TW201817805A - Resin composition suitable for rigid-flex board and application thereof capable of satisfying the characteristics of low flow amount and low dust weight loss - Google Patents

Abstract

The present invention discloses a resin composition, which comprises epoxy resin, curing agent, triallyl isocyanurate containing DOPO, and phosphazene. The resin composition can be made into various types of articles, such as prepregs, laminates, printed circuit boards, flexible multi-layer boards, or rigid-flex boards, so as to satisfy at least one, some, or all of characteristics including low flow amount, low dust weight loss, high tensile strength at room temperature and high temperature, low dielectric constant, low dielectric loss, high flame retarding capability, and high heat resistance.

Description

Resin composition suitable for flexible and rigid board and its application

The present invention relates to a resin composition, and more particularly, to a resin composition that can meet the characteristic requirements of rigid-flex boards and other products in applications.

The conventional printed circuit board mainly uses glass fiber cloth as a base material, so the texture is relatively hard, also known as a rigid board, and it is not flexible, so it causes many restrictions on the volume and shape design of the end product. Various types of electronic products made using only hard boards, due to structural restrictions, cause many restrictions on the volume and shape design of the end product.

To solve such problems, the industry uses a flexible printed circuit (FPC), which is also called a flexible board, with a flexible material such as a polyimide film (PI film) as at least a part of the body. The flexible board has the advantages of light weight, thinness, flexibility, and three-dimensional wiring that can be changed in shape according to space. However, flexible boards have disadvantages such as higher cost, difficulty in processing multilayer PCBs, and lower weight-bearing capacity. Therefore, the use of flexible boards alone cannot meet various needs in the design of electronic products.

As a result, a combination of flexible and rigid boards, also known as flexible and rigid boards, is used to meet the structural design requirements of various products by using the rigidity of rigid boards and the flexibility of flexible boards. Claim.

In terms of design and manufacturing, in order to connect the flexible board and the rigid board and at the same time to avoid staining the etched circuit pattern of the flexible board and the hard board, it is necessary to use a prepreg that meets certain characteristics as the bonding sheet, such as A prepreg with low flow properties.

However, the existing resin compositions applied to such prepregs or adhesive sheets can meet the requirements of low-flow adhesive properties, but there are still unsatisfactory aspects in other characteristics, so it is necessary to propose new solutions.

Based on this, the present invention proposes a resin composition which can not only meet the characteristics of low flow glue, but also achieve at least one other property improvement, such as low chip loss (or low cutting weight loss), room temperature and high temperature tensile force High strength, low dielectric constant, low dielectric loss, high flame retardancy and high heat resistance, etc., so it can meet the needs of a variety of different product applications, such as the low-flow adhesive prepregs required (Referred to as adhesive sheet).

For example, in one embodiment, the present invention discloses a resin composition that can meet the low flow volume. For example, the flow volume measured by referring to the method described in IPC-TM-650 2.3.17.2 is less than or equal to Equal to 60 mils, preferably less than or equal to 30, 28, 26, 25 or 21 mils, such as between 21 and 30 mils.

In one embodiment, the present invention discloses a resin composition and articles made therefrom, such as prepreg, laminated board, printed circuit board, flexible multilayer board, or rigid-flex board, in addition to satisfying the aforementioned characteristics of low glue flow. In addition, it has one, more or all of the following characteristics: (1) Low dust weight loss (or cut weight loss), such as 0.35% or less, preferably less than or equal to 0.34%, 0.29%, 0.26%, 0.21%, 0.18%, or 0.16%, such as between 0.15% and 0.35%; (2) High temperature tensile strength (P / S, that is, high temperature test substrate tensile force to copper foil) ) High strength, for example, the tensile force measured at 280 ^o C with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 5.0 lb / in, preferably greater than or equal to 5.1 lb / in, 5.2 lb / in or 5.4 lb / in, for example between 5.0 lb / in and 5.5 lb / in; (3) The tensile strength at room temperature (that is, the tensile strength of the copper substrate at room temperature test substrate) is high, such as at room temperature (about 25 ^o The pull force measured under the method described in IPC-TM-650 2.4.8 under reference C) is greater than or equal to 6.0 lb / in, preferably greater than or equal to 6.3 lb / in, 6.8 lb / in, 6.9 lb / in or 7.0 lb / in, for example between 6.0 lb / in and 7.5 lb / in; (4) Low dielectric constant (Dk), for example, refer to JIS at 2 GHz The dielectric constant (Dk) measured by the method described in C2565 is less than or equal to 3.70, preferably less than or equal to 3.68, 3.67, 3.62, 3.58, or 3.52, such as between 3.52 and 3.70; (5) Low Dielectric loss (Df), for example, the dielectric constant (Df) measured at 2 GHz with reference to the method described in JIS C2565 is less than or equal to 0.0140, preferably less than or equal to 0.0136, 0.0135, 0.0133, 0.0132 Or 0.0112, for example between 0.0112 and 0.0140; (6) High flame retardancy, for example, the flame retardancy measured by reference to the method of UL94 standard reaches V-0 level; (7) Pull force of polyimide test board High strength, polyimide tensile test board containing the aforementioned prepreg, for example, the tensile force measured at room temperature (about 25 ^o C) with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 5.0 lb / in, preferably greater than or equal to 5.1 lb / in, 5.2 lb / in, 8.0 lb / in, or 8.1 lb / in, such as between 5.0 lb / in and 8.5 lb / in; (8) more flexible The laminate has high heat resistance. The flexible multilayer board made of this composition is measured by the method described in IPC-TM-650 2.6.27. The total number of reflows before the burst (to the burst) is 15 or more. return.

