KR100869380B1 - The halogen free and phosphorus free flame retardant resin composition and the prepreg and the laminate using the same - Google Patents

Abstract

The present invention is a compound having a dihydro benzooxadine ring in the molecule, epoxy resin, novolac or resol phenol resin, cyanate ester resin having two or more cyanate groups in one molecule, non-phosphorus melamine flame retardant, zinc-based Provided are a non-halogen-based and non-phosphorus-based flame retardant resin composition comprising a flame-retardant aid and an inorganic filler, and a prepreg and a copper foil laminate using the same.

The resin composition of the present invention has a halogen, phosphorus and antimony compound content of 0.25% or less, which is excellent in flame retardancy without using halogen-based and phosphorus-based flame retardants or resins, as well as excellent heat resistance and high glass transition temperature (Tg) and copper foil. Since the peel strength and the lead heat resistance after moisture absorption are shown, it can be used in the production of copper foil laminates such as printed circuit boards.

Description

Non-halogen and non-phosphorus flame retardant resin composition, prepreg and copper foil laminate using the same {THE HALOGEN FREE AND PHOSPHORUS FREE FLAME RETARDANT RESIN COMPOSITION AND THE PREPREG AND THE LAMINATE USING THE SAME}

The present invention relates to a non-halogen-based and non-phosphorus-based flame retardant resin composition used in a printed circuit board (PCB) and a prepreg and a copper foil laminate using the same.

Recently, as electronic devices are represented as portable products, miniaturization, light weight, and high functionalization are required, and components mounted on a printed circuit board are also manufactured from QFP (Quad Flat Package), TCP (Tape Carrier Package), and BGA (Ball). Grid pins, flip chips and the like have been changed to multi-pin or narrow pitches, and in Japan, the CSP (Chip Size Package) of the same size as the Bare Chip is drawing attention. As a result of this change, in order to bond solder balls to the PCB board, it is necessary to increase the processing temperature, and further increase in the processing temperature is inevitable due to the regulation on the use of lead used in PCB manufacturing. There is a need for flame retardant materials with better thermal stability.

On the other hand, due to the increasing interest in environmental issues around the world, regulations on the generation of toxic substances in the disposal of electric and electronic products are also being tightened. Conventional resin compositions for prepregs and laminates are generally used with amine-based curing agents and curing accelerators in addition to brominated bifunctional epoxy resins and polyfunctional epoxy resins, which satisfy 94V-0 of UL (Underwriters Laboratory), a flame retardant standard. These epoxy compositions contain from 15 to 20% by weight bromine (Br).

However, although the halogen compound containing bromine has excellent flame retardancy, it generates toxic gas upon combustion, and may generate a carcinogen dioxine, so the use of the halogen-containing material will be strongly regulated in the future. The use of antimony, a carcinogenic substance, is also regulated. In addition, phosphorus-containing materials, which are widely used for improving flame retardancy along with halogen compounds, are also recognized as a factor that inhibits electrical properties in substrates for densification semiconductor packages, and their use is regulated.

For this reason, in order to increase the flame retardancy of the resin itself in place of the bromine or phosphorus-containing epoxy resin composition, a compound having a dihydro benzooxadine ring or a triazine ring containing a large amount of nitrogen atoms in a molecule has recently been introduced. Inorganic flame retardants have been introduced in place of phosphorus flame retardants.

The method of introducing a compound having a dihydro benzooxadine ring in the molecule is disclosed in Japanese Patent Application Laid-Open Nos. 2003-213077, 2003-206390, 2002-249639, 2001-302879 and the like, and US Patent No. 5,946,222. It is disclosed in the call. Japanese Patent Application Laid-Open No. 2003-206390 and US Pat. No. 5,946,222 describe a method in which a compound having a dihydro benzooxadine ring and a novolak phenol resin are reacted in a molecule. However, in this case, although high glass transition temperature (Tg) and heat resistance are shown, it was found that the flame retardancy of these compositions alone is difficult to achieve 94V-0 of UL.

