TWI426116B - Adhesive composition, adhesive layer and laminated substrate thereof - Google Patents

Description

Adhesive composition, adhesive layer and laminated structure thereof

The present invention relates to a glue composition, and more particularly to an adhesive composition.

In general, it is difficult for a single polymer material to exert the opposite characteristics at the same time. Therefore, polymer blends must be used to enhance the properties of polymer materials, and polymer blend materials are mostly controlled by blending materials. The phase separation structure is used to achieve high functionalization of the material, and excessive delamination will make the polymer blend difficult to produce.

Printed circuit boards are indispensable materials in electronic devices, which are developed in the direction of thinning, high density, high withstand voltage and high thermal conductivity. The traditional printed circuit board is made of epoxy resin and then mixed with inorganic heat conductive material. However, with the application of high frequency and high thermal conductivity, the printing with poor voltage resistance, heat resistance and adhesion is poor. The board must make a technical breakthrough. Furthermore, the laminated metal foil-clad laminate is obtained by bonding an insulating substrate and a metal foil through an adhesive film. However, the conventional adhesive or adhesive film is mainly made of epoxy or acrylic. Adhesives, because of the poor heat resistance of the adhesive, make the heat resistance of the bonded product insufficient, so that the processing conditions and conditions of use are limited.

On the other hand, polyimine having excellent heat resistance, adhesion, low dielectric constant and the like is difficult to be epoxy- or acrylic-based resin in the general concept, and the problem is the degree of phase separation between the two. Too large, making the blend difficult to apply.

One of the objects of the present invention is to provide an adhesive composition which can be applied to the blending of epoxy resin/phenoxy resin to form a composition having dynamic uniform mixing without delamination. In addition, the adhesive composition prepared has a relatively good adhesion and adhesion characteristics, and thus can be widely applied to industrial laminated materials.

The present invention provides an adhesive composition comprising: component (A): phenoxy resin, wherein the phenoxy resin has the following structural formula (Formula 1); component (B): polyfluorene Imine resin; component (C): hardener;

Wherein n is greater than 18 and R is CH ₃ .

Embodiments of the present invention provide an adhesive layer.

The embodiment of the invention further provides a laminated structure in which the two components are closely attached by using an adhesive layer.

The invention has the following beneficial effects: the adhesive composition and the adhesive layer proposed by the invention can have good adhesion to the adherend, and the adhesive layer can further improve the peel strength and heat resistance of the laminated structure in the substrate production. A very important feature. Furthermore, the adhesive composition and the adhesive layer proposed by the present invention can be applied to a high frequency field to produce a laminated structure having a low dielectric constant.

For a better understanding of the features and technical aspects of the present invention, reference should be made to the accompanying drawings.

The adhesive composition of the present invention comprises at least a polyimide resin (PI) and a phenoxy resin, and the polyimine resin and the phenoxy resin can have a dynamic homogeneous ratio at a specific ratio. Characteristics, in other words, the present invention provides an adhesive composition in which a polyimine resin and a phenoxy resin are mutually soluble; and further, since the polyimide resin in the adhesive composition of the present invention has a large molecular weight property, The adhesive composition is made easier to control during the pressing process.

The present invention provides a prepreg composition comprising: component (A): a resin comprising at least a phenoxy resin, a component (B): a polyimide resin and a group Part (C): Hardener. The composition of each of the above components will be described in detail below: a phenoxy resin in the component (A) of the present invention, which may be a phenoxy resin represented by the following (Formula 1);

Wherein, n may be greater than 18, and R may be CH ₃ , and the phenoxy resin of the present invention preferably has a weight average molecular weight (Molecular Weight) of between 5,000 and 500,000, that is, n may be between 18 and 1800. between. Component (A) may further comprise an epoxy resin, such as a halogen-free or halogen-containing resin, and preferred examples of halogen-free epoxy resins include, but are not limited to, bisphenol epoxy resin, novolak type ( Novolac) epoxy resin, tetrafunctional epoxy resin, phosphorus-containing epoxy resin.

