenzene.

Preferably, the curing agent is one or two of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, dicumyl peroxide and benzoyl peroxide.

Preferably, the resin composition further comprises an organic solvent, wherein the weight part of the organic solvent is 100-200 parts.

Preferably, the organic solvent is any one or two of acetone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide, methyl isobutyl ketone, toluene and xylene.

A prepreg, a bonding sheet or a copper-clad plate prepared by the resin composition.

Preferably, the preparation method of the prepreg comprises the following specific steps: firstly, weighing the raw materials according to the proportion, adding the nitrile-based resin and the modified maleimide resin into the organic solvent, stirring and dissolving, then sequentially adding the polybutadiene, the polydiene-styrene-ethylene terpolymer, the mixture of the ceramic powder and the volcanic ash, the cross-linking agent and the curing agent, and preparing into a resin glue solution; and then soaking the glass fiber cloth in the resin glue solution, taking out the glass fiber cloth, drying the glass fiber cloth and removing the organic solvent to obtain the prepreg.

The prepreg prepared from the resin composition has the advantages of low dielectric constant, low dielectric loss, high peel strength, good heat resistance, good processability and the like.

According to the technical scheme, compared with the prior art, the invention has the following beneficial effects: the invention adopts polydiene-styrene-ethylene terpolymer to effectively increase the compatibility between polybutadiene and composite modified resin; according to the invention, the nitrile-based resin and the modified maleimide resin are combined, and have synergistic effect, and the nitrile-based resin and the modified maleimide resin are combined with the polybutadiene matrix resin, so that the properties of heat resistance, rigidity, strength, peeling strength and the like of the polybutadiene matrix resin can be obviously improved, meanwhile, the interaction among the filler, the matrix resin and the compatilizer is further enhanced, the dispersibility of the filler in the composition is improved, and the nitrile-based resin and the modified maleimide resin have outstanding substantive characteristics and obvious progress. In addition, the mixture of the ceramic powder and the volcanic ash is adopted, so that the thermal conductivity of the composition is improved under the synergistic effect, the rigidity, the flame retardance and the strength of the composition are obviously improved, and the composition has outstanding substantive characteristics.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.