In order to achieve the improvement of any one or more of the aforementioned effects, in one embodiment, the present invention discloses a resin composition including an epoxy resin, a hardener, and DOPO-triallyl isocyanate (DOPO-TAIC). ) And phosphazene.

Unless otherwise specified, the amount of any one of the aforementioned four ingredients and the proportional relationship between the ingredients can be adjusted as needed.

In one embodiment, the present invention discloses a resin composition including 100 parts by weight of an epoxy resin; 1 to 50 parts by weight of a hardener; 10 to 30 parts by weight of a DOPO-containing trimeric isocyanate triallyl Ester and 10 to 30 parts by weight of phosphazene.

In a preferred embodiment, the amount of the hardener added is preferably 20 to 45 parts by weight.

In a preferred embodiment, compared to 100 parts by weight of the epoxy resin, the total amount of the triallyl isotricyanate and phosphazene containing DOPO is 20 to 60 parts by weight.

In a preferred embodiment, the aforementioned DOPO-containing triallyl isocyanate includes the following structure: .

In a preferred embodiment, the aforementioned phosphazene includes the following structure: , Where n is an integer from 1 to 6.

In a preferred embodiment, the aforementioned hardener may be, for example, but not limited to: amine hardener, phenoxy resin, polyvinyl butyral, polyphenylene ether, polyolefin, polyester resin, styrene maleic anhydride , Benzoxazine resin, maleimide, cyanate resin, or a combination thereof.

In addition, the resin composition may optionally include other components, such as a flame retardant, an inorganic filler, a hardening accelerator, a solvent, a silane coupling agent, or a combination thereof.

In order that those skilled in the art can understand the features and functions of the present invention, the following are general descriptions and definitions of terms and terms mentioned in the specification and the scope of patent applications. Unless otherwise specified, all technical and scientific words used herein have the ordinary meanings understood by those skilled in the art for the present invention. In case of conflict, the definitions in this specification shall prevail.

In this article, the terms "including", "including", "having", "containing" or any other similar words are open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article containing a plurality of elements is not limited to only those elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" rather than an exclusive "or". For example, the condition "A or B" is satisfied in any of the following situations: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), A Both and B are true (or exist). In addition, in this article, the interpretation of the terms “including,” “including,” “having,” and “containing” shall be deemed to have been specifically disclosed and cover both “consisting of” and “consisting essentially of”. Or semi-closed conjunctions.

In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, a description of a numerical range or percentage range should be considered as covering and specifically revealing all possible individual ranges and individual values within the range, especially integer values. For example, the range description of "1 to 8" should be regarded as having specifically revealed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, especially The sub-ranges defined by all integer values shall be considered as individual values within the ranges that have been specifically disclosed, such as 1, 2, 3, 4, 5, 6, 7, 8. Unless otherwise specified, the foregoing interpretation method applies to all aspects of the present invention, whether broad or not.

If a quantity or other value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that this document has specifically disclosed that any one of the upper or better values of the range and the lower limit of the range Or better ranges, regardless of whether these ranges are disclosed separately. In addition, where a range of numerical values is mentioned herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

Herein, before the object of the invention can be achieved, the value should be understood as having the accuracy of the significant digits of the value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

Herein, for the case where Markush group or option language is used to describe the features or examples of the present invention, those skilled in the art should understand the subgroup of all members in the Markush group or option list. Or any individual member can also be used to describe the invention. For example, if X is described as "selected from the group consisting of X _1, X ₂ and X ₃ the group consisting of," have been fully described also represents a proposition and X is X ₁ X is X ₁ and / or X ₂ Claims. Furthermore, for those who use Marcussi groups or option terms to describe features or examples of the present invention, those skilled in the art should understand any subgroups or individual members of all members in the Marcussi group or option list. Combinations can also be used to describe the invention. Thus, for example, if X is described as "selected from the group consisting of X _1, X ₂ and X ₃ consisting of Groups", as described and Y 'is selected from the Y _1, Y ₂ and Y ₃ composed of ", Then the claim that X is X ₁ or X ₂ or X ₃ and Y is Y ₁ or Y ₂ or Y ₃ has been fully described.

The following specific embodiments are merely exemplary in nature and are not intended to limit the present invention and its uses. In addition, this document is not limited by the foregoing prior art or summary or any theory described in the following detailed description or examples.

Resin composition

One of the main objects of the present invention is to provide a resin composition, which mainly includes four components, such as epoxy resin, hardener, triallyl isocyanate containing DOPO, and phosphazene.

The amount of any one of the aforementioned four ingredients and the proportional relationship between the ingredients can be adjusted as needed. For example, in one embodiment, the present invention discloses a resin composition including 100 parts by weight of an epoxy resin; 1 to 50 parts by weight of a hardener; 10 to 30 parts by weight of DOPO-containing trimeric isocyanide Triallyl acid and 10 to 30 parts by weight of phosphazene. As far as the application of flexible and rigid boards is concerned, the aforementioned group distribution ratio can achieve better comprehensive ideal characteristics, but in other applications, the amount and proportion of the components of the resin composition are not limited to this.

In one embodiment, the aforementioned epoxy resin may be various types of epoxy resins known in the art, including but not limited to, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol Phenol AD epoxy resin, phenol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene, DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin (such as naphthol epoxy resin), benzofuran ring Oxygen resin, isocyanate-modified epoxy resin. Among them, the phenolic epoxy resin can be bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde ( phenol benzaldehyde) epoxy resin, phenol aralkyl novolac epoxy resin or o-cresol novolac epoxy resin; among them, the phosphorus-containing epoxy resin may be DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin or a combination thereof. The aforementioned DOPO epoxy resin may be selected from the group consisting of DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO bisphenol A. One or two or more of DOPO-containing bisphenol-A novolac epoxy resins; the aforementioned DOPO-HQ epoxy resins may be selected from DOPO-HQ-containing phenolic novolac resins epoxy resin), DOPO-HQ-containing cresol novolac epoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin).

