KR101814313B1 - Thermosetting resin composition and use thereof - Google Patents

Abstract

The present invention relates to a thermosetting resin composition, which comprises (A) a cyanate compound and / or a cyanate prepolymer; (B) a polyphosphonate and / or a phosphonate-carbonate copolymer. The thermosetting resin composition provided in the present invention has low dielectric constant and dielectric loss tangent, and the prepreg and the copper-clad laminate produced by using the thermosetting resin composition have excellent dielectric performance and anti-wet heat performance, and the flame retardancy is UL94V-0 grade And has good processability.

Description

THERMOSETTING RESIN COMPOSITION AND USE THEREOF BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a thermosetting resin composition, and more particularly, to a halogen-free thermosetting resin composition, a prepreg, a laminate, and a high-frequency circuit board manufactured using the composition.

As the processing speed and multi-function of electronic information processing and the continuous increase of the information transmission amount are continuously increasing, the application frequency is continuously required to be improved. Also, the demand for continuous miniaturization of the communication device is increasing, The demand for electronic devices capable of conducting information transmission is becoming increasingly urgent. At present, the operating frequency of existing communication devices is generally more than 500 MHz, the majority being 1 to 10 GHz. As the demand for a large amount of information transmission within a short period of time increases, the operating frequency becomes higher and higher, and the signal integrity becomes a problem as the frequency becomes higher. Also, the dielectric performance of the copper clad laminate material, which is the basis of signal transmission, is one of the main aspects affecting signal integrity. In general, the lower the dielectric constant of the substrate material, the faster the transmission speed, and the smaller the dielectric loss tangent, the better the signal integrity. Thus, for the substrate, how to lower the dielectric constant and the dielectric loss tangent has become a major technical problem in recent years.

In addition, the copper foil coated substrate material must have good dielectric performance, heat resistance, and mechanical performance to satisfy the PCB processing performance and performance requirements of the terminal electronic products. At the same time, the copper foil coated substrate material must have good processability, high peel strength, Good humidity resistance and UL94 V-0 flame retardant rating.

As widely known, various materials have low dielectric constant and low dielectric loss tangent characteristics. For example, polyolefin, fluorine resin, polystyrene, polyphenylene ether, Polyphenylene ether, bismaleimide-triazine resin, and polyvinyl benzene resin. Although these resins have excellent dielectric properties, they all suffer from defects such as difficulty in processing and low heat resistance, and thus they do not satisfy the requirements of copper foil-clad substrates.

CN102597089A discloses a resin composition comprising a cyanate polymer and a condensed phosphate, a cured resin, a sheet-like cured resin, a laminate, a prepreg, an electronic member, a single layer and a multilayer circuit board, Layer circuit board and a multilayer circuit board. However, since the molecular weight of the condensed phosphate used is low and the plasticity thereof is high, the heat resistance of the curing system is greatly affected, so that it can not adapt to the requirement of high heat resistance.

It is an object of the present invention to provide a thermosetting resin composition, which can provide excellent dielectric performance, anti-wet heat performance, and mechanical performance required for a copper-clad laminate, and can provide good processability, It can realize halogen-free flame retardant with absorption rate, high Tg and excellent resistance to humidity and it can reach UL94 V-0 flammability rating.

To achieve the above object, the present invention adopts the following measures:

In the thermosetting resin composition, the resin composition

(A) a cyanate compound or / and a cyanate prepolymer;

(B) a polyphosphonate or / and a phosphonate-carbonate copolymer.

The present invention uses a polyphosphonate and / or a phosphonate-carbonate copolymer having a large molecular weight, excellent heat resistance and low plasticity as flame retardants.

In short, the structural formula of the polyphosphonate is as follows:

Wherein Ar is an aryl group and -O-Ar-O- is a group selected from the group consisting of a resorcinol activity group, a hydroquinone activator, a bisphenol A activator, a bisphenol F activator, a 4,4 ' (4,4'-diphenol), a phenolphthalein activating group, a 4,4'-thiobisphenol activating group, a 4,4'-sulfonyl diphenol activating group Or 3,3,5-trimethyl cyclohexyl diphenyl (3,3,5-trimethyl cyclohexyl diphenyl); X is a C1 to C20 substituted or unsubstituted straight chain alkyl group, a C1 to C20 substituted or unsubstituted branched chain alkyl group, a C2 to C20 substituted or unsubstituted straight chain olefin group, a C2 to C20 substituted or unsubstituted branched chain olefin group, A C2-C20 substituted or unsubstituted straight-chain alkylene group, a C2-C20 substituted or unsubstituted branched-chain alkylene group, a C5-C20 substituted or unsubstituted cycloalkyl group or a C6-C20 substituted or unsubstituted aryl group; n is an arbitrary integer from 1 to 75, for example, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,

Preferably, the structural formula of the phosphonate-carbonate copolymer is as follows:

or

,

,

Ar ¹ , Ar ² and Ar ³ are each independently an aryl group; The -O-Ar ³ -O- may be a resorcinol group, a hydroquinone group, a bisphenol A group, a bisphenol F group, a 4,4'-diphenol group, a phenolphthalein group, a 4,4'-thiobisphenol group, 4'-sulfonyldiphenol active group or 3,3,5-trimethylcyclohexyldiphenol, but is not limited thereto; X ¹ and X ² are each independently a straight chain alkyl group having from ¹ to 20 carbon atoms, a substituted or unsubstituted branched alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted straight chain olefin group having from 2 to 20 carbon atoms, A branched or unbranched branched olefin group, a C2-C20 substituted or unsubstituted straight-chain alkylene group, a C2-C20 substituted or unsubstituted branched-chain alkylene group, a C5-C20 substituted or unsubstituted cycloalkyl group or a C6- Lt; / RTI > m is an arbitrary integer of 1 to 100, n ₁ and n ₂ are each independently any integer of 1 to 75 and p is any integer of 2 to 50, and R ¹ and R ² are each independently substituted or unsubstituted Is selected from unsubstituted aliphatic or aromatic hydrocarbon groups, and is preferably selected from unsubstituted aliphatic or aromatic hydrocarbon groups.

