TWI763282B - A halogen-free flame retardant resin composition and its application - Google Patents

Abstract

The present invention relates to a halogen-free flame retardant resin composition and application thereof, which, in parts by weight of solid components, comprises the following components: (A) epoxy resin: 1-40 parts by weight; (B) end groups contain unsaturated Key phosphorus-containing benzoxazine resin: 1 to 30 parts by weight; (C) maleimide compound: 30 to 80 parts by weight; the present invention also provides prepregs, resins prepared with the resin composition Film or resin-coated copper foil, insulating boards, metal-clad laminates and printed circuit boards. The halogen-free flame retardant resin composition in the present invention effectively improves the dielectric properties of the resin composition while ensuring that the resin composition has high glass transition temperature (Tg) and high heat resistance; Laminates for printed circuits have excellent performance and excellent dimensional stability.

Description

A halogen-free flame retardant resin composition and its application

The invention relates to the technical field of laminates, in particular to a halogen-free flame retardant resin composition and its application.

With the development of communication technology, the requirements for the dielectric constant (D _k ) and dielectric loss (D _f ) of printed circuit substrates (CCL) are getting higher and higher. The consumer electronics field represented by mobile phones, notebook computers and tablet computers will be redesigned and manufactured as an important application node of 5G networks in the upcoming 5G era. Unlike in the past, its CCL material requires lower dielectric losses. At present, the main board structures of mainstream mobile phones and tablet PCs are all high-density interconnection (HDI) designs, which have higher requirements on the heat resistance of materials after curing for many times. In the process of PCB processing, in order to improve the yield of products, there are strict requirements on the dimensional stability of the substrate (CCL) and the bonding sheet (Prepreg). It is of great practical significance to develop low-dielectric and high-reliability sheets with high dimensional stability.

One of the difficulties in achieving the above goals is that in order to achieve low dielectric properties, many practitioners choose additive flame retardants such as condensed phosphate ester, phosphazene and their derivatives to achieve halogen-free flame retardant or low halogen flame retardant. However, the melting point or softening point of most additive flame retardants is low, which will significantly reduce the glass transition temperature of the resin system. When the temperature exceeds a certain limit during processing, especially when the glass transition temperature of the resin exceeds the glass transition temperature of the resin, the deformation of the substrate increases sharply. , the dimensional stability is greatly reduced. Some practitioners choose epoxy resin and phenolic resin containing phosphorus structure as flame retardant resin, but this part Resins are unsatisfactory in terms of heat resistance, reliability, and dielectric properties.

On the other hand, the use of low-polarity resin materials is easy to achieve low dielectric properties, but low-polarity materials often have poor rigidity or poor adhesion, and are prone to warping and wire throwing (copper wire and substrate separation) during PCB, resulting in scrapping. Increase manufacturing costs.

Therefore, how to effectively improve the dielectric properties and make it have excellent dimensional stability while ensuring high glass transition temperature (Tg) and high heat resistance of printed circuit laminates has become an urgent technical problem to be solved.

In order to solve the above technical problems, the present invention provides a halogen-free flame retardant resin composition and its application. The halogen-free flame-retardant resin composition provided by the invention effectively improves the dielectric properties of the resin composition while ensuring that it has high glass transition temperature (Tg) and high heat resistance; The laminates have excellent properties with excellent dimensional stability.

In order to achieve this purpose, the present invention adopts the following technical means: In the first aspect, the present invention provides a halogen-free flame retardant resin composition, which, in parts by weight of solid components, comprises the following components: (A) epoxy resin : 1-40 parts by weight; (B) Phosphorus-containing benzoxazine resin containing an unsaturated bond at the end group: 1-30 parts by weight; (C) Maleimide compound: 30-80 parts by weight.

The inventor found in the research process that by adding a phosphorus-containing benzoxazine resin component containing an unsaturated bond at the end group to the resin composition, (1) the oxazine ring can be opened to form a hydroxyl group at high temperature. base, carry out chemical cross-linking reaction with epoxy resin; at the same time, the unsaturated bond contained in it can carry out chemical cross-linking reaction with unsaturated C=C double bond in maleimide compound, which can make epoxy resin and maleimide compound carry out chemical cross-linking reaction. Effective cross-linking between components such as imide compounds solves the problem of ineffective reaction between epoxy resins and maleimide compounds, thereby obtaining better dielectric properties than conventional benzoxazine . (2) Due to its effective cross-linking, a stable and reliable three-dimensional cross-linked network is formed, which not only effectively improves the dimensional stability of the prepared printed circuit laminates, but also (3) introduces phosphorus elements through chemical connection. Into the benzoxazine structure, it can greatly improve the disadvantage of phosphorus element's strong hygroscopicity, achieve a balance between key properties such as dielectric properties and heat resistance, and achieve a high glass transition temperature ( Tg) and high heat resistance, while effectively improving its dielectric properties and having excellent dimensional stability.