In one embodiment, the aforementioned hardener is a commercially available hardener, such as, but not limited to, amine hardeners, phenoxy resins, polyphenylene ether resins, polyvinyl butyral, polyolefins, and polymers. Either an ester resin, a styrene maleic anhydride, a benzoxazine resin, a maleimine, a cyanate resin, or a combination thereof.

The amine-based hardener may be, for example, but not limited to, a compound having an amino functional group, preferably a compound having a diamino functional group. More specifically, the amine hardener may be diamino diphenyl sulfone, diamino diphenyl methane, diamino diphenyl ether, diamine One or a combination of diamino diphenyl sulfide, dicyandiamide (DICY).

For example, dicyandiamide can include, but is not limited to, dicyandiamide known in the industry, such as DICY purchased from Qinyu Company, or Adeka HT2844 (modified dicyandiamide) sold by Asahi Denka. Its structure is as follows: .

Based on 100 parts by weight of the epoxy resin, the added amount of dicyandiamide may be, for example, 0.5 to 3 parts by weight, preferably 1 to 3 parts by weight, and more preferably 2 to 3 parts by weight.

For example, phenoxy resins can include, but are not limited to, phenoxy resins purchased from InChem Corporation under the product names PKHA, PKHB, PKHB +, PKHC, PKHH, PKHJ, PKFE, PKHP-200, or Nippon Steel Chemical Product YP50S. Based on 100 parts by weight of the epoxy resin, the addition amount of the phenoxy resin may be 10 to 30 parts by weight, preferably 10 to 25 parts by weight.

For example, the polyphenylene ether resin includes, but is not limited to, a hydroxypolyphenylene ether resin.

For example, polyolefins include styrene-butadiene-divinyl benzene terpolymer, styrene-butadiene-maleic anhydride terpolymer -maleic anhydride terpolymer), vinyl-polybutadiene-urethane oligomer, styrene-butadiene copolymer, hydrogenated styrene butadiene copolymer (hydrogenated styrene-butadiene copolymer), styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, or a combination thereof. Preferably, the polyolefin may be a styrene-butadiene-divinylbenzene terpolymer, a styrene-butadiene-maleic anhydride terpolymer, and a vinyl-polybutadiene-urethane oligomer. Polymer or combination thereof.

For example, the polyester resin can be obtained by esterifying an aromatic compound having a dicarboxylic acid group and an aromatic compound having a dihydroxy group. Such as Dainippon Ink Chemicals sold under the trade name HPC-8000T65.

For example, in the aforementioned styrene maleic anhydride, the ratio of styrene (S) to maleic anhydride (MA) may be 1/1, 2/1, 3/1, 4/1, 6/1, 8 / 1 or 12/1, such as styrene maleic anhydride copolymers sold under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80 sold in the Cray valley. In addition, the styrene maleic anhydride copolymer may also be an esterified styrene maleic anhydride copolymer, such as SMA1440, SMA17352, SMA2625, SMA3840, and SMA31890 sold by Cray Valley.

For example, the benzoxazine resin may be a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin or a phenolphthalein type benzoxazine resin, a dicyclopentadiene benzoxazine resin, The phosphobenzoxazine resin is, for example, LZ-8270, LZ-8280 or LZ-8290 manufactured by Huntsman, or HFB-2006M manufactured by Showa Polymer Corporation.

For example, the maleimide may be 4,4'-diphenylmethane bismaleimide, an oligomer of phenylmethane maleimide. ), M-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl- 5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4- 4-methyl- 1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl ) Hexane (1,6-bismaleimide- (2,2,4-trimethyl hexane) or a combination thereof.

For example, the cyanate resin is not particularly limited, and any cyanate having an Ar-OC≡N structure is acceptable. Ar may be substituted or unsubstituted aromatic, phenolic, bisphenol A, or bisphenol. A phenolic, bisphenol F, bisphenol F phenolic or phenolphthalein.

Examples of the aforementioned cyanate resin may be, for example, trade names primaset PT-15, PT-30S, PT-60S, CT-90, BADCY, BA-100-10T, BA-200, BA-230S, BA-300S, BTP-2500, BTP-6020S, DT-4000, DT-7000, Methylcy, ME-240S and other cyanate resins produced by Lonza.

In one embodiment, the aforementioned DOPO-containing triallyl isocyanate (DOPO-TAIC) includes the following structure: , Such as NPEP-208, which can be purchased from, but not limited to, Nanya Plastics.

In one embodiment, the aforementioned phosphazene may be a phosphazene having a reactive functional group at the terminal and a phosphazene having no reactive functional group at the terminal, and the structure of the phosphazene may be a cyclic or acyclic phosphazene.

The phosphazene without a reactive functional group at the terminal has, for example, the following structural formula, but is not limited thereto: Where n is an integer from 1 to 6, preferably n is an integer from 3 to 6.

The phosphazene having a reactive functional group at the terminal may be, for example, a phosphazene having a hydroxyl group, a vinyl group, and a vinyl benzyl group at the terminal, such as: hydroxyphosphazene, allylphosphazene, and vinylbenzyl ether phosphazene.