The aryl group refers to any functional group or substituent derived from an aromatic ring and exemplary aromatic rings include, but are not limited to, toluene, ethylbenzene, N-propylbenzene, isopropylbenzene, styrene, phenol, acetophenone, anisole, Benzoyl chloride, benzoic acid, benzonitrile, nitrobenzene, nitrosobenzene, aniline, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, benzenesulfonic acid, diphenylketone, diphenyldicetone, Benzenesulfonyl chloride, benzenesulfonyl chloride, diphenylmethane, triphenylmethane, triphenylmethanol, triphenylchloromethane, tetraphenylmethane, triphenylmethane, triphenylmethane, triphenylmethane, triphenylmethane, Dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene), phthalic acid ((o-dihydroxybenzene, (O-toluidine, m-toluidine, p-toluidine), 1 (o-phenylenediamine, m-phenylenediamine, p-phenylenediamine) Benzenesulfonic acid, p-toluenesulfonic acid, p-aminobenzoic acid, salicylic acid, acetylsalicylic acid, paracetamol, phenacetin, m-chloroperbenzoic acid, mesitylene, pseudocumene ), Durene, gallic acid, pyrogallol, picric acid, trinitrotoluene, tribromophenol, pentachlorophenol, melitic acid, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, quinone ), And the aryl group may be a functional group or a substituent derived from any of the aromatic rings.

In a preferred embodiment, the polyphosphonate and / or phosphonate-carbonate copolymer

,

,

or

중에서 선택되는 어느 1종 또는 적어도 2종의 혼합물을 포함하나, 이에 한정되지 않으며;

, Or a mixture of at least two selected from the group consisting of, but not limited to;

Among them, R ³ and R ⁴ are each independently selected from a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, preferably an unsubstituted aliphatic or aromatic hydrocarbon group; m ₁ is any integer of 1 to 100, n ₃ , n ₄ and n ₅ are each independently any integer of 1 to 75, and p ₁ is any integer of 2 to 50.

Preferably, m and m ₁ are each independently any integer of 5 to 100, and m and m ₁ are each independently any integer of 10 to 100.

Preferably, n ₁ , n ₂ , n ₃ , n ₄ and n ₅ are independently integers from 5 to 75, and preferably n ₁ , n ₂ , n ₃ , n ₄ and n ₅ are each independently Is an arbitrary integer in the range of 10 to 75.

Preferably, p and p ₁ are each independently any integer of 5 to 50, and p and p ₁ are each independently any integer of 10 to 50.

M and m ₁ are each independently selected from the group consisting of 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, Or 95 days.

N ₁ , n ₂ , n ₃ , n ₄ and n ₅ may each independently be, for example, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, , 65, 70, or 72, respectively.

P and p ₁ may each independently be 3, 5, 10, 14, 18, 22, 26, 30, 34, 38, 42, 45,

Preferably, the weight average molecular weight of the polyphosphonate and / or phosphonate-carbonate copolymer is independently from 1000 to 60000, preferably from 2000 to 50000, more preferably from 2500 to 10000. When the weight average molecular weight is 1000 or less, the heat resistance of the cured product after being added to the resin cured product is low, for example, the glass transition temperature is low. When the weight average molecular weight is 60000 or more, the polyphosphonate and / It is impossible to obtain an excellent and homogeneous resin adhesive liquid which can satisfy the requirement of the processability of the copper-clad laminate because the solubility thereof in the organic solvent is too low.

Cyanate, that is, a resin containing two or more cyanato groups (-OCN) in the molecular structure.

Preferably, in the present invention, the cyanate compound has the following structure:

,

,

,

혹은

에서 선택되며, R₂, R₃, R₁₀, R₁₁은 각각 독립적으로 수소 원자, 치환 또는 비치환된 C1-C4 직쇄 알킬기 혹은 치환 또는 비치환된 C1-C4분지쇄 알킬기 중에서 선택되는 어느 1종 이며 R₂, R₃, R₁₀, R₁₁은 같거나 다르며; In the above structural formula, R ₁ is -CH ₂ -,

,

,

,

or

And R ₂ , R ₃ , R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom, a substituted or unsubstituted C 1 -C 4 straight-chain alkyl group or a substituted or unsubstituted C 1 -C 4 branched- And R ₂ , R ₃ , R ₁₀ and R ₁₁ are the same or different;

Preferably, the cyanate prepolymer of the present invention has the following structure:

R ₄ , R ₁₂ and R ₁₃ are each independently selected from a hydrogen atom, a substituted or unsubstituted C 1 -C 4 straight-chain alkyl group or a substituted or unsubstituted C 1 -C 4 branched-chain alkyl group, k Is an arbitrary integer of 1 to 7.

Preferably, the component (A) is selected from the group consisting of 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) , 5-dimethyl-4-cyanatophenyl) methane, 2,2-bis- (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, (4-cyanatophenyl) -1,3-diisopropylbenzene, cyclopentadiene type cyanate, phenol novolak type cyanate, cresol novolak type cyanate, 2,2- Bis (4- cyanatophenyl) ethane prepolymer, bis (3,5-dimethyl-4-cyanatophenyl) methane prepolymer, 2,2- 3,3,3-hexafluoropropane prepolymer,?,? '-Bis (4-cyanatophenyl) -1,3-diisopropylbenzene prepolymer, cyclopentadiene-type cyanate prepolymer, phenol novolak-type cyanate prepolymer Or a cresol novolak type cyanate prepolymer Or mixtures of at least two of them. Exemplary cyanate compounds and / or cyanate prepolymers include, for example, 2,2-bis (4-cyanatophenyl) propane and bis (4-cyanatophenyl) Mixture, a mixture of bis (3,5-dimethyl-4-cyanatophenyl) methane and 2,2-bis- (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane , a mixture of?,? '- bis (4-cyanatophenyl) -1,3-diisopropylbenzene and cyclopentadiene cyanate, a mixture of phenol novolac cyanate and cresol novolac cyanate, 2 , A mixture of 2-bis- (4-cyanatophenyl) propane prepolymer and bis (4-cyanatophenyl) ethane prepolymer and bis (3,5-dimethyl-4-cyanatophenyl) methane prepolymer, - (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane prepolymer and α, α'-bis (4-cyanatophenyl) -1,3-diisopropylbenzene prepolymer / RTI > A mixture of a pentadiene-type cyanate prepolymer, a phenol novolak-type cyanate prepolymer and a cresol novolac-type cyanate prepolymer, and preferably a mixture of 2,2-bis- (4-cyanatophenyl) propane, (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis- (4-cyanatophenyl) propane prepolymer,? , at least one selected from the group consisting of α'-bis (4-cyanatophenyl) -1,3-diisopropylbenzene prepolymer and bis (3,5-dimethyl-4-cyanatophenyl) / RTI >