In Japanese Patent Application Laid-Open Nos. 2003-213077 and 2001-302879, non-halogen condensed phosphate esters or reactive phosphate esters and inorganic flame retardants are reacted with a compound in which a compound having a dihydro benzooxadine ring, an epoxy resin and a phenol resin is reacted in a molecule. Japanese Patent Application Laid-Open No. 2002-249639 discloses a melamine-modified phenolic resin, a non-halogen condensed phosphate ester, and an inorganic flame retardant as a non-halogen flame retardant to a compound having a dihydro benzooxadine ring in a molecule. The introduced method and the like are described. However, most of the non-halogen condensed phosphate esters or reactive phosphate esters used in the above-mentioned documents are easily dissolved in organic solvents, so that varnishes are easy to prepare and have good compatibility with epoxy resins. On the other hand, the appearance of the prepreg is good, while the phosphorus is contained in the molecular structure, the heat resistance is weak, and the water absorption rate is high. Therefore, the heat resistance of the resin composition and the lead heat resistance after moisture absorption are greatly reduced. Because of melting, the flowability increased at the time of pressing, making it difficult to control the thickness. In particular, the reactive phosphate ester forms a single phase because it participates in the curing reaction, but has a disadvantage of dropping the glass transition temperature much. In addition, aluminum trihydroxide (ATH), which is an inorganic flame retardant, helps to improve flame retardancy by releasing a large amount of water during pyrolysis, but has a disadvantage in that pyrolysis starts at around 220 ° C., which degrades heat resistance. Magnesium Hydroxide (MH), another inorganic flame retardant, does not begin to decompose at temperatures above 300 ° C, which lowers its heat resistance.However, it is necessary to add a large amount to improve flame retardancy. It causes dropping. In Japanese Patent Application Laid-Open No. 2001-302870, phosphorus or nitrogen is included in an epoxy resin or a phenol resin to improve flame retardancy, but in this case, the glass transition temperature (Tg) is also helpful for flame retardancy and forms a single phase. Problems arise that is lowered and the heat resistance is lowered.

As such, conventional flame retardant resin compositions do not provide a balanced balance of various physical properties required for prepreg and copper foil laminate.

Therefore, an object of the present invention is to solve the problems of the prior art as described above and the technical problem that has been requested from the past.

The inventors have carried out in-depth studies and various experiments, and a compound having a dihydro benzooxadine ring, an epoxy resin, a novolak or a resol phenol resin, and a cyanate ester system having two or more cyanate groups in one molecule after extensive research and various experiments. A non-halogen non-phosphorous flame retardant epoxy resin composition for copper foil laminates comprising resins, melamine-based flame retardants, zinc-based flame retardants, and inorganic fillers has been developed, and since these compositions do not use halogen-based flame retardants, Since it does not generate toxic carcinogens and does not use phosphorus-based epoxy resins, it is possible to improve the disadvantage of deteriorating the electrical properties of the semiconductor package of the phosphorus-based flame retardant, and by introducing a compound containing a dihydrobenzoxadine ring in the molecule Resin than when using epoxy resin alone Improve the flame resistance, and was found that to increase the heat resistance and the glass transition temperature. In addition, it has been found that various physical properties required for the copper-clad laminate composition can be obtained in a balanced manner by the above-described composition, and have completed the present invention.

Specifically, the first object of the present invention is to provide a flame retardant resin composition for copper foil laminates that exhibits excellent flame resistance without generating carcinogenic substances during thermal decomposition, and has excellent heat resistance, glass transition temperature (Tg), and lead heat resistance after moisture absorption. .

A second object of the present invention is to provide a prepreg and a copper foil laminate using the composition.

In order to achieve this object, the flame-retardant resin composition according to the present invention, (A) a compound having a dihydro Benzooxadine ring in the molecule, (B) epoxy resin, (C) novolac or resol phenol resin And (D) cyanate ester resins having two or more cyanate groups in one molecule, (E) melamine flame retardants, (F) zinc flame retardant aids, and (G) inorganic fillers.

In general, it is very difficult to balance various physical properties in the resin composition for copper foil laminate. On the other hand, this invention provides the resin composition for copper foil laminated sheets which can express desired physical properties by the combination of the above-mentioned specific component.

Moreover, this invention provides the prepreg and copper foil laminated board using the composition mentioned above.

Hereinafter, the present invention will be described in detail.

The compound (A) having a dihydro benzooxadine ring in the molecule of the composition of the present invention is not particularly limited as long as it has a dihydro benzooxadine ring and is cured by a ring-opening reaction of dihydro benzooxadine. For example, the compound may be synthesized from a compound having a phenolic hydroxyl group, primary amine and formaldehyde.

Such compounds include a structure of Formula 1 below.

[Formula 1]

In which R ₁ Is an alkyl group, a cyclohexyl group, a phenyl group, or a phenyl group substituted from an alkyl group or an alkoxy group.