Phosphazene can be purchased from, for example, but not limited to, SPB-100 (phosphazene without reactive functional group at the end), SPH-100 (phosphazene with hydroxyl group at the end), SPV-100 (allyl group with allyl end Phosphazene), but not limited to this.

In addition, the resin composition may further include various additives, such as a flame retardant, an inorganic filler, a hardening accelerator, a solvent, a silane coupling agent, or a combination thereof, as necessary.

For example, the flame retardant may be various types of flame retardants, including, but not limited to, phosphorus-containing compounds, nitrogen-containing compounds, or a combination thereof.

The phosphorus-containing compound may be at least one of the following compounds, but is not limited thereto: bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (diphenyl) Hydroquinone bis- (diphenyl phosphate), bisphenol A-bis- (diphenyl phosphate), bisphenol A bis- (diphenylphosphate), tris (2-carboxyethyl) phosphine (tri (2 -carboxyethyl) phosphine (TCEP), tris (chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol Resorcinol bis (dixylenyl phosphate), RDXP, such as PX-200, purchased from Daba Chemical), m-phenylene methylphosphonate (PMP), melamine polyphosphate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO), DOPO-containing phenol resin (such as DOPO-HQ , DOPO-PN, DOPO-BPN), DOPO-containing epoxy resin, DOPO-HQ-containing epoxy resin, etc., among which DOPO-BPN can be DOPO-BPAN, DOPO-BPFN, DOPO-BPSN, etc. Phenolic novolac compounds, diphenyl phosphine oxide (DPPO) compounds, diphenylphosphine derivatives, and the like.

The nitrogen-containing compound may be at least one of the following compounds, but is not limited thereto: amino triazine novolac (ATN), melamine cyanurate, and tris-hydroxyethyl isocyanate Cyanurate (trihydroxy ethyl isocyanurate).

For example, the inorganic filler can be various types of inorganic fillers, including but not limited to silicon dioxide (fused, non-fused, porous or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide , Calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), incinerated talc, talc, silicon nitride, incinerated At least one or more of kaolin.

For example, the hardening accelerator may be various types of hardening accelerators, including but not limited to catalysts such as Lewis base, Lewis acid, or peroxide. Among them, the Lewis base may include imidazole, boron trifluoride complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), and 2-benzene 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethyl One or more of 4-dimethylaminopyridine (DMAP). Lewis acid may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc and other metal salt compounds, such as zinc octoate, cobalt octoate and other metal catalysts. Among them, the peroxide may include dicumyl peroxide, tert-butyl peroxybenzoate, and di-tert-butyl dicumyl peroxide, and preferably di-tert-butyl dicumyl peroxide.

For example, the solvent may be various solvents, including but not limited to methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexane Ketone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, etc. Solvents or mixed solvents.

For example, the silane coupling agent may be various types of silane coupling agents, including but not limited to silane and siloxane.

In a preferred embodiment, the resin composition includes: 100 parts by weight of epoxy resin; 1 to 50 parts by weight of hardener; 10 to 30 parts by weight of DOPO-containing triallyl isocyanate; and 10 To 30 parts by weight of phosphazene, wherein DOPO-containing triallyl isocyanate includes the following structure: , And phosphazene includes the following structures: , Where n is an integer from 1 to 6, and wherein the benzene ring structure is unsubstituted or optionally substituted by a reactive functional group.

Resin composition products

Another object of the present invention is to provide a product manufactured from the aforementioned resin composition, such as, but not limited to, a prepreg, a laminated board, a printed circuit board, a flexible multilayer board, or a rigid-flexible board.

For example, the resin composition of each embodiment of the present invention can be made into a prepreg, which has a reinforcing material and a layer (insulating layer) disposed on the reinforcing material. The layer is made of the resin as described above. composition between heated to high temperatures by curing the semi-cured state (B-stage), the production of a prepreg, for example, the baking temperature of 120 ^o C to 190 ^o C is formed. The reinforcing material may be a fibrous material, a woven fabric, or a non-woven fabric, such as glass fiber cloth, to increase the mechanical strength of the prepreg. Preferably, the reinforcing material can also be pretreated selectively through a silane coupling agent.

In a preferred embodiment, the prepreg is a low flow prepreg.

For example, the resin composition of each embodiment of the present invention can also be made into a laminate or copper foil substrate, which includes two metal foils and an insulating layer (ie, the aforementioned layer), and the insulating layer is disposed on the between the metal foil and the like, and the insulating layer may be the resin composition to a high temperature, high pressure is formed by curing, suitable curing temperature, for example ranging between 150 ^o C to 230 ^o C. The insulating layer may be the aforementioned prepreg or resin film; the material of the metal foil may be copper, aluminum, nickel, platinum, silver, gold, or an alloy thereof, such as a copper foil.

For example, the resin composition of each embodiment of the present invention can also be made into a rigid-flex board. The method may be, for example, combining a soft-hard combined board with a soft board, combining a soft-hard combined board with a hard board, combining both sides of the soft-hard combined board with a soft board and a hard board, and the like. For example, cut the low-flow glue prepreg into a suitable shape and size, in the order of double-sided circuit flexible board, low-flow glue prepreg, or double-sided circuit flexible board, film (such as cover layer or Adhesive film), low-flow glue prepreg, or single-sided soft board, low-flow glue prepreg (single-sided soft board without circuit surface and low-flow glue prepreg in contact), or hard copper There are four lamination methods, such as the order of foil substrate and low-flow glue prepreg. Permutations and combinations of any one or more of the foregoing laminated one method, and then at a temperature of between 150 ^o C to high temperature and pressure for curing process between 230 ^o C under vacuum, to give the desired rigid-flex board.

