TW201336955A - Adhesive composition and uses thereof - Google Patents

Abstract

The invention relates to an adhesive composition comprising a main component containing an epoxy monomer and a rubber monomer. The adhesive composition has advantages of low dielectric constant, high glass transition temperature, good resin flow and flexibility. A laminate material and an electronic component are also provided in the invention.

Description

Adhesive composition and application thereof

The present invention relates to an adhesive; in particular, it provides an adhesive composition having a low dielectric constant, a high glass transition temperature, a good flow and a good flexibility, a method for producing the same, and an application thereof.

The flexible printed circuit board is an important electronic component of various electronic products. Because of its flexible or curved characteristics, it is easy to fit the space and shape of the product and perform three-dimensional wiring in three dimensions, and its wiring density is high, light weight and volume. Small, has been widely used in notebook computers, mobile phones, digital cameras and LCD monitors.

The flexible printed circuit board is constructed by disposing a metal wire or a metal pattern on an insulating base film and fixing a metal wire or a metal pattern on the insulating base film by an adhesive, and the metal wire or the metal pattern A cover film may be covered as needed to protect the wire or metal pattern to maintain its mechanical and electrical properties. Common materials for insulating base film are Polyimide (PI) or Polyester film (Polyester; PET); common materials for metal wires or metal patterns are copper foil; common materials for adhesives are polyester resins. Polyester, Acrylic and Modified Epoxide; a common material for the cover film is a polyimide film.

Today's flexible printed circuit boards usually have the following structure: (1) glueless double-layer board (2-FCCL), which uses a coating method to bond an insulating base film to a metal wire or a metal pattern to one side. Or double-panel; (2) There is a glue three-layer board (3-FCCL), which is formed by pressing one or both sides of the insulating base film with an adhesive and a copper foil.

In order to meet the demand for light and thin electronic products, the development of flexible printed circuit board adhesives is an important issue. Due to the increasing complexity of metal wires or metal patterns and the shortening of the distance between them, if a suitable insulation barrier is not achieved, a short circuit is easily generated. The conventional technique is to apply a layer of polypropylene usually on a metal wire or a metal pattern. Coverlay and Bond ply, which is coated with an adhesive on one or both sides of the insulating base film to protect between the printed circuit board layers and the layers or the upper and lower layers. However, the thickness of the overall printed circuit board is greatly increased by the application of the laminated glue. The material of the laminated glue is usually a polymer with a good amount of glue, for example, adding glass fiber to the epoxy resin to enhance the supporting ability of the epoxy resin. However, due to the addition of glass fibers, the mechanical properties of the laminated adhesive become hard and brittle, which reduces the flexibility of the flexible printed circuit board.

Furthermore, when a three-dimensional multilayer circuit board is produced, it is necessary to repeatedly apply a build-up glue and an adhesive layer between the layers. This adhesive layer takes into account the flexibility of the flexible printed circuit board, and thus uses a high proportion of rubber, but this high ratio The addition of rubber is not conducive to the amount of glue, and can not be directly applied to the gap between the metal wire or the metal pattern, increasing the process and manufacturing cost.

Therefore, there is an urgent need in the art to propose novel adhesives to meet the development requirements of electronic products.

The invention develops an adhesive composition which can be used as an adhesive and a laminating adhesive at the same time, which has excellent flow glue amount, can fully fill the gap between metal wires or metal patterns, and has excellent flexibility and low medium. Electrical constant and high glass transition temperature.

Accordingly, the present invention provides an adhesive composition comprising a primary agent, and the adhesive composition has a flux of from about 10% to about 30%; wherein: the secondary agent comprises an epoxy resin monomer And a rubber monomer; the epoxy resin monomer comprising at least two epoxy groups; the rubber monomer comprising a cyano group and at least one selected from the group consisting of a carboxyl group, a secondary amine group, and an epoxy group; The content of the oxyresin monomer is 100 parts by weight, and the content of the rubber monomer is from about 5 to about 20 parts by weight.

The present invention further provides a laminate material comprising a substrate and the aforementioned adhesive composition on a surface of one of the substrates and contacting the surface.

The invention further provides an electronic component comprising the aforementioned laminate material.