The phosphorus-containing benzoxazine resin component whose terminal group contains unsaturated bonds adopted in the present invention can effectively solve the problem of halogen-free flame retardant because of the phosphorus element in its molecular structure; The existence of the oxazine ring balances the drawbacks caused by the easy water absorption of phosphorus elements to the greatest extent, and effectively reduces the problem of water absorption of the board, thereby improving the dielectric stability and reliability of the resin composition. Compared with additive flame retardants, phosphorus-containing benzoxazine resins whose end groups contain unsaturated bonds can effectively ensure that phosphorus elements and the host resin are in a chemically cross-linked state, and prevent phosphorus elements from being free and easy to precipitate. Even at temperatures exceeding the melting point of most additive flame retardants, it can still maintain good performance, and it is more stable in temperature cycle tests and damp heat resistance tests. Therefore, in the resin composition of the present invention, due to the addition of the phosphorus-containing benzoxazine resin component containing unsaturated bonds at the end groups, the phosphorus-containing group and the benzoxazine structure cooperate with each other, and at the same time solve the problem of non-saturation. Reactive flame retardants are prone to problems of increased water absorption, decreased dimensional stability, and decreased heat resistance.

Compared with the existing benzoxazine resin, the phosphorus-containing benzoxazine resin component with unsaturated bond at the end group adopted in the present invention can provide more cross-linking due to the unsaturated bond in its molecular structure. The junction reacts with the maleimide compound, and it is easier to form a dense cross-linked network, and has Effectively reduces the dielectric constant and dielectric loss factor.

In the resin composition of the present invention, the content of the epoxy resin (A) is 1 to 40 parts by weight, such as 1 part by weight, 2 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight Parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, or 40 parts by weight, ideally 5 to 30 parts by weight.

In the resin composition of the present invention, the content of the phosphorus-containing benzoxazine resin (B) whose end groups contain unsaturated bonds is 1 to 30 parts by weight, such as 1 part by weight, 2 parts by weight, 5 parts by weight parts, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight, ideally 5 to 25 parts by weight.

In the resin composition of the present invention, the content of the maleimide compound (C) is 30 to 80 parts by weight, such as 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight parts, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or 80 parts by weight, ideally 35 to 70 parts by weight.

In the resin composition of the present invention, the epoxy resin (A) can be selected from dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate modified epoxy resin, biphenyl epoxy resin, bisphenol A type epoxy resin, phenol type novolac epoxy resin, o-cresol type epoxy resin, epoxidized polybutadiene resin, epoxy resin containing naphthalene ring, bisphenol F type epoxy resin, trifunctional epoxy resin, Any one or a combination of at least two of hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F type epoxy, wherein typical but non-limiting combinations are: dicyclopentadiene epoxy resin and phosphorus-containing epoxy Resin, biphenyl epoxy resin and bisphenol A type epoxy resin, o-cresol type epoxy resin and epoxidized polybutadiene resin, o-cresol type epoxy resin and dicyclopentadiene type epoxy resin.

In the resin composition of the present invention, the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond at the end group is a phosphorus-containing benzoxazine resin containing an unsaturated group at the molecular end group.

Ideally, the phosphorus-containing benzoxazine resin (B) containing unsaturated bonds at the end group has the following structure:

或

；其中m為重複單元數量的平均值，為3~10的任意數，例如3、3.5、4、4.5、5、5.5、6、7、8、9、10等；n為重複單元數量的平均值，為0~10的任意數，例如0、0.1、1、1.5、2、3、4、5、6、7、8、9、10等；R₁為H、C1~C4(例如C2或C3)的直鏈或支鏈烷烴、取代或未取代的芳基、取代或未取代的芳氧基中的一種；Y選自下列結構：

其中，

中穿過苯環的兩條直線代表鏈接鍵，在羥基鄰位的為甲基；Z為共價鍵或選自下列結構：

Q is a substituted or unsubstituted unsaturated bond-containing group; X is

or

; where m is the average number of repeating units, which is any number from 3 to 10, such as 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, 9, 10, etc.; n is the average number of repeating units The value is any number from 0 to 10, such as 0, 0.1, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.; R ₁ is H, C1~C4 (such as C2 or C3) a kind of straight-chain or branched alkane, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy; Y is selected from the following structures:

in,

The two straight lines passing through the benzene ring represent the linking bond, and the one in the ortho-position of the hydroxyl group is a methyl group; Z is a covalent bond or is selected from the following structures:

Ideally, Q is a group that forms a hydrophobic alkyl chain after curing, further ideally a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted styryl group, a substituted or unsubstituted acrylate group one of substituted or unsubstituted vinyl groups, substituted or unsubstituted allyl groups, substituted or unsubstituted styryl groups, and substituted or unsubstituted phenyl-containing acrylate groups.