Further, the hydroxyl group (OH) on both sides of the formula (Formula 1) may be substituted by a phosphorus-containing compound which may, for example but not limited to, DOPO, a compound represented by (Formula 2) (DOPO-NQ) , 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphinophen-10-oxide (10-(2,5-dihydroxyphenyl)-10h, represented by (Formula III) -9 oxa-10-phosphaphenanthrene-10-oxide, DOPO-HQ) or DOPO precursor:

Component (B) of the present invention: a polyimine resin, and in a specific embodiment of the present invention, the polyimide resin has good electrical properties, for example, a dielectric constant (Dk) of about 2.6 at 1 GHz. Up to 3.5 (@1 GHz).

The polyimine resin of the present invention can be represented by the following (Formula 2), which can be obtained by reacting a diamine of the following (one of the formula II) with a dianhydride of the following (Formula II):

H ₂ NR ₁ -NH ₂ (one of formula 2)

Wherein R1 in the above (Formula 2) and (Formula 2) may be as follows: (i) a covalent bond; (ii) a C _2-12 aliphatic hydrocarbon group; (iii) a C _4-30 alicyclic group. (iv) a C _6-30 aromatic group; (v) a functional group of the formula -Ph-O-X1-O-Ph- (wherein X1 may represent a stretching phenyl group (-Ph-) or -Ph-X- a group of Ph- and X represents a covalent bond, a C _1-4 alkyl group which may be substituted by halogen, -O-phenyl-O-, -O-, -CO-, -S-, -SO- or - SO ₂ -yl); or (vi)-X2-(SiX3 ₂ -O) _m -SiX3 ₂ -X2- (wherein X2 is -(CH ₂ ) _s -, -(CH ₂ ) _s -Ph-, -(( CH ₂ ) _s -O-Ph- or -Ph-, m is an integer from 1 to 100; s is an integer from 1 to 4; X3 is C _1-6 alkyl, phenyl or C _1-6 alkylphenyl ).

And R2 in (Formula 2) and (Formula 2) represents a tetravalent aliphatic group having 2 to 12 carbon atoms, a tetravalent cycloaliphatic group having 4 to 8 carbon atoms, and a C _6-14 single a ring or polycyclic fused tetravalent aromatic group, a group of >Ph-X4-Ph< (wherein X4 represents a covalent bond, a C _1-4 alkyl group which may be substituted by a halogen, -O-phenyl-O- , -O-, -CO-, -S-, -SO- or -SO ₂ - group).

Specifically, examples of the diamine of the formula (one of the formula II) prepared in the present invention may be, for example but not limited to, p-phenylenediamine (PDA), 4,4'-diaminodiyl Phenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, 4,4'-di (m-Aminophenoxy)diphenylanthracene, 4,4'-bis(p-aminophenoxy)diphenylanthracene, o-phenylenediamine, m-phenylenediamine, P-phenylenediamine, benzidine, 2,2'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-2 , 2'-propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4-dimethyl Hepta-methylene diamine, 2,11-dodecanediamine, bis(p-aminophenoxy)dimethyl decane, 1,4-bis(3-aminopropyldimethyl decyl) Benzene, 1,4-diaminocyclohexane, o-xylenediamine, m-xylylenediamine, acetoguanamine, benzoquinone, 1,3-bis(3-aminophenoxy) Benzene (APB), bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]B 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, 2,2 - bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]butane, 2,2-bis[4- (3-Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4 -(3-Aminophenoxy)phenyl]methanone, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl Anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]ether, etc., the above bisamine may be used alone or Used in a variety of combinations.

Examples of the dianhydride (formula bis) used in the preparation of the polyaminic acid in the present invention may be, for example but not limited to, pyromellitic dianhydride (PMDA), 4,4'-oxydicindole anhydride. (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), B Tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2',3 , 3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, Bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, Bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic acid dianhydride, 4 , 4'-(m-phenyldioxy)diphthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6, 7-fluorene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc.; Dianhydride may be used singly or in a variety of mixtures. Among them, pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-biphenylphosphonium tetracarboxylic dianhydride (DSDA), and the like.