(A) a cyanate compound and / or a cyanate prepolymer, and 10 to 50 parts by weight of (B) a polyphosphonate and / or a phosphonate-carbonate copolymer ≪ / RTI > Preferably, the resin composition contains 60 to 80 parts by weight of (A) a cyanate compound or / and a cyanate prepolymer, and 20 to 40 parts by weight of (B) a polyphosphonate and / or a phosphonate- ; More preferably, the resin composition comprises 70 to 80 parts by weight of (A) a cyanate compound and / or a cyanate prepolymer, and 20 to 30 parts by weight of (B) a polyphosphonate and / or a phosphonate- . 54 parts by weight, 57 parts by weight, 61 parts by weight, 65 parts by weight, 72 parts by weight, 76 parts by weight and 78 parts by weight, for example, by weight of the cyanate compound and / or cyanate prepolymer (A) 82 parts by weight, 86 parts by weight and 88 parts by weight; The weight parts of the (B) polyphosphonate and / or phosphonate-carbonate copolymer are, for example, 12 parts by weight, 15 parts by weight, 18 parts by weight, 24 parts by weight, 27 parts by weight, 42 parts by weight, 46 parts by weight and 48 parts by weight.

The skilled artisan will appreciate that suitable thermosetting resin compositions of the present invention can be prepared by combining appropriate components (A) and (B) by selecting appropriate blending components such as a curing agent and an accelerator based on the blending method of the thermosetting resin composition disclosed in the prior art Can be obtained.

If necessary, the thermosetting resin composition of the present invention may further comprise (C) a halogen-free epoxy resin, wherein the halogen-free epoxy resin is preferably a halogen-free bisphenol A type epoxy resin, a bisphenol F type epoxy resin, A cresol novolak epoxy resin, a bisphenol A novolac epoxy resin, a triphenol novolac epoxy resin, a nitrogen-containing epoxy resin, a silicon-containing epoxy resin, a dicyclopentadiene novolac epoxy resin, Benzene-type novolac epoxy resin, or naphthol-type novolac epoxy resin, or a mixture of at least two of them. The mixture may be, for example, a mixture of a bisphenol A epoxy resin and a bisphenol F epoxy resin, a mixture of an o-cresol novolak epoxy resin and a bisphenol A novolac epoxy resin, a mixture of a triphenol novolac epoxy resin and a nitrogen- A mixture of a silicon-containing epoxy resin and a dicyclopentadiene novolac epoxy resin, a mixture of a biphenyl-type novolac epoxy resin and an alkylbenzene-type novolac epoxy resin, a mixture of a naphthol-type novolac epoxy resin and a bisphenol A- to be.

Preferably, the component (C) halogen-free epoxy resin is selected from epoxy resins having the following structure:

또는

에서 선택되며, R₅는 수소원자, 치환 또는 비치환된 C1-C5 직쇄 알킬기 혹은 치환 또는 비치환된 C1-C5 분지쇄 알킬기 중에서 선택되는 1종이다.X ₁ , X ₂ and X ₃ are each independently

or

And R ₅ is a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group, or a substituted or unsubstituted C1-C5 branched alkyl group.

,

,

,

혹은

중에서 선택되는 어느 1종 이고, a는 1~10중의 임의의 정수이며, 예를 들어 2, 3, 4, 5, 6, 7, 8 혹은 9이며, 그중에서 R₆은 수소원자, 치환 또는 비치환된 C1-C5 직쇄 알킬기 혹은 치환 또는 비치환된 C1-C5 분지쇄 알킬기 중에서 선택되는 1종 이다.Y ₁ and Y ₂ each independently represents a single bond, -CH ₂ -

,

,

,

or

, A is an arbitrary integer of 1 to 10, and is, for example, 2, 3, 4, 5, 6, 7, 8 or 9, wherein R ₆ is a hydrogen atom, A substituted or unsubstituted C1-C5 straight chain alkyl group or a substituted or unsubstituted C1-C5 branched chain alkyl group.

Preferably, the halogen-free epoxy resin is an epoxy resin having the following structure:

A ₁ is an arbitrary integer from 1 to 10, for example, 2, 3, 4, 5, 6, 7, 8 or 9; R ₇ is a hydrogen atom, a substituted or unsubstituted C1- An alkyl group or a substituted or unsubstituted C1-C5 branched alkyl group;

or

Wherein a ₂ is any integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8 or 9;

or

Wherein a ₃ is any integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8 or 9;

or

In the above formula, a ₄ is an arbitrary integer from 1 to 10, and is, for example, any one or a mixture of at least two selected from epoxy resins having 2, 3, 4, 5, 6, 7,

Preferably, the halogen-free epoxy resin is selected from epoxy resins having the following structure:

A ₅ is any integer from 2 to 10, for example 3, 4, 5, 6, 7, 8 or 9; R ₈ , R ₉ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C1-C5 branched alkyl group.