The substitution referred to throughout the present invention refers to substitution by halogen, alkyl, alkoxy and other substituents.

Ideally, the terminal group-containing unsaturated phosphorus-containing benzoxazine resin is obtained by reacting a phosphorus-containing diphenol compound, an unsaturated bond-containing amine compound and methanol.

式(a)、式(b)中，所述m、n、R₁、Q、Z和Y均具有與式(B)中相同的選擇範圍。 The phosphorus-containing benzoxazine resin whose terminal group contains an unsaturated bond according to the present invention is selected from one of formula (a) and formula (b) or a combination of at least two of them: formula (a)

In formula (a) and formula (b), the m, n, R ₁ , Q, Z and Y all have the same selection range as in formula (B).

Ideally, Y and Z can be the same or different. Y and Z are independently selected from the following structures:

Ideally, formula (a) is selected from at least one or a combination of two or more of the following formulae (a1), (a2) or (a3):

式(a1)至(a3)中所述Q具有與式(B)中相同的選擇範圍。

The Q in the formulae (a1) to (a3) has the same selection range as in the formula (B).

Ideally, formula (b) is selected from at least one or a combination of two or more of the following formulae (b1), (b2), (b3), (b4) or (b5):

In the formulae (b1) to (b5), both of the n and Q have the same selection range as in the formula (B).

Further desirably, the terminal unsaturated bond in the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond in the terminal group of the present invention is selected from vinyl, styryl, allyl or phenyl group. Any one or a combination of at least two of the acrylate groups.

Further ideally, the phosphorus-containing benzoxazine resin (B) whose terminal group contains an unsaturated bond according to the present invention is exemplified but not limited to the following structure:

Wherein, the n has the same selection range as in formula (B).

In the resin composition of the present invention, the maleimide compound (C) is a compound, monomer, mixture, oligomer or polymer containing a maleimide functional group in the molecule. Unless otherwise specified, the maleimide compound used in the present invention is not particularly limited, and can be any one or more types of prepregs suitable for prepregs, copper-clad prepregs, resin films, resin-coated copper foils, laminates or printed circuits Maleimide compound made of plates. Specific examples include, but are not limited to: 4,4'-diphenylmethanebismaleimide, polyphenylenemethanemaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3- phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2 , any one or at least two of 6-dimethylbenzenemaleimide, N-phenylmaleimide, maleimide compounds containing aliphatic long-chain structure and prepolymers thereof Combinations, where typical but non-limiting combinations are: 4,4'-diphenylmethanebismaleimide and polyphenylenemethanemaleimide, m-phenylene bismaleimide, and bisphenol A Diphenyl ether bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane and 2,3-dimethylbenzylmaleimide Wait.

Ideally, described prepolymer is selected from the prepolymer of diallyl compound and maleimide compound, the prepolymer of diamine and maleimide compound, polyfunctional amine and maleimide compound. Prepolymers of imide compounds or prepolymers of acidic phenolic compounds and maleimide compounds any one or a combination of at least two.

For example, the maleimide compound may be traded under the trade names BMI-70, BMI-80, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI -3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H are maleimide compounds produced by Daiwakasei Corporation. The trade names are BMI, BMI-70, BMI-80 and other maleimide compounds produced by Japan KI Chemical. The trade names are D936, D937, D939, D950 and other maleimide compounds produced by Sichuan Dongcai Technology Co., Ltd.

For example, the maleimide compound containing aliphatic long chain structure can be traded under the trade names of BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000 and other maleimide compounds produced by Designer Molecular Company.

The resin composition of the present invention may further contain a flame retardant (D).

Ideally, the flame retardant (D) is selected from resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6- Any one or a combination of at least two of xylyl phosphate), dimethyl methyl phosphate, additive phosphazene compound or reactive phosphazene compound.

Ideally, in the resin composition, the content of the flame retardant (D) is 0.1 to 20 parts by weight, such as 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight parts by weight, 10 parts by weight, 12 parts by weight or 20 parts by weight.

The resin composition of the present invention may further contain a filler (E).

Ideally, the filler (E) is selected from any one of aluminum hydroxide, silica, stone powder, diaspore, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay or mica or A combination of at least two.