The present invention provides an adhesive composition comprising a binder, and the binder composition has a flux of from about 10% to about 30%; wherein: the binder comprises epoxy resin monomer and rubber a monomer; the epoxy resin monomer comprising at least two epoxy groups; the rubber monomer comprising a cyano group and at least one selected from the group consisting of a carboxyl group, a secondary amine group, and an epoxy group; and the epoxy resin The content of the monomer is from about 5 to about 20 parts by weight based on 100 parts by weight of the monomer.

In one embodiment of the invention, the amount of the gel is tested according to the method of IPC-TM-650 No. 2.3.17, and preferably, the amount of the gel is from about 15% to about 20%.

The epoxy resin single system according to the present invention is a main adjunct component in the subsequent main component, and the epoxy resin monomer contains at least two epoxy groups in order to carry out a polymerization reaction. In a specific embodiment of the invention, the epoxy resin monomer is a phenolic resin, a phenol A type epoxy resin, an aromatic epoxy resin, an aliphatic epoxy resin or a halogenated epoxy resin.

In a preferred embodiment of the present invention, the epoxy resin single system has the structure shown by the following formula (1):

Wherein: n is an integer of 0 or more; and R ₁ represents an OR ₂ or a structure represented by the following formula (2);

R ₂ and R ₃ independently represent an alkyl group or an aromatic group having 1 to 6 carbon atoms; preferably an alkyl group having 1 to 6 carbon atoms; more preferably an alkyl group having 2 to 4 carbon atoms.

In a preferred embodiment of the present invention, the aromatic groups of R ₂ and R ₃ have the structure represented by the following formula (3) or formula (4):

In a more specific embodiment of the present invention, the epoxy resin single system is diethylene glycol diglycidoyl ether, butanediol diglycidoyl ether or isophthalic acid. Resorcin glycol diglycidoyl ether.

The epoxy resin monomer according to the present invention may use one monomer or a mixture of a plurality of monomers.

The rubber single system according to the present invention is a component which provides flexibility in the following main agent, which has high flexibility after high temperature curing, and contains cyano group and at least one selected for the rubber monomer to undergo polymerization reaction. A group consisting of a free carboxyl group, a secondary amine group, and an epoxy group. On the other hand, in order for the adhesive to have a high flow amount, the content of the rubber monomer is from about 5 to about 20 parts by weight based on 100 parts by weight of the epoxy resin monomer; more preferably, The rubber monomer is present in an amount of from about 10 to about 15 parts by weight;

In a specific embodiment of the invention, the rubber single system is selected from the group consisting of carboxyl-terminated butadiene-acrylonitrile (CTBN) and amine-terminated butadiene- A group of acrylonitrile, ATBN) and epoxide-terminated butadiene-acrylonitrile (ETBN).

In a preferred embodiment of the present invention, the carboxyl-terminated nitrile copolymer has a structure represented by the following formula (5):

Wherein R ₄ has the structure represented by the following formula (6):

Wherein x, y, z and m are independently an integer of 1 or more.

On the other hand, in a preferred embodiment of the present invention, the amine-terminated nitrile copolymer has a structure represented by the following formula (7):

Wherein R ₅ has the structure represented by the following formula (8):

Wherein x, y, z and m are independently an integer of 1 or more.

On the other hand, in a preferred embodiment of the present invention, the epoxy-terminated butyronitrile copolymer has a structure represented by the following formula (9):

Wherein: R ₆ represents an alkyl group or an aromatic group having 1 to 6 carbon atoms; preferably an alkyl group having 1 to 6 carbon atoms; more preferably an alkyl group having 2 to 4 carbon atoms; and R ₇ has the following formula (10) ) the structure shown:

Wherein x, y, z and m are independently an integer of 1 or more.

The rubber monomer according to the present invention may use one monomer or a mixture of a plurality of monomers.

In a preferred embodiment of the present invention, the adhesive agent comprises a further hardener which, when applied to a substrate by, for example, a coater, can be dried during drying and high temperature curing. A crosslinking reaction occurs with the epoxy resin monomer. In a preferred embodiment of the present invention, the hardener is selected from the group consisting of cyanoguanidine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, diaminodiphenylphosphonium, A group consisting of phthalic anhydride, tetrahydrophthalic anhydride, anhydrous pyrophoric acid, boron trifluoride amine complex, polyfunctional epoxy resin, and phenolic resin.