Examples of the compound having a phenolic hydroxyl group include polyfunctional phenols, biphenol compounds, bisphenol compounds, trisphenol compounds, tetraphenol compounds, and phenols. Resins (Phenolic Resins) and the like. As the multifunctional phenol, catechol, hydroquinone, resorcinol, and the like are used, and bisphenol compounds include bisphenol A, bisphenol F, and isomers thereof. Bisphenol S (Bisphenol S) and the like are used. Examples of the phenol resins include phenol novolak resins, resol phenol resins, phenol-modified xylene resins, alkyl phenol resins, melamine phenol resins, and phenol-modified polybutadiene resins.

Examples of the primary amine include methyl amine, cyclohexylamine, aniline, substituted aniline, and the like. When the aliphatic amine is used among the primary amines, the curing rate of the cured product is increased but the heat resistance is poor. When the aromatic amine such as aniline is used, the heat resistance is improved, but the curing rate is slowed.

In the present invention, 0.5-1.5 mol, preferably 0.6-1.0 mol of primary amine is added to 1 mol of the compound having a phenolic hydroxyl group in order to produce the compound (A) having a dihydrobenzoxadine ring in the molecule. The mixture is heated to 50 to 60 ° C., and then formaldehyde is added to 1.5 to 2.5 moles, preferably 1.9 to 2.1 moles per 1 mole of primary amine, followed by 60 to 120 ° C., preferably 90 After heating to 110 to 110 ℃ for 60 to 120 minutes the product can be obtained by drying under reduced pressure at a temperature of 100 ℃ or more.

The content of the compound (A) having the dihydro benzooxadine ring is 100 parts by weight in total of the compound (A) and the epoxy resin (B) having a dihydro benzooxadine ring in the molecule [(A) + (B) = 100] to 20 to 95 parts by weight, preferably 50 to 90 parts by weight. At this time, when the content of the compound (A) having a dihydro benzooxadine ring in the molecule is less than 20 parts by weight, the flame retardancy of the resin itself is lowered, making it difficult to achieve 94-V0 of UL, and the glass transition temperature is lowered. Heat resistance and hygroscopicity are inferior. In addition, when the content of the compound exceeds 95 parts by weight, the curing reaction time is long when pressing, the chemical skeleton of the cured product is hardened, so cracks are easily generated during the drilling process, and high temperature is required when preparing the prepreg. This causes a problem of deteriorating the appearance of the prepreg.

Examples of the epoxy resin (B) include the following compounds, but are not necessarily limited thereto.

<Bisphenol A type epoxy>

<Phenol novolac epoxy>

<Tetra phenyl ethane epoxy>

<Dicyclopentadiene epoxy>

<Bisphenol A novolac epoxy>

The content of the epoxy resin (B) used in the composition of the present invention is used in 5 to 80 parts by weight based on 100 parts by weight of the total of the compound (A) and the epoxy resin (B) [(A) + (B) = 100] It is preferably used in 10 to 50 parts by weight. When the content of the epoxy resin (B) is less than 5 parts by weight, the curing reaction time is long, and the chemical skeleton of the cured product is hard, so that cracks are easily generated during the drilling process, and high temperatures are required in manufacturing the prepreg. This causes a problem of deteriorating the appearance of the prepreg. In addition, if the content of the material exceeds 80 parts by weight, the flame retardant properties of the resin itself is lowered, it is difficult to achieve the UL 94-V0, the glass transition temperature is lowered, heat resistance and hygroscopicity is greatly reduced.

In addition, in using an epoxy resin (B), in order to prevent the fall of heat resistance and glass transition temperature, the polyfunctional epoxy resin which has three or more epoxy functional groups can be used. Examples thereof include tri-functional, tetra-functional, novolac resins, and the like, and polyfunctional epoxy resins commonly used include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, Tetraphenylmethane epoxy resins, dicyclopentadiene epoxy resins, polyglycidyl amine epoxy resins, and the like.