In the present invention, the physical form of the filler can be flake, rod, spherical, hollow Heart-shaped, angular, granular, fibrous or plate-shaped, etc., can be selectively treated with silane coupling agent.

Ideally, in the resin composition, the content of the filler (E) is 10 to 250 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 40 parts by weight, 50 parts by weight , 70 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 200 parts by weight, or 250 parts by weight.

The resin composition of the present invention may further contain a polyphenylene ether resin (F).

The polyphenylene ether resin (F) is selected from hydroxyl-terminated polyphenylene ether and/or unsaturated double bond-terminated polyphenylene ether resin, commercially available hydroxyl-terminated polyphenylene ether and/or unsaturated bis Examples of bond-terminated polyphenylene ether resins include OPE-2ST and OPE-2EA available from MITSUBISHI GAS CHEMICAL, SA-90 and SA-9000 available from SABIC , PP807 products that can be purchased from Jinyi Chemical, and polyphenylene ether resins that can be purchased from Asahi Kasei (ASAHI KASEI).

In the resin composition, the content of the polyphenylene ether resin (F) is 0.1 to 30 parts by weight, such as 0.1 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight , 25 parts by weight or 30 parts by weight.

The resin composition of the present invention may further contain an active ester resin (G). The active ester resin is not particularly limited, and refers to a resin having an active ester group in its structure. Desirable are active ester compounds containing dicyclopentadiene-type diphenol structure, active ester compounds containing naphthalene structure, active ester compounds containing phenol novolak acetylated compounds, and phenol novolac-containing benzyl compounds Among them, the active ester compound containing naphthalene structure and the active ester compound containing dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" means a divalent structural unit formed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester resin, active esterification containing dicyclopentadiene-type diphenol structure "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.), etc.; active ester compounds containing a naphthalene structure include "EXB9416-70BK", "EXB-8150-65T" (manufactured by DIC Co., Ltd.), etc.; Examples of active ester compounds of acetylated compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation) and the like; examples of active ester compounds of benzyl compounds of phenol novolaks include "YLH1026" (manufactured by Mitsubishi Chemical Corporation) and the like; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) etc. can be mentioned as the active ester curing agent of the acetylated compound of phenol novolak; "YLH1026" can be mentioned as the active ester curing agent of the benzyl compound of phenol novolak (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation), etc.

Ideally, the number average molecular weight of the active ester resin is below 1800, and the molecular weight can be, for example, 500, 550, 600, 750, 820, 1050, 1200, 1450 or 1800.

In the resin composition, the content of the active ester resin (G) is 0.1 to 30 parts by weight, such as 0.1 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight.

The resin composition of the present invention may further contain a curing accelerator (H).

The curing accelerator is selected from any one or a combination of at least two of imidazole accelerators and derivatives thereof, pyridines, Lewis acids, amines, phenolic compounds or cyanate ester compounds.

In the resin composition, the content of the curing accelerator (H) is 0.1 to 5 parts by weight, such as 0.1 parts by weight, 0.5 parts by weight, 1 part by weight or 5 parts by weight.

As an optional technical means, in the resin composition of the present invention, organic solid In terms of parts by weight, it includes the following components: (A) epoxy resin: 1 to 40 parts by weight; (B) phosphorus-containing benzoxazine resin whose end groups contain unsaturated bonds: 1 to 30 parts by weight; (C) Maleimide compound: 30-80 parts by weight; (D) flame retardant: 0.1-15 parts by weight; (E) filler: 10-250 parts by weight; (F) hydroxyl-terminated polyphenylene ether resin or/and Unsaturated double bond-terminated polyphenylene ether resin: 0.1 to 30 parts by weight; (G) active ester resin: 0.1 to 30 parts by weight; (H) accelerator: 0.1 to 5 parts by weight.

In a second aspect, the present invention provides a prepreg, resin film or resin-coated copper foil, the prepreg, resin film or resin-coated copper foil comprising the halogen-free flame retardant resin composition described in the first aspect.

Prepreg is a resin matrix impregnated with continuous fibers or fabrics under strictly controlled conditions to make a composition of resin matrix and reinforcement, which is an intermediate material in the manufacture of composite materials.

The prepreg of the present invention includes a base material and a halogen-free resin composition attached to the base material. The base material is a non-woven fabric or other fabric, and typically but not limitedly includes natural fibers, organic synthetic fibers or inorganic fibers and the like.

Ideally, the prepreg is obtained by impregnating and drying the base material in the halogen-free flame retardant resin composition provided in the first aspect; The halogen-free flame-retardant resin composition adhered to the base material after impregnation and drying.