Component (C) The amount of the halogen-free epoxy resin to be added is 10 to 50 parts by weight, for example, 12 parts by weight and 14 parts by weight, based on 100 parts by weight of the cyanate compound and / or cyanate prepolymer. 18 parts by weight, 22 parts by weight, 24 parts by weight, 29 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 42 parts by weight, 46 parts by weight and 48 parts by weight, preferably 20 to 40 parts by weight .

If necessary, the thermosetting resin composition of the present invention further comprises a filler (D), and there is no particular limitation on the filler to be added as needed, but the filler may be selected from organic fillers and / or inorganic fillers , Preferably an inorganic filler, more preferably a surface-treated inorganic filler, and most preferably a surface-treated silica.

The surface treatment agent used in the surface treatment may be any one or a mixture of at least two selected from a silane coupling agent, a silicone oligomer or a titanate coupling agent. The silane coupling agent may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidylpropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyl Isobutyltrimethoxysilane, 3-isobutyltrimethoxysilane, 3-isobutylpropylmethyldimethoxysilane, 3-isobutentpropylmethyl, 3-isobutyltrimethoxysilane, (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N-2 Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- -Aminopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane, or a mixture of at least two of them. It is selected. There is no particular limitation on the capacity of the silane coupling agent, but when the inorganic filler is used in an amount of 100 parts by weight, the amount of the surface treatment agent is usually 0.1 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, Is 0.75 to 2.0 parts by weight.

The inorganic filler is selected from among a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphor or a mixture of at least two of them. The inorganic filler is preferably selected from the group consisting of crystalline silica, At least one of silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, calcium silicate, calcium carbonate, ≪ / RTI > For example, a mixture of crystalline silica and fused silica, a mixture of spherical silica and hollow silica, a mixture of glass powder and aluminum nitride, a mixture of boron nitride and silicon carbide, a mixture of aluminum hydroxide and titanium dioxide, a mixture of strontium titanate and barium titanate, A mixture of aluminum oxide, barium sulfate and talcum powder, a mixture of calcium silicate and calcium carbonate and mica.

The organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, organic phosphorus salt compound and polyethersulfone powder. The mixture is, for example, a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, or a mixture of organic phosphorus salt compound and polyethersulfone powder.

There is no particular limitation on the shape and particle size of the filler. Preferably, the filler has an average particle diameter of 0.01 to 50 탆, for example, 1 탆, 3 탆, 7 탆, 12 탆, 25 탆, 37 탆, 43 탆, 47 탆, 49 탆, preferably 0.01 to 20 탆, more preferably 0.01 to 10 탆, and the inorganic filler having such a particle diameter is more easily dispersed in the resin solution.

The addition amount of the filler of the component (D) is not particularly limited. When the total weight of the component (A), the component (B) and the component (C) is 100 parts by weight, 5 parts by weight and 5 parts by weight based on 100 parts by weight of the total amount of the polymerizable composition of the present invention is 10 parts by weight, 80 parts by weight, 120 parts by weight, 230 parts by weight, 350 parts by weight, 450 parts by weight, 520 parts by weight, 680 parts by weight, 740 parts by weight, 970 parts by weight, preferably 5 to 300 parts by weight, more preferably 5 to 200 parts by weight, and particularly preferably 15 to 150 parts by weight.

If necessary, the thermosetting resin composition of the present invention may further comprise a component (E) catalyst, and the catalyst is not particularly limited and may be used if it can promote curing reaction of cyanate, cyanate and epoxy resin have. The catalyst may be selected from any one or a mixture of at least two selected from organic metal salt compounds (for example, copper, zinc, cobalt, nickel, iron), imidazole compounds and derivatives thereof, or tertiary ammonium. Illustratively, the component (E) catalyst is selected from the group consisting of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, tributylamine, triphenylphosphine, boron trifluoride complex, Metal salt, acetylacetone metal salt, naphthenic acid metal salt, salicylic acid metal salt or stearic acid metal salt, and the mixture is selected from, for example, a mixture of a metal stearate salt and a metal salicylate salt, a metal naphthenate salt and an acetyl Mixtures of acetone metal salts, mixtures of metal octanoate and boron trifluoride complexes, mixtures of triphenylphosphine and tributylamine, mixtures of 2-ethyl-4-methylimidazole and 2-phenylimidazole, metal octanoate A mixture of tributylamine and tributylamine, a mixture of 2-ethyl-4-methylimidazole, tributylamine and 2-phenylimidazole, wherein the metal is selected from zinc, copper, iron, tin, cobalt or aluminumOne or a mixture of at least two of them.

When the total weight of the component (A), the component (B) and the component (C) is 100 parts by weight, the addition amount of the catalyst of the component (E) is 0.01 to 1.0 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight or 0.9 part by weight.

In the thermosetting resin composition, the resin composition comprises:

(A) 50 to 90 parts by weight of a cyanate compound and / or a cyanate prepolymer;

(B) a polyphosphonate and / or phosphonate-carbonate copolymer; 10 to 50 parts by weight.

In the thermosetting resin composition, the resin composition comprises:

(A) 50 to 90 parts by weight of a cyanate compound and / or a cyanate prepolymer;

(B) a polyphosphonate and / or phosphonate-carbonate copolymer; 10 to 50 parts by weight;

(C) Halogen-free epoxy resin: When the component (A) is used in an amount of 100 parts by weight, the amount of the halogen-free epoxy resin is 10 to 50 parts by weight.

In the thermosetting resin composition, the resin composition comprises:

(A) 50 to 90 parts by weight of a cyanate compound and / or a cyanate prepolymer;

(B) a polyphosphonate and / or phosphonate-carbonate copolymer; 10 to 50 parts by weight;

(C) a halogen-free epoxy resin; When the component (A) is used in an amount of 100 parts by weight, the amount of the halogen-free epoxy resin is 10 to 50 parts by weight;

(D) a filler; When the total weight of the components (A), (B) and (C) is 100 parts by weight, the amount of the filler (D) is 5 to 1000 parts by weight;

(E) catalyst; When the total weight of the component (A), the component (B) and the component (C) is 100 parts by weight, the amount of the component (E) added is 0.01 to 1.0 part by weight.