In order to effectively control the amount of overflow, the hardener of the present invention preferably uses a prepolymerized polyamine hardener, for example, selecting at least one acid anhydride and at least one diamine hardener to be hardened by diamines. The long molecular chain of the agent to achieve the purpose of preventing spillage. In a preferred embodiment of the present invention, the mixed ratio of the acid anhydride and the diamine hardener is 1:1, and then 10 times by weight of the solvent similar to the main agent is added, and then the reaction temperature is controlled. After uniformly stirring at 50 to 60 ° C for 3 hours, the polyamine prepolymer required for the present invention can be formed.

The hardener according to the present invention may use one component or a mixture of a plurality of components.

The amount of the hardener may be adjusted as needed. In a preferred embodiment of the present invention, the hardener is present in an amount of from about 1 to about 20 parts by weight based on 100 parts by weight of the epoxy resin monomer.

In a preferred embodiment of the present invention, the adhesive composition further comprises a filler to improve dimensional stability, heat resistance and mechanical perforation of the adhesive composition after high temperature curing. In a preferred embodiment of the present invention, the filler is selected from the group consisting of cerium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, antimony trioxide, calcium citrate, calcium carbonate, magnesium carbonate, a group consisting of magnesium oxide, zinc oxide, and boron nitride.

The filler according to the present invention may use one component or a mixture of a plurality of components.

The amount of the filler may be adjusted as needed. In a preferred embodiment of the present invention, the filler is contained in an amount of from about 2 to about 12 parts by weight based on 100 parts by weight of the epoxy resin monomer.

In a preferred embodiment of the invention, the adhesive composition further comprises a solvent for thoroughly mixing the ingredients and for each reaction. In a preferred embodiment of the invention, the solvent is selected from the group consisting of methyl ethyl ketone, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, n-propanol, toluene, and xylene.

The solvent according to the present invention may use one component or a mixture of a plurality of components.

The amount of the solvent may be adjusted as needed. In a preferred embodiment of the present invention, the solvent is contained in an amount of from about 125 to about 170 parts by weight based on 100 parts by weight of the epoxy resin monomer.

In a preferred embodiment of the invention, the adhesive composition further comprises at least one auxiliary agent to impart different characteristics to the adhesive composition. In a preferred embodiment of the invention, the adjuvant is selected from the group consisting of ion inhibitors and flame retardants.

The ion inhibitor can generate anions and cations to avoid conductive and short circuits caused by migration of cations and cations, for example: Sb ₂ O ₅ ‧2H ₂ O, Bi(OH) _0.7 (NO ₃ ) _0.3 , BiO(OH) _0.74 (NO ₃ ) _0.15 (HsiO ₃ ) _0.11 , BiO ( OH ), East Asia Synthetic Co., Ltd. IXE Or MgO/Al ₂ O ₃ .

The ion inhibitor according to the present invention may use one component or a mixture of a plurality of components.

The amount of the ion inhibitor may be adjusted as needed. In a preferred embodiment of the present invention, the solvent is contained in an amount of from about 1 to about 10 parts by weight based on 100 parts by weight of the epoxy resin monomer.

The flame retardant is to prevent the adhesive composition from burning due to high temperature or explosion. In a preferred embodiment of the present invention, the flame retardant is a phosphorus-based flame retardant or an inorganic flame retardant of an organic phosphorus salt. The phosphorus-based flame retardant is, for example, Exolit OP or DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide); the inorganic flame retardant is, for example, Al(OH) ₃ or Mg(OH) ₂ .

In a specific embodiment of the present invention, the method for producing the adhesive composition according to the present invention may be a method for polymerizing a general epoxy resin monomer and a rubber monomer, for example, in the presence or absence of a catalyst. Under the environment. In a preferred embodiment of the invention, the step of polymerizing is carried out in an environment free of catalyst to produce a preferred amount of adhesive composition.

In another aspect, in one preferred embodiment of the invention, the polymerization is carried out in the presence of a phosphorus-containing catalyst.