For the preparation method of the prepreg according to the present invention, those with ordinary knowledge in the technical field can refer to the existing preparation method of the prepreg, which is not specifically limited in the present invention. The typical but non-limiting preparation of the prepreg The method includes the following steps:

Using the glue liquid impregnation base material of the halogen-free flame retardant resin composition provided in the first aspect, the impregnated glass cloth is heated at 140~210°C (for example, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C). ℃, etc.) in an oven by heating and drying for 1 to 15 minutes (for example, 2 minutes, 4 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, etc.).

The resin film is formed by semi-curing the resin composition described in the first aspect after baking and heating. Specifically, the resin film can be obtained by coating the resin composition described in the first aspect on the release material, baking, heating, and semi-curing, and then removing the release material.

The resin-coated copper foil is formed by coating the resin composition described in the first aspect on the copper foil and then semi-curing after baking and heating.

In a third aspect, the present invention provides an insulating board, the insulating board includes at least one piece of the prepreg described in the second aspect.

In a fourth aspect, the present invention provides a metal foil clad laminate, the metal foil clad laminate comprising at least one prepreg according to the second aspect and one or both sides of the laminated prepreg metal foil.

Laminate is a kind of laminate, which is a whole by lamination and thermocompression of one or more layers of fibers or fabrics (ie prepregs) impregnated with resin.

In a fifth aspect, the present invention provides a printed circuit board, the printed circuit board comprising at least one prepreg according to the second aspect, or at least one insulating board according to the third aspect, or at least one first The metal-clad laminate described in the four aspects.

In the present invention, the terms "comprising", "including", "having", "containing" or any other similar terms are open linkers intended to encompass non-exclusive inclusions. For example, a composition or article of manufacture containing a plurality of elements is not limited to only those elements listed herein, but may also include other elements not expressly listed, but which are generally inherent to the composition or article of manufacture.

Compared with the prior art, the present invention has at least the following effects:

(1) In the present invention, by adding a phosphorus-containing benzoxazine resin component containing an unsaturated bond at the end group to the resin composition, it enables effective cross-linking between components such as epoxy resin and maleimide compound. It solves the problem of ineffective reaction between epoxy resin and maleimide compound. At the same time, because of its effective cross-linking to form a stable and reliable three-dimensional cross-linked network, it not only effectively improves the printed circuit performance. The dimensional stability of the laminate is also balanced between key properties such as dielectric properties and heat resistance. Improve its dielectric properties and have excellent dimensional stability.

(2) In the resin composition of the present invention, the phosphorus-containing benzoxazine resin whose end group contains unsaturated bonds provides the unsaturated bonds to react with maleimide, increases the crosslinking density, and at the same time, due to the benzoxazine The role of the oxazine ring effectively inhibits the increase in hygroscopicity and the decrease in thermal reliability and dielectric properties caused by phosphorus elements. Dimensional stability is also significantly improved.

(3) The phosphorus-containing benzoxazine resin component whose end groups contain unsaturated bonds used in the present invention can effectively solve the problem of halogen-free flame retardant due to the phosphorus element contained in its molecular structure.

(4) The halogen-free flame-retardant resin composition provided in the present invention effectively improves the dielectric properties of the resin composition while ensuring that the resin composition has high glass transition temperature (Tg) and high heat resistance; Prepregs and laminates for printed circuits have excellent properties with excellent dimensional stability.

(5) The glass transition temperature (Tg) of the laminate prepared from the halogen-free flame-retardant resin composition provided by the present invention can reach above 200° C., the dielectric constant can reach below 3.5, the dielectric loss can reach below 0.004, and the thermal delamination can be achieved. The time is up to 60 minutes, and it can pass the 168-hour high temperature and high humidity test and the cold and heat shock cycle test. The center value of the dimensional stability test is below 500 (preferably below 300).

In order to facilitate the understanding of the present invention, examples of the present invention are as follows. Technical field It should be understood by those with ordinary knowledge in the present invention that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

The following preparation example exemplarily provides the preparation method of the phosphorus-containing benzoxazine resin whose terminal group contains an unsaturated bond:

Preparation Example 1

將350g(0.5mol)的OL-1001(購於美國FRX公司，n為3)和1000g適量的甲苯置於三口燒瓶中，向其中加入28.5g(0.5mol)的烯丙胺，75g(1mol)的甲醇水溶液(40%)。加完後以低於2℃/分鐘的升溫速率升至90℃，反應5小時。然後將溫度升至120℃，在小於30 tor的壓力下，60分鐘內將溶劑抽乾，並將樹脂轉移至燒杯中，冰水中冷卻得到含磷的不飽和鍵苯並噁嗪樹脂。

350g (0.5mol) of OL-1001 (purchased from FRX company in the United States, n is 3) and 1000g of appropriate amount of toluene were placed in a three-necked flask, to which was added 28.5g (0.5mol) of allylamine, 75g (1mol) of Aqueous methanol (40%). After the addition, the temperature was raised to 90°C at a heating rate of less than 2°C/min, and the reaction was carried out for 5 hours. Then the temperature was raised to 120°C, and the solvent was drained within 60 minutes under a pressure of less than 30 tor, and the resin was transferred to a beaker and cooled in ice water to obtain a phosphorus-containing unsaturated bond benzoxazine resin.