The reaction of the above-mentioned dianhydride and diamine can be carried out by ring-opening polymerization into a polyglycine intermediate (PAA) in a strong polar solvent, and then forming a polyfluorene by a dehydration ring-closing reaction by heat or other chemical hydrazine imidization. The imine; and the kind of the strong polar solvent is not particularly limited as long as it does not react with the reactants and the product, and specific examples thereof may be, for example, an aprotic strong polar solvent such as N,N-dimethylacetamide (DMAc). , N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), dioxane, chloroform (CHCl ₃ ), dichloromethane, etc. N-methylpyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Further, the reaction of the dianhydride with the diamine is generally carried out at a temperature ranging from room temperature to 90 ° C, preferably from 30 to 75 ° C, and the equivalent ratio of the aromatic bisamine to the aromatic dianhydride (aromatic bisamine / The aromatic dianhydride) is in the range of from 0.5 to 2.0, preferably in the range of from 0.75 to 1.25.

The component (C) of the present invention: a hardener, the hardener may be a phosphorus-containing hardener such as a bisphenol A phenol resin or a bisphenol F phenol resin and reacted with HCA. Specifically, phosphorus can be used in the present embodiment. PPN resin, such as a halogen-free hardener produced by SHIN-A T&C, having a molecular weight of 700 to 2200 g/mol; a phosphorus content of 5 to 12%, preferably about 9.4%; In a variant embodiment, component (C) is a modified form of PPN, for example physically or chemically incorporated into a specific inorganic component, for example 0.1 to 3% by weight of hydrazine.

In the following, a plurality of sets of examples will be described for the above-mentioned adhesive composition to demonstrate optimum laminate characteristics by composition ratio composition of the adhesive composition. Please refer to the following table 1:

As shown in Table 1, in each of the experimental examples, in addition to the above components (A) (B) (C), a polyfunctional epoxy resin, a chain extender, an inorganic filler powder, or the like may be further included.

Preferred examples of chain extenders include, but are not limited to, dicyandiamide, diphenyl diamino sulfone, novolac resin, melamine phenol novolac resin, benzene. And a benzoxazine resin, a bisphenol A/F type benzoxazine resin, a polyphenylene oxide or the like, or a chain extender may be a styrene-cis represented by the following formula Butene hydride copolymer (SMA):

Wherein x is an integer from 1 to 8, and n is an integer from 1 to 12. Wherein, the ratio of the styrene/maleic anhydride monomer may be 1/1, 2/1, 3/1, 4/1, 6/1 or 8/1, and examples thereof include trade names: SMA1000, SMA2000, Styrene/maleic anhydride copolymers such as SMA3000, SMA EF-30, EF-40, EF-60 and EF-80, which have a weight average molecular weight ranging from 1400 to 15000, preferably between 7000 to 10000.

The inorganic filler powder is added in an amount of 10 to 50% by weight of the adhesive composition, preferably 20 to 25% by weight; and the above inorganic powder may be crystalline, spherical or melted or free of crystals. One or a combination of water type powders, more specifically, the inorganic powder selected for the present invention may be ceria, aluminum nitride, aluminum hydroxide, aluminum borate, magnesium hydroxide, boron nitride, Calcium carbonate, talc, zinc borate, calcined kaolin, aluminum oxide, titanium dioxide glass powder, mica powder, powder particle size of about 0.1 μm to 40 μm.

As can be seen from Experimental Examples 1 to 5, the weight ratio of the component (B): the combination of the polyimine resin and the phenoxy resin of the component (A) and the component (B) is greater than "0" and less than " Between 1"; and component (B): the weight percentage of the sum of the polyimine resin and the component (A) and the component (B) is between more than "0%" and less than "50%".

The weight average molecular weight of the above component (B) may be in the range of 10,000 to 200,000, preferably 10,000 to 100,000, more preferably 20,000 to 80,000, so that the adhesive composition of the present invention is formed into a thin sheet. The adhesive layer in the form of a film or a film has characteristics such as strength, flexibility, and adhesion.

Furthermore, according to the composition of the above embodiment, the present invention can provide an adhesive composition which has dynamic non-layering and is uniformly dispersed at 20 ° C to 60 ° C, and the adhesive composition of the present invention is used for the adhesion of the laminated material. A preferred peeling strength can be achieved.