"Included " in accordance with the present invention means that, in addition to the above components, other components that impart different characteristics to the halogen-free resin composition may be further included. Further, "including" in accordance with the present invention may be replaced with " composed of "

For example, the thermosetting resin composition of the present invention may contain a suitable thermosetting resin. Specific examples thereof include a polyphenylene ether resin, a phenol resin, a polyurethane resin, and a melamine resin. The curing agent of the thermosetting resin A curing accelerator may also be added.

The thermosetting resin composition may further contain various additives. Specific examples thereof include antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants. These various additives may be used alone or in combination of two or more.

(A), the component (B), the component (C), the catalyst, the filler, various thermosetting resins and various additives are mixed, stirred and mixed by using a method known in the art for producing the resin composition of the present invention .

The above-mentioned thermosetting resin composition can be dissolved or dissolved in a solvent to obtain a resin adhesive solution.

The solvent of the present invention is not particularly limited and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether ; Ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and mesitylene; Esters such as ethoxy ethyl acetate and ethyl acetate; Nitrogen-containing solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. The solvent may be used singly or two or more of them may be used in admixture. The solvent may be any one selected from the group consisting of aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, acetone, butanone, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone, and other ketone solvents may be mixed and used. The amount of the solvent to be used may be selected according to the experience of the skilled artisan in the art, and the resin adhesive liquid obtained may have a viscosity suitable for use.

An emulsifier may be added in the course of dissolving or dispersing the above-mentioned resin composition in a solvent. As the powder is dispersed through the emulsifier, the powder filler or the like can be uniformly dispersed in the adhesive liquid.

It is still another object of the present invention to provide a prepreg comprising the above-mentioned thermosetting resin composition attached to a reinforcing material and a reinforcing material after impregnation and drying. The reinforcing material is not particularly limited, but may be an organic fiber, an inorganic fiber cloth or a nonwoven fabric. The organic fiber may be preferably an aramid nonwoven fabric. The inorganic fiber pile may include E glass fiber, D glass fiber, S glass fiber, T Glass fibers, NE glass fibers, and quartz fabrics. There is no particular limitation on the thickness of the reinforcing material, but the thickness of the fabric or nonwoven fabric is preferably 0.01 to 0.2 mm in consideration of good dimensional stability in application to a laminated board, and surface treatment with carding treatment or silane coupling agent The silane coupling agent is preferably a mixture of at least one of an epoxy silane coupling agent, an amino silane coupling agent and a vinyl silane coupling agent in order to provide good water resistance and heat resistance. The prepreg impregnated with the thermosetting resin composition was baked at 100 to 200 ° C for 2 to 10 minutes and dried to obtain the prepreg.

Another object of the present invention is to provide a laminate including at least one of the prepregs. After the prepreg laid along one sheet or several sheets of a given sequence by curing in a hot press machine was producing a laminated board, the curing temperature is 150-250 ℃ and curing pressure is 25-60kg / cm ^2.

The prepreg is laminated on one or more sheets in a predetermined order, and then a copper foil is coated on one side or both sides of the prepregs stacked on each other and cured in a hot press machine to produce a copper clad laminate having a curing temperature of 150 to 250 ° C The curing pressure is 25 to 60 kg / cm ² . The prepreg, the laminate and the copper-clad laminate of the present invention have excellent dielectric performance and heat resistance, have a high glass transition temperature, a lower absorption rate, can realize halogen-free flame retardation, and can reach UL94 V-0 .

It is still another object of the present invention to provide a high frequency circuit board including copper foil on both sides of at least one of the prepreg and the overlapping prepreg.

Compared to the prior art, the present invention has the following advantageous effects:

(1) The thermosetting resin provided in the present invention has a low dielectric constant, dielectric loss tangent; (2) The present invention uses a copolymer of polyphosphonate and / or phosphonate-carbonate as a flame retardant and realizes halogen-free flame retardancy while maintaining the heat resistance, low water absorption and excellent dielectric performance of the original cured product, Also, the flame retardancy of the cured product can reach UL94 V-0 rating; (3) The prepreg and the copper-clad laminate made of the thermosetting resin composition used in the present invention have excellent dielectric performance and anti-wet heat performance, and the flame retardancy reaches UL94 V-0 grade and has excellent processability.

For a more detailed description of the present invention and for a better understanding of the technical solution of the present invention, exemplary embodiments of the present invention include, but are not limited to,

The dielectric constant, the dielectric loss factor, the glass transition temperature, the flame retardancy and the resistance to humid heat of the copper clad laminate were measured and the following examples are described in more detail.

Example 1

80 parts by weight of a bisphenol A cyanate resin BA230S (LONZA company, equivalent weight of cyano group: 139 g / eq) was added to the vessel and 20 parts by weight of a phosphonate-carbonate copolymer FRX CO6000 10.8%) was added and stirred uniformly. Thereafter, 0.08 parts by weight of zinc cadrate as a catalyst and a solvent butanone were added and the mixture was uniformly stirred to prepare an adhesive liquid. The glass fiber cloth (2116 model, thickness 0.08 mm The prepared prepregs were stacked on each other, and the copper foils were pressed on both sides of the stacked prepregs one by one. Then, and cured in a hot press to prepare a copper-clad laminate. the curing temperature is 150 ~ 250 ℃ and curing pressure is 25 ~ 60 kg / cm ^2, and curing time is from 90 ~ 120min.