Preparation Example 2

將400g(0.25mol)的端羥基磷酸酯(購於ICL，n為6)和1000g適量的甲苯置於三口燒瓶中，向其中加入14.25g(0.25mol)的烯丙胺，75g(0.5mol)的甲醇水溶液(40%)。加完後以低於2℃/分鐘的升溫速率升至90℃，反應5小時。然後將溫度升至120℃，在小於30 tor的壓力下，60分鐘內將溶劑抽乾， 並將樹脂轉移至燒杯中，冰水中冷卻得到含磷的不飽和鍵苯並噁嗪樹脂。

400g (0.25mol) of terminal hydroxy phosphate (purchased from ICL, n is 6) and 1000g appropriate amount of toluene were placed in a three-necked flask, 14.25g (0.25mol) of allylamine was added to it, 75g (0.5mol) of Aqueous methanol (40%). After the addition, the temperature was raised to 90°C at a heating rate of less than 2°C/min, and the reaction was carried out for 5 hours. Then the temperature was raised to 120°C, and the solvent was drained within 60 minutes under a pressure of less than 30 tor, and the resin was transferred to a beaker and cooled in ice water to obtain a phosphorus-containing unsaturated bond benzoxazine resin.

Preparation Example 3

370g (0.5mol) of SPH-100 (purchased from Japan Otsuka Chemical) and 1000g appropriate amount of toluene were placed in a three-necked flask, 28.5g (0.5mol) of allylamine, 75g (1.0mol) of methanol aqueous solution ( 40%). After the addition, the temperature was raised to 90°C at a heating rate of less than 2°C/min, and the reaction was carried out for 5 hours. Then the temperature was raised to 120°C, and the solvent was drained within 60 minutes under a pressure of less than 30 tor, and the resin was transferred to a beaker and cooled in ice water to obtain a phosphorus-containing unsaturated bond benzoxazine resin.

In order to better illustrate the present invention and facilitate the understanding of the technical means of the present invention, typical but non-limiting embodiments of the present invention are as follows:

In the examples and comparative examples, unless otherwise specified, the parts represent parts by weight, and the % represent "weight%".

The materials and model information involved in the examples and comparative examples are as follows:

(A) Epoxy resin:

A1: DCPD type epoxy resin with model HP-7200H-75M purchased from DIC in Japan, epoxy equivalent 270;

A2: Biphenyl epoxy resin with model NC-3000H purchased from Nippon Kayaku, epoxy equivalent 290;

A3: Trifunctional epoxy resin with model TFE-1250 purchased from Changchun Ruizao Resin Factory, epoxy equivalent 215;

(B-1) Phosphorus-containing benzoxazine resin whose terminal group contains unsaturated bond

B-11: Phosphorus-containing benzoxazine resin (OL1001) containing an unsaturated bond in the terminal group obtained in Preparation Example 1;

B-12: Phosphorus-containing benzoxazine resin (PMP) containing an unsaturated bond in the terminal group obtained in Preparation Example 2;

B-13: Phosphorus-containing benzoxazine resin (SPH100) containing an unsaturated bond in the terminal group obtained in Preparation Example 3;

(B-2) Benzoxazine resin

B-21: KZH-5031 of KOLON;

B-22: ODA type benzoxazine resin D129, purchased from Sichuan Dongcai Technology;

B-23: Phosphorus-containing benzoxazine resin (9-BZ) disclosed in CN103421192A;

(C) Maleimide compound

C1: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, model BMI-70, purchased from KI CHEMICAL in Japan;

C2: D950 modified maleimide purchased from Sichuan Dongcai Technology;

(D) Flame Retardant

D1: Product model SPB-100 purchased from Otsuka Chemical Co., Ltd., Japan;

D2: The product of model PX-200 purchased from Japan's Daiba Chemical;

(E) Packing

E1; spherical silica NQ2025W purchased from Jiangsu Lianrui New Materials Co., Ltd.;

E2: Talc powder AG-609 purchased from U.S. Special Mine;

(F) Polyphenylene ether resin

F1: methacrylate-terminated polyphenylene ether resin, model SA-9000, purchased from SABIC

F2: Hydroxy-terminated polyphenylene ether resin, model SA-90, purchased from SABIC

(G) Active ester resin

G1: Active ester resin with model HPC-8000-65T purchased from DIC Corporation of Japan

G2: Active ester resin with model HPC-8150-62T purchased from DIC Corporation of Japan

(H) Curing accelerator

H1: 2-ethyl-4-methylimidazole purchased from Shikoku Chemicals, Japan.