For example, the resin composition of each embodiment of the present invention can also be made into a flexible multilayer board. The method can be, for example, laminating one or more copper foil-containing polyimide films (belonging to a single-sided flexible board), one or more prepregs, flexible circuit boards and other materials in a certain order, and under vacuum conditions, 180 Press and hold at C for 1 hour to form a multi-layer flexible board, in which the polyimide film surface and the prepreg are in contact and superposed.

In an embodiment, the laminated board according to the present invention can be further processed into a printed circuit board after being processed through a circuit process. For example, the printed circuit board manufacturing method may use a conventional printed circuit board manufacturing method for manufacturing a rigid-flex board.

The following examples illustrate various types of products or samples to be tested made from the resin composition of the present invention, and methods for manufacturing the same.

Pre-cured sheet: The resin composition of the following examples and the resin composition of the following comparative examples are selected, each resin composition is evenly mixed to form a varnish, and the gel is placed in an impregnation tank, and then the glass is Fiber cloth (E-glass fiber fabric (E-glass fiber fabric, specifications: 1080, 1067, 106, and 7628, purchased from Asahi)) was immersed in the impregnation tank to make the resin composition adhere to the glass fiber cloth, and then Bake at 180 ^o C for about 4 minutes to obtain a prepreg.

Copper foil substrate (5-ply, that is, five-layer laminate): Prepare two sheets of HTE copper foil with a thickness of 18 micrometers and five prepregs made from each of the samples to be tested (E-glass fiber cloth (E -glass fiber fabric), the resin content of each prepreg is about 63%, and the prepregs are laminated in the order of copper foil, five prepregs and copper foils, and laminated under vacuum at 180 ^o C for 1 hour to form copper. Foil substrate. Among them, five superimposed prepregs are cured to form an insulating layer between two copper foils, and the resin content of the insulating layer is about 63%.

Copper-free substrate (5 layers): The above copper foil substrate is etched to remove two copper foils to obtain a copper-free substrate (5 layers), wherein the copper-free substrate (5 layers) is laminated by five prepregs The resin content without copper substrate (5 layers) is about 63%.

Copper-free substrate (2 layers): Prepare two pieces of HTE copper foil with a thickness of 18 microns and two prepregs (made of E-glass fiber cloth with a size of 1067) for each sample to be tested. The resin content is about 70%. The copper foil, two prepregs, and copper foil are laminated in this order. They are laminated under vacuum at 180 ° C for 1 hour to form a copper foil-containing substrate (two layers). Next, the copper foil substrate is etched to remove two copper foils to obtain a copper-free substrate (two layers). The insulating substrate is formed by laminating two prepregs, and the resin content of the copper-free substrate (two layers) is about 70%.

Fire resistance test substrate: Prepare two sheets of 18 micron HTE copper foil and eight prepregs (E-glass fiber fabric with 7628 specifications) made of each sample to be tested. The resin content of the prepreg is about 43%), one prepreg (made of E-glass fiber fabric with a size of 106, and the resin content of each prepreg is about 69%), according to copper foil, four pieces The 7628 prepreg, one 106 prepreg, four 7628 prepregs and copper foil were laminated in this order. They were laminated under vacuum at 180 ° C for 1 hour. After the lamination, the obtained substrate was etched to remove the copper foil to form a flame resistance test substrate ( Substrate thickness is about 59 mils).

For polyimide (PI) tensile test board (one of the flexible and rigid boards): prepare a sheet of HTE copper foil with a thickness of 18 microns, a commercially available polyimide film, a One prepreg and one copper-faced browning board, each with a resin content of about 63%, laminated in the order of copper foil, polyimide film, prepreg and copper-faced browning board, under vacuum conditions, 180 ° Press and hold at C for 1 hour to form a PI tensile test board. The polyimide film is FHK0525 purchased from Taihong Baojiao; the copper-faced brown board is a core board made by the applicant's Taiwan Optoelectronic Materials Co., Ltd. product EM-285. The core board is made of 18 microns HTE copper foil, EM-285 prepreg and 18 micron HTE copper foil are laminated and laminated. The copper foil on the surface can be obtained after browning, but the source of the copper-faced browning board does not affect the test results.

Flexible multilayer board: prepare one browned circuit board, two prepregs, two copper foil-containing polyimide films, copper foil-containing polyimide films, prepregs, browned circuit soft boards, prepregs, The copper foil-containing polyimide film is sequentially laminated, and laminated under vacuum conditions at 180 ° C for 1 hour to form a multilayer flexible board. The polyimide film surface of the copper foil-containing polyimide film is in contact with the prepreg. Overlap. The copper foil-containing polyimide film is 20RL810 purchased from Changjieshi; the soft board of the browned circuit soft board is purchased from PDTL7123250, which is a copper foil, a polyimide film, and a copper foil. The laminated structure is formed by compression bonding. After etching the circuit on the surface of the flexible board, the surface copper circuit pattern is browned to obtain a browned circuit flexible board.