In a preferred embodiment of the present invention, the phosphorus-containing catalyst is selected from the group consisting of triphenyl phosphite (TPP), ethyl triphenyl phosphine bromide (ETPPB), and ethyl iodide. a group consisting of ethyltriphenyl phosphine iodide (ETPPI). It is preferably triphenylphosphine. Since the polymerizable monomer according to the present invention has a large steric hindrance, when the epoxy resin is subjected to an etherification reaction, the reaction is difficult to proceed because the functional group is in the middle of the molecular chain, and the touch is used for the above reasons. The medium can effectively promote the polymerization reaction between the epoxy resin monomer and the resin monomer at the end of the molecular chain, and can also catalyze the etherification reaction of the epoxy resin monomer and the rubber monomer, when the rubber monomer is After the reaction, the epoxy resin portion does not continue to react, so that the viscosity of the reactants can be effectively controlled.

The catalyst according to the present invention may use one component or a mixture of a plurality of components.

The amount of the catalyst can be adjusted as needed. In a preferred embodiment of the present invention, the amount of the epoxy resin is from about 0.1 to about 1.0 part by weight based on 100 parts by weight of the epoxy resin monomer.

In a preferred embodiment of the invention, the method further comprises polymerizing the epoxy resin monomer with a rubber monomer and a hardener. The polymerization step may be a method in which a general epoxy resin monomer and a hardener are polymerized, for example, in the presence or absence of a catalyst.

According to the present invention, the polymerization step of the epoxy resin monomer and the rubber monomer and the polymerization step of the epoxy resin monomer and the rubber monomer and the hardener may be carried out separately or in combination.

In a preferred embodiment of the present invention, the filler and a part of the solvent are first ground in a ball mill, and then the epoxy resin monomer, the rubber monomer and the optional catalyst are completely dissolved in the solvent, and The polymerization reaction is carried out. In order to suppress the amount of overflow of the finished product, the reaction temperature of the polymerization reaction is preferably from 70 to 120 ° C, and the viscosity is preferably between 250 and 1000 cps. The binder of the present invention can be obtained by uniformly mixing a predetermined ratio of the polymerization product and the hardener.

The present invention further provides a laminate material comprising a substrate and the aforementioned adhesive composition on a surface of one of the substrates and contacting the surface.

In a preferred embodiment of the invention, the substrate is selected from the group consisting of a soft substrate, a hard substrate, a release material, and a metal. Specific examples of the soft substrate and the hard substrate are polyimide, polyethylene, polyester, polyphenylene, polyvinyl chloride or polypropylene. In a preferred embodiment of the invention, the metal is a conductive metal; more preferably copper.

In a preferred embodiment of the present invention, the laminate material according to the present invention is a single-sided flexible board comprising a substrate, a first adhesive layer formed from the adhesive composition, and a conductive layer. Metal layer. The first adhesive layer is on a surface of one of the substrates and contacts the surface, and the conductive metal layer is on the first adhesive layer. Preferably, the substrate is a polyimide film.

In another preferred embodiment of the present invention, the laminate material according to the present invention is a double-sided flexible board comprising a substrate, a first adhesive layer, a second adhesive layer, and a first And a second conductive metal layer, wherein the first adhesive layer and the second adhesive layer are formed of the adhesive composition. The first adhesive layer is on a first surface of the substrate, and the first conductive metal layer is on the first adhesive layer. The second adhesive layer is on a second surface of the substrate, and the second conductive metal layer is on the second adhesive layer. Preferably, the substrate is a polyimide film.

In still another preferred embodiment of the present invention, the laminate material according to the present invention comprises a substrate, a first adhesive layer and a second adhesive layer formed by the adhesive composition, and a first layer. a release layer and a second release layer. The first adhesive layer is on a first surface of the substrate, the first release layer is on the first adhesive layer, and the second adhesive layer is on a second surface of the substrate And the second release layer is on the second adhesive layer. Preferably, the substrate is a polyimide film.

In still another preferred embodiment of the present invention, the laminate material according to the present invention comprises a substrate, a first adhesive layer and a second adhesive layer formed by the adhesive composition, and a conductive metal. Layer and a release layer. Wherein the first adhesive layer is on a first surface of the substrate, the conductive metal layer is on the first adhesive layer, and the second adhesive layer is on a second surface of the substrate And the release layer is on the second adhesive layer. Preferably, the substrate layer is a polyimide film.

The laminate materials according to the present invention may be bonded to each other or to other laminate materials or to an adhesive composition or other adhesive according to the present invention to produce a multi-layer laminate material.

In a preferred embodiment of the invention, the adhesive composition is applied to the substrate by a coater and dried. The drying conditions are, for example, dried at 100 to 150 ° C for 1 to 3 minutes.