The resin compositions provided in the examples and comparative examples shown in Table 1 and Table 2 below were used to prepare laminates for printed circuits according to the following methods, and the performance tests were carried out on the prepared laminates.

通過加熱和加壓作用分別使上述實施例和對比例的樹脂組成物製備得到的預浸料黏合在一起，製成的層壓板；

在步驟

製得的層壓板的兩面上黏合金屬箔；

在層壓機中進行層壓；在步驟

和

的過程中，使用8片預浸料和2片一盎司(35μm厚)的銅箔疊合在一起；在步驟

的過程中，層壓的操作條件為：料溫100℃，控制升溫速率為2.3℃/分鐘；外層料溫90℃，施加滿壓，滿壓壓力為350psi；固化時，控制料溫在210℃，並保溫120分鐘以上。 The preparation method of the printed circuit laminate comprises:

The prepregs prepared from the resin compositions of the above examples and comparative examples are bonded together by heating and pressing, respectively, to form a laminate;

in step

Bonding metal foils on both sides of the prepared laminate;

Lamination in a laminator; in step

and

, use 8 pieces of prepreg and 2 pieces of one ounce (35μm thick) copper foil laminated together; in step

In the process of lamination, the operating conditions of lamination are: the material temperature is 100°C, and the heating rate is controlled to be 2.3°C/min; the material temperature of the outer layer is 90°C, the full pressure is applied, and the full pressure is 350 psi; during curing, the material temperature is controlled at 210°C , and keep warm for more than 120 minutes.

The formulations and performance test results of the resin compositions provided in Examples and Comparative Examples are shown in Table 1 and Table 2.

In the above table, "failed" in the thermal shock cycle test results means that the sheet has defects such as bubbling and delamination in the thermal shock cycle test; "failed" in the 168-hour high temperature and high humidity test means the sheet has undergone high temperature and high humidity treatment. When the immersion tin test was performed after 300 seconds, defects such as bubbling and delamination occurred within 300 seconds, and "pass" means that the aforementioned defects did not appear.

As can be seen from the data shown in Tables 1 to 3, the present invention can ensure that the resin composition has a high glass transition temperature (Tg) by adding a phosphorus-containing benzoxazine resin whose end groups contain unsaturated bonds in the resin composition formula. ), high heat resistance, and at the same time, the dielectric properties of the resin composition are effectively improved; and the prepreg and printed circuit laminates have excellent performance and excellent size. Dimensional stability, high temperature and high humidity resistance and thermal shock resistance. Whether it is to replace the phosphorus-containing benzoxazine resin with an unsaturated bond in the end group with other resins (Comparative Examples 2 to 4), or to change the ratio of each component in the formula (Comparative Examples 1, 5, 6, 7 and 8), which will reduce the overall performance of the product.

In the dimensional stability test of the resin composition provided by the present invention, the resin shrinkage values are all less than 500 ppm, which greatly reduces the difficulty of production control, is beneficial to improve the yield of downstream products and reduce the scrap ratio.

The items and specific methods of performance testing are:

(a) Glass transition temperature:

According to differential scanning calorimetry, it measured according to the TMA method prescribed|regulated by IPC-TM-650.

(b) Fire resistance:

Determined according to UL94 method.

(c) Water absorption:

Measure according to the method specified in 2.6.2.1 of IPC-TM-650.

(d) Dielectric constant and dielectric loss factor

The dielectric constant and dielectric loss factor at 1 GHz were measured according to the method specified in 2.5.5.5 of IPC-TM-650 by the resonance method using the strip line.

(e) Thermal delamination time T288

Measured according to the method specified in 2.4.24.1 of IPC-TM-650, unit: minute.

(f) 168 hours high temperature and high humidity test

According to IPC-TM-650.

(g) 1000 cycle of thermal shock cycle

A sheet of 1.00mm thickness is produced. A thermal shock cycle refers to: cooling from room temperature to -40°C at 5°C/min, then heating up to 120°C at a heating rate of 5°C/min, holding for 10 minutes, and then pressing 5°C/min. minute cooling rate down to room temperature.

(h) Dimensional stability test (center value)

Tested according to the method specified in IPC-TM-650. Use a 0.076mm thick plate to test its dimensional change data after baking at 150°C, and take the absolute value of the central value of at least 6 sets of data, unit: ppm.