Feature description

The resin composition according to the present invention and various kinds of articles made from it, such as prepreg, laminated board, printed circuit board, flexible multilayer board, or rigid-flex board, can achieve one, more or all of the following ideal characteristics: Low flow volume: For example, the flow volume measured by referring to the method described in IPC-TM-650 2.3.17.2 is less than or equal to 60 mil, preferably less than or equal to 30, 28, 26, 25 Or 21 mils, such as between 21 and 30 mils. Generally speaking, resin compositions with a low flow rate are suitable for use in flexible and rigid boards, while resin compositions with a high flow rate are relatively unsuitable for use in flexible and hard boards. Low dust weight loss: For example, the dust loss is less than or equal to 0.35%, preferably less than or equal to 0.34%, 0.29%, 0.26%, 0.21%, 0.18%, or 0.16%, such as between 0.15% and 0.35%. Generally speaking, excessive chip loss indicates that the chip loss is serious (for example, greater than 0.50%), which causes the circuit pattern on the surface of the circuit board to be contaminated, and then affects the quality and yield of the laminated product. The conventional low-flow adhesive prepreg often has the disadvantage of large chip loss. If these products are used for back-end processing and pressing after circuit board drilling, the circuit pattern will be contaminated due to chip loss, which is easy to cause. The circuit is abnormally connected and short-circuited, or unevenness occurs when the circuit board is increased in layer, which increases the scrap rate of the finished product. High tensile strength at high temperature: For example, the tensile force measured at 280 ^o C with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 5.0 lb / in, preferably greater than or equal to 5.1 lb / in, 5.2 lb / in or 5.4 lb / in, for example between 5.0 lb / in and 5.5 lb / in. Generally speaking, the copper foil substrate with the copper foil and the substrate insulation layer under high temperature pull-down force is less than 5.0 lb / in. When soldering electronic components to the circuit board at high temperature, the probability of the pads falling off is high, which easily leads to manufacturing. The yield of the finished product is reduced. In the embodiment where the high-temperature tensile force is greater than 5.0 lb / in, the probability of the pads falling off is low when the electronic component is soldered to the circuit board, and the yield of the finished product is high. High tensile strength at room temperature: For example, the tensile force measured at room temperature (about 25 ^o C) with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 6.0 lb / in, preferably greater than or equal to 6.3 lb / in, 6.8 lb / in, 6.9 lb / in, or 7.0 lb / in, such as between 6.0 lb / in and 7.5 lb / in. Low dielectric constant (Dk): For example, the dielectric constant (Dk) measured at 2 GHz with reference to the method described in JIS C2565 is less than or equal to 3.70, preferably less than or equal to 3.68, 3.67, 3.62 3.58 or 3.52, for example between 3.52 and 3.70. Low dielectric loss (Df): For example, the dielectric constant (Df) measured at 2 GHz with reference to the method described in JIS C2565 is less than or equal to 0.0140, preferably less than or equal to 0.0136, 0.0135, 0.0133, 0.0132 or 0.0112, for example between 0.0112 and 0.0140. High flame retardancy: For example, the flame retardancy measured according to the method of UL94 standard reaches V-0 level. Polyimide test board with high tensile strength: Polyimide test board made of prepreg, measured at room temperature (approximately 25 ^o C) with reference to the method described in IPC-TM-650 2.4.8 The pulling force is greater than or equal to 5.0 lb / in, preferably greater than or equal to 5.1 lb / in, 5.2 lb / in, 8.0 lb / in or 8.1 lb / in, such as between 5.0 lb / in and 8.5 lb / in . The flexible multilayer board has high heat resistance: the flexible multilayer board is measured with reference to the method described in IPC-TM-650 2.6.27 and the total number of reflows to the burst is 15 or more.

Unlike conventional resin compositions that use different composition components or ratios, the present invention encompasses resin compositions and their products that can achieve any of the foregoing, any combination of two or more, or all of the foregoing characteristics, and are therefore more capable of Meet the needs of the industry.

Specific embodiment

Using various raw materials from the following sources, the resin compositions of the examples (E1 to E6) and the comparative examples (C1 to C15) of the present invention were prepared according to the dosages in Table 1, and various test samples were further prepared. Phenolic novolac epoxy resin: Phenolic novolac epoxy resin, PNE-177, purchased from Changchun artificial resin. Biphenyl epoxy resin: Biphenyl epoxy resin, NC-3000, purchased from NIPPON KAYAKU. DCPD epoxy resin: Dicyclopentadiene epoxy resin, HP-7200H, purchased from Dainippon Ink Chemistry. Bisphenol A novolac epoxy resin: Bisphenol A novolac epoxy resin, BE-188, purchased from Changchun artificial resin. DICY: Dicyandiamide, purchased from Kingyorker Enterprise Co. Ltd. PVB: polyvinyl butyral, polyvinyl butyral, purchased from Eastman. Phenoxy: phenoxy resin, YP50S, purchased from Nippon Steel Corporation. DOPO-TAIC: Tripolytriallyl isocyanate containing DOPO, NPEP-208, purchased from Nanya Plastics. Phosphazene: Phosphazene compound, SPB-100, purchased from Otsuka Chemical Company. Melamine polyphosphate: Melamine polyphosphate, MP-200, purchased from BASF. Phosphinate: Hypophosphite, OP-935, purchased from Clariant. DOPO-BPAN: DOPO phenolic flame retardant, XZ92741, purchased from The Dow Chemical. 2E4MI: 2-ethyl-4-methylimidazole, purchased from Shikoku Chemical. Silica: Fused Silica, 525, purchased from Silco. MEK: methyl ethyl ketone, from any source. DMAC: dimethylacetamide, unlimited sources. Table 1 (continued)

The test methods for each characteristic are explained below.

Flow-in: Take 3 in. × 4 in. Prepregs mentioned above and punch out two circular holes with a diameter of 25 mm by using a manual punching machine. 4 in. × 4 in. Prepreg after round hole), refer to the definition of IPC-TM-650 2.3.17.2 standard, according to "steel plate / release film / buffer material / release film / three prepregs / 15 mil substrate / Steel plate ”, and heat-pressed under the conditions of temperature 171 ± 3 ^o C and pressure 1452 ± 70 kgf / 16in ² for 5 minutes. The hot-pressed sample was placed in a glue flow measurement system (Resin Flow Analysis System, Model SP-IMSV7 (purchased from Sanpeng Instrument Co., Ltd.) was used to measure the amount of flow glue. 15 mil substrate is the same as defined in IPC-TM-650 2.3.17.2.