Example 2

55 parts by weight of a bisphenol A cyanate resin BA230S (LONZA company, equivalent weight of cyano group: 139 g / eq) was added to the vessel and 45 parts by weight of a phosphonate-carbonate copolymer FRX CO95 %) Was added and stirred homogeneously. Then, 0.035 part by weight of zinc cadrate as a catalyst and butanone as a solvent were added and the mixture was homogeneously stirred to prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 3

90 parts by weight of novolac cyanate resin PT-30 (LONZA company, equivalent weight of cyano group: 139 g / eq) was added to the vessel and 10 parts by weight of polyphosphonate HM1100 (FRP Polymers Co., phosphorus content: 10.8% And homogeneously stirred. Then, 0.035 part by weight of zinc cadrate as a catalyst, and butanone as a solvent were added, and the mixture was uniformly stirred to prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 4

55 parts by weight of a novolak type cyanate resin PT-30 (LONZA company) and 30 parts by weight of dicyclopentadiene type novolak epoxy resin HP7200H (Japan DIC resin, EEW: 278 g / eq) The phosphonate-carbonate copolymer FRX CO3000 (FRX Polymers Ltd., phosphorus content: 10.6%) was added and stirred uniformly, then 0.035 parts by weight of zinc cadrate zinc, and butanone as solvent were added uniformly Followed by stirring to prepare an adhesive solution. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 5

55 parts by weight of a novolak type cyanate resin PT-30 (LONZA company) and 30 parts by weight of an aralkylbenzene type novolak epoxy resin NC-2000L (Japan Gunpower Company, EEW: 238 g / eq) (Content of 10.8% by FRX Polymers Ltd., phosphorus content: 10%) was added and homogeneously stirred. Then, 0.035 part by weight of zinc cadrate as a catalyst, and butanone as a solvent were added, and the mixture was uniformly stirred To prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 6

60 parts by weight of a novolak type cyanate resin PT-30 (LONZA company) and 30 parts by weight of a naphthol type novolac epoxy resin NC-7000L (Japan Gunpower Company, EEW: 232 g / eq) The mixture was stirred homogeneously, and then 0.035 parts by weight of zinc cadrate, a catalyst, and butanone were added as a solvent, and the mixture was homogeneously stirred To prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 7

60 parts by weight of bisphenol A cyanate resin BA230S (LONZA company, equivalent weight of cyano group: 139 g / eq) and 15 parts by weight of phenol-type novolac epoxy resin N690 (Japan DIC Company, EEW: 205 g / eq) , 25 parts by weight of a phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Co., phosphorus content: 10.6%) were added and stirred homogeneously. Thereafter, 0.035 part by weight of zinc catechol as a catalyst and butanol as a solvent And the mixture was uniformly stirred to prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 8

60 parts by weight of a novolac cyanate resin PT-30 (LONZA company) and 15 parts by weight of a phenol-type novolac epoxy resin N690 (Japan DIC Co., Ltd., EEW: 205 g / eq) were added to a vessel, and 25 parts by weight of phosphonate -Carbonate copolymer FRX CO6000 (FRX Polymers Co., phosphorus content: 10.6%) was added and homogeneously stirred. Then, 0.035 part by weight of zinc catalyst, zinc caprylate, and butanone were added as a solvent, Lt; / RTI > The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 9

60 parts by weight of bisphenol A cyanate resin BA230S (LONZA company, equivalent weight of cyano group: 139 g / eq) and 15 parts by weight of phenol-type novolac epoxy resin N690 (Japan DIC Company, EEW: 205 g / eq) , 30 parts by weight of polyphosphonate FRX 100 (FRX Polymers Ltd., phosphorus content: 10.8%) were added and stirred uniformly, then 0.035 parts by weight of zinc cadrate zinc as a catalyst, and butanone as a solvent, Followed by stirring to prepare an adhesive solution. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 10

60 parts by weight of novolak type cyanate resin PT-30 (LONZA company, equivalent weight of cyano group: 139 g / eq), 6 parts by weight of dicyclopentadiene type novolac epoxy resin HP7200H (Japan DIC company, 278 g / , 40 parts by weight of a phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Ltd., phosphorus content: 10.6%) was added and stirred uniformly, then butanone was added as a solvent, and the mixture was homogeneously stirred To prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 11

70 parts by weight of novolak type cyanate resin PT-30 (LONZA company) and 35 parts by weight of dicyclopentadiene type novolac epoxy resin HP7200H (Japan DIC company, EEW of 278 g / eq) Phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Ltd., phosphorus content: 10.6%) was added and stirred homogeneously. Butanone was added as a solvent, and the mixture was uniformly stirred to prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 12

60 parts by weight of novolac cyanate resin PT-30 (LONZA company) and 12 parts by weight of aralkyl benzene novolac epoxy resin NC-2000L (Japan Powder Company, EEW: 238 g / eq) , 40 parts by weight of a phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Ltd., phosphorus content: 10.6%) was added and stirred uniformly, 15.6 parts by weight of silica and butanone were added to the solvent, Followed by stirring to prepare an adhesive solution. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 13

70 parts by weight of novolak type cyanate resin PT-30 (LONZA company) and 30 parts by weight of naphthol type novolak epoxy resin NC-7000L (Japanese explosive company, 232 g / eq of EEW) Carbonate-phosphate copolymer FRX CO6000 (FRX Polymers Ltd., phosphorus content: 10.6%) was added and stirred uniformly. Thereafter, silica surface-treated with 150 parts by weight of vinyltrimethoxysilane and further treated with butanone as a solvent And the mixture was uniformly stirred to prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Example 14

30 parts by weight of novolak type cyanate resin PT-30 (LONZA company) and 30 parts by weight of biphenyl type novolak epoxy resin NC-3000H (Nippon Bunko KK, 288 g / eq of EEW) Phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Ltd., phosphorus content: 10.6%) was added and homogeneously stirred, then 100 parts by weight of silica SC2050 (Admatechs, D50: 0.5 占 퐉) And the mixture was uniformly stirred to prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Comparative Example 1

60 parts by weight of a novolak type cyanate resin PT-30 (LONZA company) and 15 parts by weight of a phenol novolak type epoxy resin N690 (Japan DIC Company, EEW: 205 g / eq) were added to a vessel, and 25 parts by weight of phosphite PX-200 (manufactured by Daihachi Chemical Co., Ltd., phosphorus content: 9%) was added and homogeneously stirred, 0.035 parts by weight of zinc cadrate as a catalyst, and butanone as a solvent were added, Respectively. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Comparative Example 2