In the novolak or resol phenol resin (C), examples of the novolak-type phenol resins include phenol novolak resins, bisphenol A novolak resins, cresol novolak resins, phenol-modified xylene resins, alkyl phenol resins, and melamine-modified resins. And the like, and examples of the resol type phenol resin include those made of a phenol type, a cresol type, an alkyl type, a bisphenol A type or a copolymer thereof. The general phenol novolak resin has a number average molecular weight of about 600 to 800, and when using a phenol novolak resin having greatly increased it to 2000 or more, the glass transition temperature is lowered but the copper foil peeling strength tends to be greatly improved. The content of the phenol resin (C) is 5 to 80 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the total of the compound (A) and the epoxy resin (B) [(A) + (B) = 100]. do. When the content of phenol resin is used less than 5 parts by weight, the curing time is long, the crosslinking density is lowered, and heat resistance and mechanical properties are deteriorated.In addition, when the phenol resin is used in excess of 80 parts by weight, the crosslinking density is also lowered. Glass transition temperature, mechanical properties are lowered, there is a disadvantage that the water absorption is increased.

As the cyanate ester resin having two or more cyanate groups in one molecule of (D) used in the present invention, it is preferable to use a compound represented by the following formula (2). Specifically, the cyanate ester resin may be 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, or 2,2-bis (4-cyanate). Natephenyl) -1,1,1,3,3,3, -hexafluoro propane and the like. It is preferable that the said cyanate ester type resin prepolymerized the monomer. In this case, when varnishing with a solvent using a monomer, recrystallization may occur and impregnation may be impossible, and the monomer change rate of the cyanate compound is preferably reacted to be 10 to 70 mol%, more preferably. Preferably 30 to 60 mole%. When the monomer change rate of the cyanate compound is less than 10 mol%, there is a problem that recrystallization may occur. When the monomer change rate exceeds 70 mol%, the viscosity of the varnish becomes too high to impregnate the substrate, etc., and the preservation of the varnish There is a problem that the stability is also lowered.

[Formula 2]

In the formula (2),

, 또는

이고, R₂, R₃, R₄ 및 R₅ 는 각각 독립적으로 수소 또는 CH₃ 이다.R ₁ silver

, or

R ₂ , R ₃ , R ₄ and R ₅ Are each independently hydrogen or CH ₃ .

The content of the cyanate ester resin (D) is 3 to 50 parts by weight, preferably 5 to 5 parts based on 100 parts by weight of the total of the compound (A) and the epoxy resin (B) [(A) + (B) = 100]. 30 parts by weight is used. When the content of the cyanate ester resin is used in less than 3 parts by weight, the adhesion and glass transition temperature is lowered, when used in excess of 50 parts by weight varnish has a problem that the storage stability of the prepreg is sharply lowered.

The resin composition of this invention may further contain a hardening accelerator, and an imidazole series hardening accelerator is especially preferable as a hardening accelerator. Such examples include 1-methyl imidazole, 2-methyl imidazole, 2-ethyl 4-methyl imidazole, 2-phenyl imidazole ( 2-phenyl imidazole, 2-cyclohexyl 4-methyl imidazole, 4-butyl 5-ethyl imidazole, 2-methyl 5-ethyl imidazole 2-methyl 5-ethyl imidazole, 2-octhyl 4-hexyl imidazole, 2,5-chloro-4-ethyl imidazole (2,5-chloro-4-ethyl imidazole), imidazole such as 2-butoxy 4-allyl imidazole, and imidazole derivatives, and the like, due to its excellent reaction stability and low cost, such as 2-methyl imidazole or 2-phenyl. Imidazole is particularly preferred. In this case, the content of imidazole is used in an amount of 0.01 to 0.15 parts by weight, and more preferably 0.05 to 0.1 parts by weight, based on 100 parts by weight of the total resin component. If the content of the imidazole is used less than 0.01 parts by weight, the curing time is long, there is a problem that the glass transition temperature does not come out sufficiently, when used in excess of 0.15 parts by weight of varnish (varnish) storage stability is poor.

Since the non-phosphorus melamine-based flame retardant (E) contains nitrogen in the chemical skeleton, a large amount of inert gas is produced during combustion, thereby suppressing the progress of combustion. Examples thereof include melamine (2,4,6-triamino-1,3,5 trianzine), melamine cyanurate, melamine borate, and the like. On the other hand, melamine-based flame retardants containing phosphorus such as melamine polyphosphate, melamine phosphate, and the like are not applicable thereto. Among the three melamine-based flame retardants not containing phosphorus, melamine cyanurate having a pyrolysis temperature of more than 300 ° C is preferred. Melamine cyanurate is decomposed into melamine and cyanuric acid at about 320 ° C. In this process, a large amount of heat is absorbed to suppress the progress of initial combustion, and a stable char is formed during combustion. By suppressing contact with the gas, the progress of combustion is suppressed.