Dust weight loss: Cut the prepreg into a width of 10 cm × 10 cm. First weigh its weight W0. Use a blade to cut the prepreg at a length of 9 cm per knife, perpendicular to the same specific side of the prepreg, and cut in parallel. Cut 30 knives, and then at a frequency of 2 times per second, the amplitude of the hand is about 10 cm, and re-weigh after shaking up and down 50 times. The weight obtained is W1. Use the following formula to calculate the amount of chips. Repeat 4 times. Take the average.

Dielectric constant (Dk): In the measurement of the dielectric constant, the above copper-free substrate (2 layers) was selected as the sample to be measured, and a microwave dielectrometer (purchased from AET Japan) was used according to JIS The method described in C2565 measures each sample to be tested at room temperature and a frequency of 2 GHz. The lower the dielectric constant, the better the dielectric characteristics of the sample to be measured, and the difference in Dk value less than 0.05 indicates that there is no significant difference in the dielectric constant of the substrate.

Dielectric loss (Df): In the measurement of dielectric loss, the above copper-free substrate (2 layers) was selected as the sample to be measured, and a microwave dielectrometer (purchased from AET Japan) was used, in accordance with JIS The method described in C2565 measures each sample to be tested at room temperature and a frequency of 2 GHz. The lower the dielectric loss, the better the dielectric characteristics of the sample to be tested. The difference in Df value is less than 0.0005, which means that there is no significant difference in the dielectric loss of the substrate. The difference in Df value is greater than 0.0005, which means that there is a significant difference between the dielectric losses of different substrates. .

Flame retardance test (UL94): In the flame retardance test, the above-mentioned flame resistance test substrate of 125 mm × 13 mm was selected as the sample to be tested; the measurement was performed according to the UL94 standard method, and the flame retardancy analysis results were V-0, The V-1 and V-2 grades indicate that the flame retardancy of V-0 is better than the flame retardance of V-1, the flame retardance of V-1 is better than the flame retardance of V-2, and the burned sample represents resistance. The worst flammability.

Tension of copper foil on room temperature substrate (room temperature P / S): Cut the copper foil substrate (5 layers) into rectangular samples with a width of 24 mm and a length of more than 60 mm, and etch the surface copper foil, leaving only a width of 3.18 mm and a strip of copper foil with a length greater than 60 mm, measured with a universal tensile strength tester at room temperature (approximately 25 ^o C) according to the method described in IPC-TM-650 2.4.8. The force (lb / in) required for the foil to pull away from the substrate surface.

Tension of copper foil on high temperature substrate (high temperature P / S): Cut the copper foil substrate (5 layers) into rectangular samples with a width of 24 mm and a length of more than 60 mm, and etch the surface copper foil, leaving only the width of 3.18 mm. The strip copper foil uses a universal tensile strength tester (purchased from Shimadzu). The test method refers to the method described in IPC-TM-650 2.4.8. The difference is that the high temperature substrate is used to test the copper foil tensile force further using a closed high temperature. Furnace (purchased from Shimadzu) heated the tensile test kit and substrate of the universal tensile strength tester to 280 ^o C, so that the temperature of the substrate and the surrounding environment was 280 ^o C, and then measured the force required to pull the copper foil away from the surface of the substrate (lb / in).

Polyimide pull (PI P / S): Cut the polyimide pull test board into a rectangle with a width of 24mm and a length of more than 60mm, and etch the surface copper foil to leave only a copper foil with a width of 3.18 mm. Tensile strength testing machine, the test method refers to the method described in IPC-TM-650 2.4.8, the difference is that the test position is the bonding surface of the polyimide film and the prepreg. The test will be performed at room temperature (about 25 ^o C). The force required to separate the polyimide film from the insulating substrate (lb / in).

Multilayer flexible board reflow test (referred to as PI reflow): In the multilayer flexible board reflow test, the flexible multilayer board is placed in a 260 ^o C reflow furnace and tested in accordance with the IPC-TM-650 2.6.27 reflow test standard. After each pass through the reflow machine, the person visually observes whether there is a bump on the surface of the substrate. If there is no bump, it means that the board is not burst. If there is a bump, it means that the board is burst. .

The test results are shown in Table 2 below. Table 2 Characteristic test results of the examples and comparative examples Table 2 (continued)

The following phenomena can be observed by comparing Tables 1 and 2.

It can be seen from Example E1 and Comparative Examples C1 to C9 that the combination of DOPP-containing tripolyisocyanate and phosphazene, compared with other types of flame retardants, does not affect electrical properties. , With lower chip removal and higher adhesion.

Observation of Example E1 and Comparative Example C14 revealed that the use of phosphazene alone had poor adhesion performance and poor heat resistance.

Observation of Example E1 and Comparative Example C15 shows that the use of DOPP-containing triallyl isocyanate alone has higher chip removal and higher dielectric loss.

By comprehensively observing each of the examples and comparative examples, it can be seen that the present invention uses a resin composition formed by combining an epoxy resin with a hardener, DOPP-containing triallyl isocyanate, and phosphazene, which has a low glue flow. (Less than or equal to 30 mils), low chip loss (chip reduction below 0.35%), low dielectric constant (less than 3.7), low dielectric loss (not more than 0.0140), flame retardancy reaching V-0 level, Strong tensile strength at room temperature (more than 6 lb / in), and high temperature (280 ^o C) good tensile strength (more than 5 lb / in), strong PI tensile strength (more than 5 lb / in) and high heat resistance (flexible multilayer board) Reflow test is greater than 15 times) and other advantages.