In another preferred embodiment of the invention, the release material is thermocompression bonded to the adhesive composition, for example, at a temperature of 75 ° C.

In still another preferred embodiment of the present invention, the conductive metal is etched, and the adhesive composition is overlaid on the etched conductive metal, and then heated and pressed by a crimping machine, and Made by baking.

The laminate material according to the present invention is simpler in production and material saving than the conventional laminate material, and has a thinner overall thickness and a lighter weight.

The invention further provides an electronic component comprising the aforementioned laminate material.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

Adhesive composition

The adhesive composition was configured in the proportions shown in Table 1 below:

Each of the adhesive compositions prepared in Table 1 was prepared according to Table 2, and various tests were carried out. The test results are shown in Table 2.

It is understood that when the rubber monomer content is from about 5 to about 20 parts by weight, the resulting adhesive composition has the advantages of a low dielectric constant, a high glass transition temperature, and a high flow amount.

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (18)

An adhesive composition comprising a binder, wherein the binder composition has a flux of from about 10% to about 30%; wherein: the binder comprises an epoxy resin monomer and a rubber monomer; The epoxy resin monomer comprises at least two epoxy groups; the rubber monomer comprises a cyano group and at least one group selected from the group consisting of a carboxyl group, a secondary amine group and an epoxy group; and the content of the epoxy resin monomer The rubber monomer is contained in an amount of from about 5 to about 20 parts by weight based on 100 parts by weight. The composition according to claim 1, wherein the epoxy resin single system has a structure represented by the following formula (1): Wherein: n is an integer of 0 or more; and R ₁ represents an OR ₂ or a structure represented by the following formula (2); R ₂ and R ₃ independently represent an alkyl group or an aromatic group having 1 to 6 carbon atoms. The composition according to claim 2, wherein the aromatic group has a structure represented by the following formula (3) or formula (4): The composition according to claim 1, wherein the rubber single system is selected from the group consisting of carboxyl-terminated butadiene-acrylonitrile (CTBN) and amine-terminated butadiene- A group of acrylonitrile, ATBN) and epoxide-terminated butadiene-acrylonitrile (ETBN). The composition according to claim 4, wherein the carboxyl-terminated nitrile copolymer has a structure represented by the following formula (5): Wherein R ₄ has the structure represented by the following formula (6): Wherein x, y, z and m are independently an integer of 1 or more. The composition according to claim 4, wherein the amine-terminated nitrile copolymer has a structure represented by the following formula (7): Wherein R ₅ has the structure represented by the following formula (8): Wherein x, y, z and m are independently an integer of 1 or more. The composition according to claim 4, wherein the epoxy-terminated butyronitrile copolymer has a structure represented by the following formula (9): Wherein: R ₆ represents an alkyl group or an aromatic group having 1 to 6 carbon atoms; and R ₇ has a structure represented by the following formula (10): Wherein x, y, z and m are independently an integer of 1 or more. The composition according to claim 1, wherein the subsequent main component comprises a further hardener selected from the group consisting of cyanoguanidine, diethylenetriamine, triethylenetetramine, and diaminodiphenylmethane. A group consisting of diaminodiphenylphosphonium, phthalic anhydride, tetrahydrophthalic anhydride, anhydrous pyroghuric acid, boron trifluoride amine complex, polyfunctional epoxy resin, and phenolic resin. The composition of claim 1 further comprising a filler. The composition according to claim 9, wherein the filler is selected from the group consisting of cerium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, antimony trioxide, calcium citrate, calcium carbonate, magnesium carbonate, magnesium oxide, a group consisting of zinc oxide and boron nitride. According to the composition of claim 1, it further comprises a solvent. The composition of claim 11, wherein the solvent is selected from the group consisting of methyl ethyl ketone, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, n-propanol, toluene, and xylene. According to the composition of claim 1, it further comprises at least one auxiliary. The composition of claim 13, wherein the adjuvant is selected from the group consisting of an ion inhibitor and a flame retardant. A laminate material comprising a substrate and an adhesive composition according to any one of claims 1 to 14 disposed on a surface of the substrate. The laminate material according to claim 15, wherein the substrate is selected from the group consisting of a soft substrate, a hard substrate, a release material, and a metal. The laminate material of claim 16, wherein the metal is a conductive metal. An electronic component comprising the laminate material according to any one of claims 15 to 17.