In addition, the adhesive composition of the present invention can be applied to various fields to form a laminated structure. For example, the adhesive layer formed by the adhesive composition of the present invention can be used for fixing the wafer (ie, the first component) to the aluminum substrate (ie, The second component) solves the problem of drilling caused by the conventional use of thermal film for fixing. For the application of high-frequency communication, the adhesive layer formed by the adhesive composition of the present invention can effectively adhere to an electrically stable industrial material, such as a thin plate of a Teflon material having a low Dk value, for example, utilized. The adhesive layer of the present invention fixes two layers of Teflon sheets (ie, two corresponding components) to form a relatively thin low Dk laminate material, or passes a layer of Teflon sheet through the adhesive layer of the present invention. The adhesive layer of the present invention is adhered to the outer casing of the electronic product, so that the structural strength of the laminated material can be improved to improve the reliability of the product.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the equivalents of the present invention are intended to be included within the scope of the present invention.

Claims (20)

An adhesive composition comprising: component (A): a resin comprising at least a phenoxy resin and an epoxy resin, wherein the phenoxy resin has the following structural formula (Formula 1): Wherein n is greater than 18 and R is CH ₃ ; component (B): polyimine resin, wherein component (B) accounts for more than the total weight of component (A) and component (B) 0%, less than 50%; component (C): hardener. The adhesive composition according to claim 1, wherein the component (B): the weight ratio of the polyimine resin to the total of the phenoxy resin and the component (B) in the component (A) is It is greater than 0 and less than 1. The adhesive composition according to claim 1, wherein the epoxy resin is a halogen-free or halogen-containing resin. The adhesive composition according to claim 1, wherein the phenoxy resin in the component (A) has a weight average molecular weight of from 5,000 to 500,000. The adhesive composition of claim 1, wherein the formula (n) has a structural formula n between 18 and 1800. An adhesive composition according to claim 1, wherein a) The (OH) on both sides of the structural formula may be replaced by a phosphorus-containing compound. The adhesive composition according to claim 6, wherein the phosphorus-containing compound is a compound represented by (Formula 2) and (Formula III): The adhesive composition according to claim 1, wherein the component (B): the polyamidene resin has a weight average molecular weight of from 10,000 to 200,000, and the polyamidene resin is at 1 GHz. The dielectric constant under the conditions is 2.6 to 3.5. The adhesive composition according to claim 1, further comprising an inorganic filler powder, wherein the inorganic filler powder is added in an amount of 10 to 50% by weight of the adhesive composition. The adhesive composition according to claim 9, wherein the inorganic filler powder has a particle diameter of from 0.1 μm to 40 μm. The adhesive composition of claim 1, further comprising a chain extender. The adhesive composition according to claim 11, wherein the chain extender is dicyandiamide, diaminodiphenyl hydrazine, phenolic resin, melamine phenolic resin, benzoxazine resin, double Phenolic A/F type benzoxazine resin or bis/polyfunctional polyphenylene ether resin. The adhesive composition according to claim 11, wherein the chain extender is a styrene-maleic anhydride copolymer represented by the following formula: Wherein x is an integer from 1 to 8, and n is an integer from 1 to 12. The adhesive composition according to claim 1, wherein the component (C) is a phosphorus-containing hardener. The adhesive composition according to claim 14, wherein the component (C) is a phosphorus-containing phenolic resin hardener having a phosphorus content of 5 to 12%. The adhesive composition according to claim 14, wherein the component (C) is a modified product of a phosphorus-containing phenolic resin to which cerium is added in a weight ratio of 0.1 to 3%. The adhesive composition of claim 1, wherein the adhesive composition has a dynamic non-layering and uniform dispersion at 20 ° C to 60 ° C. An adhesive layer formed of the adhesive composition according to any one of claims 1 to 17. A laminate structure comprising the adhesive layer according to item 18 of the application and two corresponding components, the two components being closely adhered by the adhesive layer. The laminate structure of claim 19, wherein at least one of the two components is a Teflon sheet.