The above implementations are merely auxiliary descriptions in nature, and are not intended to limit the subject matter of the application or the applications or uses of the embodiments. In this article, the term "exemplary" means "as an example, example, or illustration." Any of the exemplary implementation aspects herein are not necessarily interpreted as being better or more advantageous than other implementation aspects.

In addition, although at least one illustrative example or comparative example has been proposed in the foregoing embodiment, it should be understood that the present invention may have a large number of variations. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the subject matter of the application requested in any way. Rather, the foregoing embodiments will provide a simple guide for those of ordinary skill in the art to implement one or more of the embodiments described. In addition, various changes can be made to the function and arrangement of the elements without departing from the scope defined by the scope of the patent application, and the scope of the patent application includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

no

Claims (19)

A resin composition includes an epoxy resin, a hardener, a triallyl isocyanate containing DOPO, and phosphazene. The resin composition according to claim 1, comprising: 100 parts by weight of an epoxy resin; 1 to 50 parts by weight of a hardener; 10 to 30 parts by weight of a DOPO-containing triallyl isocyanate; and 10 to 30 parts by weight of phosphazene. The resin composition according to claim 1, wherein the total amount of the triallyl tripolyisocyanate and phosphazene containing DOPO is 20 to 60 parts by weight relative to 100 parts by weight of the epoxy resin. The resin composition according to claim 1, wherein the DOPO-containing triallyl isocyanate includes the following structure: . The resin composition according to claim 1, wherein the phosphazene includes the following structure: Where n is an integer from 1 to 6. The resin composition according to claim 1, wherein the hardener is an amine hardener, a phenoxy resin, polyphenylene ether, polyvinyl butyral, polyolefin, polyester resin, styrene maleic anhydride, benzene And oxazine resin, maleimide, cyanate resin, or a combination thereof. The resin composition according to claim 1, further comprising: a flame retardant, an inorganic filler, a hardening accelerator, a solvent, a silane coupling agent, or a combination thereof. A resin composition comprising: 100 parts by weight of an epoxy resin; 1 to 50 parts by weight of a hardener; 10 to 30 parts by weight of a DOPO-containing tripolytriallyl isocyanate; and 10 to 30 parts by weight Phosphazene, where: DOPO-containing triallyl isocyanate includes the following structures: ; And phosphazene includes the following structures: , Where n is an integer from 1 to 6. An article made of the resin composition according to claim 1, comprising a prepreg, a laminated board, a printed circuit board, a flexible multilayer board, or a rigid-flexible board. The article according to claim 9, which is a prepreg, and the prepreg volume of the prepreg is less than or equal to 30 mils. The article according to claim 9, which is a prepreg, and the chip loss of the prepreg is less than or equal to 0.35%. The article according to claim 9, which is a laminated board, and the tensile force of the laminated board measured at 280 ^o C with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 5.0 lb / in. The article according to claim 9, which is a laminated board, and the tensile force of the laminated board measured at room temperature with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 6.0 lb / in. The article according to claim 9, which is a prepreg, and a polyimide tensile test board made of the prepreg is measured at room temperature with reference to the method described in IPC-TM-650 2.4.8. Greater than or equal to 5.0 lb / in. The article as described in claim 9, which is a flexible multilayer board, and the flexible multilayer board is measured with reference to the method described in IPC-TM-650 2.6.27 and the total number of reflows to the burst is 15 or more return. The article according to claim 9, which is a laminated board, and the dielectric constant (Dk) of the laminated board measured at a frequency of 2 GHz with reference to the method described in JIS C2565 is less than or equal to 3.7. The article according to claim 9, which is a laminated board, and the dielectric loss (Df) of the laminated board measured at a frequency of 2 GHz with reference to the method described in JIS C2565 is less than or equal to 0.0140. The article as described in claim 9, which is a laminated board, and the laminated board has a flame retardancy of V-0 measured according to the method of UL94 standard. A prepreg for combining a soft board and a hard board, comprising a reinforcing material and an insulating material covering the reinforcing material, the insulating material is made by baking the resin composition described in claim 1 to a semi-cured state, Among them: The prepreg has the following characteristics: After hot pressing under the condition of a pressure of 1452 ± 70 kgf / 16in ² and measuring with the method described in IPC-TM-650 2.3.17.2, the amount of glue flowing is less than or equal to 30 densities. Ears; and the loss of cut weight or chip loss is less than or equal to 0.35%; the laminated board made of the prepreg has the following characteristics: measured at 280 ^o C with reference to the method described in IPC-TM-650 2.4.8 The tensile force obtained is greater than or equal to 5.0 lb / in; the tensile force measured at room temperature with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 6.0 lb / in; referenced at a frequency of 2 GHz The dielectric constant (Dk) measured by the method described in JIS C2565 is less than or equal to 3.7; the dielectric loss (Df) measured by reference to the method described in JIS C2565 at a frequency of 2 GHz is less than or equal to 0.0140 ; And the flame retardancy measured according to the method of UL94 specification reaches V-0 level; The polyimide tensile test board made of the cured sheet has the following characteristics: a tensile force measured at room temperature with reference to the method described in IPC-TM-650 2.4.8 is greater than or equal to 5.0 lb / in; and The flexible multi-layer board made of the prepreg has the following characteristics: The total number of reflows when the board is blasted is 15 or more times measured by referring to the method described in IPC-TM-650 2.6.27.