60 parts by weight of bisphenol A cyanate resin BA230S (LONZA company, equivalent weight of cyano group: 139 g / eq) and 15 parts by weight of phenol-type novolac epoxy resin N690 (Japan DIC Company, EEW: 205 g / eq) , 25 parts by weight of a phosphazene flame retardant SP-100 (Otsuka Chemical Co., phosphorus content: 13.4%) were added and homogeneously stirred, and 0.035 parts by weight of zinc cadrate as a catalyst and butanol as a solvent were added, To prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Comparative Example 3

60 parts by weight of bisphenol A cyanate resin BA230S (LONZA company, equivalent weight of cyano group: 139 g / eq) and 15 parts by weight of phenol-type novolac epoxy resin N690 (Japan DIC Company, EEW: 205 g / eq) , 30 parts by weight of phosphite FP-600 (ADEKA, phosphorus content: 8.9%), which is a flame retardant, was added and uniformly stirred, 0.035 part by weight of zinc cadrate as a catalyst, and butanone as a solvent were added, To prepare an adhesive liquid. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Comparative Example 4

55 parts by weight of novolak type cyanate resin PT-30 (LONZA company) and 30 parts by weight of dicyclopentadiene type novolak epoxy resin HP7200H (Japan DIC company, EEW: 278 g / eq) were added to a vessel and uniformly stirred , 0.035 parts by weight of zinc cadrate as a catalyst, and butanone as a solvent were added, and the mixture was uniformly stirred to prepare an adhesive solution. The adhesive liquid was impregnated with a glass fiber cloth (2116 model, thickness: 0.08 mm), controlled to an appropriate thickness, and then dried to remove the solvent to prepare a prepreg. Several sheets of the prepared prepregs were superimposed on each other, and then the copper foils were pressed on both sides of the overlapped prepregs one by one and cured by a hot press machine to produce a copper clad laminate. The curing temperature is 150 to 250 ° C, the curing pressure is 25 to 60 kg / cm ^2, and the curing time is 90 to 120 min.

Table 1 Physical properties of each example and comparative example

Table 2 Physical properties of each example and comparative example (continued)

Table 3 Physical properties of each example and comparative example (continued)

Table 4 Physical properties of each example and comparative example (continued)

 The test method for the above characteristics is as follows:

(1) Glass transition temperature (Tg): Measured using DMA and measured by the DMA measurement method specified in IPC-TM-650 2.4.24.

(2) Dielectric constant and dielectric loss factor: Measured by the SPDR method.

(3) Evaluation of damp heat resistance: After the copper foil on the surface of the copper-clad laminate was etched, the substrate was evaluated; The substrate is placed in a pressure cooker and treated at 120 ° C and 105 KPa for 4 hours and then immersed in a tin stove at 288 ° C .; when the substrate is delaminated, record the corresponding time; Evaluation is terminated when blistering does not occur or the delamination is not performed so that the substrate passes the tin stove 5 minutes later.

(4) Flame retardancy: Proceed according to UL94 standard method.

Property Analysis

As is known from the results of the physical properties data of Tables 1 to 4, when the conventional phosphates are used as flame retardants in Comparative Examples 1 to 3, they belong to the non-reactive because they have a small molecular weight and correspond to plasticizers in the system. , The glass transition temperature is significantly lowered, so that the heat resistance is low, the water absorption rate is high, and the flame retardancy is low, thereby failing to meet the heat resistance requirement of the current lead-free process. In Comparative Example 4, very good heat resistance and low water absorption can be achieved in the absence of a flame retardant agent. However, since the flame retardancy is lowered to meet the requirement of V-0 grade, the laminate does not meet the requirements.

As described above, the copper-clad laminate of the present invention is capable of realizing halogen-free flame retardation, exhibiting excellent dielectric performance, a higher glass transition temperature, and excellent anti-wet heat performance, It can be applied to applications.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as defined by the appended claims. And should fall within the scope of protection of the claims of the invention.

While the present invention has been described in detail with reference to the preferred embodiments thereof, it is to be understood that the invention is not limited to the details of the foregoing description, . It will be apparent to those skilled in the art that any improvements to the present invention, the equivalent replacement of each ingredient in the product of the present invention, the addition of auxiliary ingredients, and the selection of the specific manner all fall within the scope and spirit of the present invention .

Claims (20)

In the thermosetting resin composition,
(A) a cyanate compound, a cyanate prepolymer or both;
(B) a polyphosphonate, a phosphonate-carbonate copolymer or both; And
(C) a halogen-free epoxy resin,
Wherein the amount of the halogenated epoxy resin (C) to be added is 10 to 50 parts by weight based on 100 parts by weight of the cyanate compound (A), the cyanate prepolymer, or both. The method according to claim 1,
The structural formula of the polyphosphonate is as follows:

Ar represents an aryl group, and -O-Ar-O- represents a resorcinol group, a hydroquinone group, a bisphenol A group, a bisphenol F group, a 4,4'-diphenol group, a phenolphthalein group, A thiobisphenol group, a 4,4'-sulfonyl diphenol group or 3,3,5-trimethylcyclohexyldiphenol; X is a C1 to C20 substituted or unsubstituted straight chain alkyl group, a C3 to C20 substituted or unsubstituted branched chain alkyl group, a C2 to C20 substituted or unsubstituted straight chain olefin group, a C3 to C20 substituted or unsubstituted branched chain olefin group, A C2-C20 substituted or unsubstituted straight-chain alkylene group, a C3-C20 substituted or unsubstituted branched-chain alkylene group, a C5-C20 substituted or unsubstituted cycloalkyl group or a C6-C20 substituted or unsubstituted aryl group; and n is an arbitrary integer of 1 to 75. The method according to claim 1,
The structural formula of the phosphonate-carbonate copolymer is as follows:

or

ego,
Wherein Ar ¹ , Ar ² and Ar ³ are each independently an aryl group, and -O-Ar ³ -O- represents a resorcinol active group, a hydroquinone active group, a bisphenol A active group, a bisphenol F active group, - any one member selected from the group consisting of diphenol, phenolphthalein active group, 4,4'-thiobisphenol active group, 4,4'-sulfonyl diphenol active group and 3,3,5-trimethylcyclohexyldiphenol; X ¹ and X ² are each independently a straight chain alkyl group having from ¹ to 20 carbon atoms, a substituted or unsubstituted branched alkyl group having from 3 to 20 carbon atoms, a substituted or unsubstituted straight chain olefin group having from 2 to 20 carbon atoms, A branched or unbranched branched olefin group, a C2-C20 substituted or unsubstituted straight-chain alkylene group, a C3-C20 substituted or unsubstituted branched alkylene group, a C5-C20 substituted or unsubstituted cycloalkyl group or a C6- Lt; / RTI > m is an arbitrary integer of 1 to 100, n ₁ and n ₂ are each independently any integer of 1 to 75 and p is any integer of 2 to 50, and R ¹ and R ² are each independently substituted or unsubstituted. An unsubstituted aliphatic or aromatic hydrocarbon group. The method according to claim 1,
The polyphosphonate, the phosphonate-carbonate copolymer, or both,

,

or

Or a mixture of at least two of them;
R ³ and R ⁴ are each independently selected from substituted or unsubstituted aliphatic or aromatic hydrocarbon groups, m ₁ is an arbitrary integer from 1 to 100, and n ₃ , n ₄ and n ₅ are each independently Is an arbitrary integer of 1 to 75, and p < _{1 >} is an arbitrary integer of 2 to 50. The thermosetting resin composition of claim 1, The method according to claim 1,
Wherein the weight average molecular weight of the polyphosphonate, the phosphonate-carbonate copolymer or both of them is independently 1,000 to 60,000. The method according to claim 1,
The cyanate compound has the following structure:

,
In the above structural formula, R ₁ is -CH ₂ -,

,

,

,

or

Lt; / RTI > R ₂ , R ₃ , R ₁₀ and R ₁₁ are each independently any one selected from a hydrogen atom, a substituted or unsubstituted C 1 -C 4 straight-chain alkyl group, or a substituted or unsubstituted C 3 -C 4 branched-chain alkyl group; R ₂ , R ₃ , R ₁₀ and R ₁₁ are the same or different from each other. The method according to claim 1,
The cyanate prepolymer has the following structure:

,
R ₄ , R ₁₂ and R ₁₃ are each independently any one selected from the group consisting of a hydrogen atom, a substituted or unsubstituted C1-C4 linear alkyl group, and a substituted or unsubstituted C3-C4 branched alkyl group, and k is an arbitrary integer of 1 to 7. The method according to claim 1,
Characterized in that it comprises 50 to 90 parts by weight of (A) a cyanate compound, a cyanate prepolymer or all of them, and 10 to 50 parts by weight of (B) a polyphosphonate, a phosphonate-carbonate copolymer or both Thermosetting resin composition. delete The method according to claim 1,
The halogen-free epoxy resin may be a halogen-free bisphenol A epoxy resin, a bisphenol F epoxy resin, an o-cresol novolak epoxy resin, a bisphenol A novolac epoxy resin, a triphenol novolac epoxy resin, Containing epoxy resin, a dicyclopentadiene novolac epoxy resin, a biphenyl-type novolac epoxy resin, an alkylbenzene-type novolac epoxy resin, or a naphthol-type novolac epoxy resin, or a mixture of at least two selected from And a thermosetting resin composition. The method according to claim 1,
The halogen-free epoxy resin is selected from epoxy resins having the following structure:

X ₁ , X ₂ and X ₃ are each independently

or

Lt; / RTI > R ₅ is a hydrogen atom, a substituted or unsubstituted C 1 -C 5 straight-chain alkyl group or a substituted or unsubstituted C 3 -C 5 branched-chain alkyl group;
Y ₁ and Y ₂ each independently represents a single bond, -CH ₂ -

,

,

,

or

And a is an arbitrary integer from 1 to 10, and among them, R ₆ represents a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C3-C5 branched alkyl group Wherein the thermosetting resin composition is a thermosetting resin composition. The method according to claim 1,
The halogen-free epoxy resin is an epoxy resin having the following structure:

,
Wherein a ₁ is any integer of 1 to 10 and R ₇ is any one selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C3-C5 branched alkyl group ;
or

Wherein a ₂ is any integer from 1 to 10;
or

Wherein a ₃ is any integer from 1 to 10;
or

Wherein a ₄ is any one or a mixture of at least two selected from any of integers from 1 to 10. The method according to claim 1,
The halogen-free epoxy resin is selected from epoxy resins having the following structure:

Wherein a ₅ is any integer from 2 to 10; R ₈ , R ₉ is independently a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group, or a substituted or unsubstituted C3-C5 branched alkyl group. The method according to claim 1,
Wherein the amount of the halogenated epoxy resin (C) to be added is 20 to 40 parts by weight based on 100 parts by weight of the cyanate compound (A), the cyanate prepolymer, or both. The method according to claim 1,
Wherein the thermosetting resin composition further comprises (D) a filler. 16. The method of claim 15,
Wherein the total amount of the component (A), the component (B) and the component (C) is 100 parts by weight, the amount of the filler (D) is 5 to 1000 parts by weight. The method according to claim 1,
Wherein the thermosetting resin composition further comprises a component (E) catalyst. 18. The method of claim 17,
Wherein the total amount of the component (A), the component (B) and the component (C) is 100 parts by weight based on 100 parts by weight of the component (E). In the prepreg,
Reinforcing material; And
A prepreg characterized by comprising a thermosetting resin composition according to any one of claims 1 to 8 and 10 to 18 attached to a reinforcing material after impregnation and drying. And at least one prepreg according to claim 19.