The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those with ordinary knowledge in the technical field should understand that any improvement of the present invention, equal replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention. .

Claims (15)

A halogen-free flame retardant resin composition is characterized in that, in parts by weight of solid components, it comprises the following components: (A) epoxy resin: 1 to 40 parts by weight; (B) end groups containing unsaturated bonds containing Phosphorus benzoxazine resin: 1～30 weight part; (C) maleimide compound: 30～80 weight part; This end group contains the phosphorus benzoxazine resin (B) of unsaturated bond, its structure The formula is as follows:

Q is a substituted or unsubstituted unsaturated bond-containing group; X is

or

; where m is the average value of the number of repeating units, which is any number from 3 to 10; n is the average value of the number of repeating units, which is any number from 0 to 10; R ₁ is the straight chain or branched chain of H, C1~C4 One of alkane, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy; Y is selected from the following structures:

Z is a covalent bond or is selected from the following structures:

The halogen-free flame retardant resin composition according to claim 1, wherein Q is one of substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted styryl groups, and substituted or unsubstituted acrylate groups a kind of. The halogen-free flame retardant resin composition according to claim 1, wherein the terminal group contains unsaturated phosphorus-containing benzoxazine resin selected from one or at least two of formula (a) and formula (b). combination:

Formula (b)

In formula (a) and formula (b), the m, n, R ₁ , Q, Z and Y all have the same limited range as in formula (B). The halogen-free flame retardant resin composition according to claim 3, wherein formula (a) is selected from at least one or two or a combination of more than one of the following formulas (a1), (a2) or (a3):

The Q in formulae (a1) to (a3) has the same limited range as in formula (B). The halogen-free flame retardant resin composition according to claim 3, wherein the formula (b) is selected from at least one of the following formulas (b1), (b2), (b3), (b4) or (b5) or A combination of two or more:

In the formulae (b1) to (b5), both of the n and Q have the same limited ranges as in the formula (B). The resin composition according to claim 1, wherein, in the resin composition, the maleimide compound (C) is selected from 4,4'-diphenylmethanebismaleimide, polyphenylenemethane lyimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-di Phenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl ) Hexane, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-phenylmaleimide, allyl compound modified maleimide Any one or a combination of at least two of imide, amine-modified maleimide or acid phenolic compound-modified maleimide. The halogen-free flame retardant resin composition according to claim 1, wherein the resin composition further comprises a flame retardant (D); the flame retardant (D) is selected from resorcinol-bis(phosphoric acid) diphenyl ester), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6-xylyl phosphate), dimethyl methyl phosphate, additive type phosphazene compound or reactive type Any one or a combination of at least two of the phosphazene compounds; in the resin composition, the content of the flame retardant (D) is 0.1 to 15 parts by weight. The halogen-free flame retardant resin composition according to claim 1, wherein the resin composition further comprises a filler (E); the filler (E) is selected from aluminum hydroxide, silicon dioxide, stone powder, hydrated aluminum Stone, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay or a combination of at least two of them; in the resin composition, the content of filler (E) is 10 to 250 parts by weight . The halogen-free flame retardant resin composition according to claim 1, wherein the resin composition further comprises a polyphenylene ether resin (F); the polyphenylene ether resin (F) is selected from hydroxyl-terminated polyphenylene ether and/or unsaturated double bond-terminated polyphenylene ether resin; in the resin composition, the content of the polyphenylene ether resin (F) is 0.1 to 30 parts by weight. The halogen-free flame retardant resin composition according to claim 1, wherein the resin composition further comprises an active ester resin (G); In the resin composition, the content of the active ester resin (G) is 0.1 to 30 parts by weight. The halogen-free flame retardant resin composition according to claim 1, wherein the resin composition further comprises a curing accelerator (H); the curing accelerator is selected from imidazole accelerators and derivatives thereof, pyridines , Lewis acid, amine, phenolic or cyanate ester compound in any one or a combination of at least two; in the resin composition, the content of the curing accelerator (H) is 0.1 to 5 parts by weight. A prepreg, characterized in that the prepreg comprises the halogen-free flame retardant resin composition according to any one of claims 1 to 11. A resin-coated copper foil is characterized in that the resin-coated copper foil comprises the halogen-free flame-retardant resin composition according to any one of claims 1 to 11. A metal foil clad laminate, characterized in that the metal foil clad laminate comprises at least one prepreg as claimed in claim 12 and metal foils covering one or both sides of the laminated prepreg. A printed circuit board, characterized in that the printed circuit board comprises at least one prepreg as claimed in claim 12, or at least one metal foil-clad laminate as claimed in claim 14.