Since the non-phosphorus melamine flame retardant (E) has a superior flame retardant effect than the conventional inorganic flame retardant, the flame retardancy satisfies UL 94V-0 even when not excessively added like an inorganic flame retardant. Pyrolysis temperature by thermal gravimetric analysis (TGA) is at least 300 ° C or higher, which is characterized by high heat resistance and high nitrogen content.

It is preferable that a particle size of a non-phosphorus melamine type flame retardant (E) is 0.1-15 micrometers, and it is more preferable that it is 1-5 micrometers. When the particle size is less than 0.1 ㎛, filler dispersing is easy, but the specific gravity is not easy to handle, the specific surface area is wide, the viscosity rises sharply, and the manufacturing yield is low, the cost is high, the dispersion is more than 15 ㎛ Difficult and poor adhesion occurs.

The non-phosphorus melamine-based flame retardant (E) contains 30 to 80% of nitrogen in the molecular skeleton, and preferably 45 to 65%. In the case of containing less than 45% of nitrogen in the molecular skeleton, introduction of inorganic flame retardant is inevitable in order to achieve sufficient flame retardancy, which is caused by the addition of excess fillers, resulting in poor appearance of prepreg and poor adhesion. Occurs. On the other hand, when it contains more than 65% of nitrogen, the thermal decomposition temperature is lowered and the heat resistance is inferior.

The content of the non-phosphorus melamine flame retardant (E) is preferably such that the nitrogen content of the melamine flame retardant in the total resin composition is 5 to 25%, more preferably 10 to 20%.

In some cases, suitable surface treatment and / or dispersion methods may be applied to uniformize the dispersion of the non-phosphorus melamine-based flame retardant and prevent settling.

The non-phosphorus zinc-based flame retardant aid (F) has the effect of promoting the formation of char (char), suppress the generation of smoke, and prevent the generation of arc (arc). Examples include zinc borate, zinc stannate, and the like.

The content of the non-phosphorus zinc-based flame retardant aid (F) is preferably used in an amount of 2 to 20 parts by weight, and more preferably 3 to 15 parts by weight, based on 100 parts by weight of the total resin composition. If the content of the flame retardant auxiliary (F) is less than 2 parts by weight, it is difficult to exert the effect, while if it exceeds 20 parts by weight it is difficult to disperse and the adhesive strength is lowered.

Since the inorganic filler (G) has high heat resistance, low water absorption, and high specific gravity, it improves heat resistance of the resin composition and lead heat resistance after moisture absorption, and is effective in improving mechanical properties such as flexural modulus. Preferred examples of such a filler (G) include talc, silica, and the like, but are not limited thereto.

The content of the inorganic filler (G) is preferably used in an amount of 3 to 50 parts by weight, and more preferably 5 to 40 parts by weight, based on 100 parts by weight of the total resin composition. If the content of the inorganic filler (G) is less than 3 parts by weight, it is difficult to exert the effect, while if it exceeds 50 parts by weight, filler dispersion is difficult, the viscosity of the resin composition may increase rapidly and the adhesive strength may drop.

In some cases, in order to uniformly disperse the inorganic filler and prevent sedimentation, an appropriate surface treatment and / or dispersion method may be applied.

The present invention also provides a prepreg containing the non-halogen non-phosphorous flame retardant resin composition in a glass fiber. The prepreg preferably contains 40 to 70% by weight of the non-halogen non-phosphorous flame retardant resin composition in 30 to 60% by weight of glass fibers.

In addition, the present invention provides an integrated copper foil laminate by heating and pressing at least one or more laminates of the prepregs and an outer layer of copper foil located outside of the laminate. The present invention can provide a copper foil laminate by integrating the prepreg by using 1 to 8 sheets by heating and pressing a conductive material sheet (for example, copper foil) on both surfaces thereof.

The flame-retardant resin composition for copper foil laminate according to the present invention does not use a halogen-based flame retardant that has been conventionally used as a flame retardant, and does not generate toxic carcinogens such as dioxins during combustion, and does not use a phosphorus-based epoxy resin to have a phosphorus-based flame retardant. It improves the disadvantage of deterioration of electrical characteristics of semiconductor package, and improves flame resistance of resin itself than using epoxy resin alone by introducing compound containing dihydrobenzoxadine ring in molecule, heat resistance and glass transition temperature. Can exert an excellent effect.

Although the content of the present invention is described in the following Examples and Comparative Examples, the scope of the present invention is not limited thereto.

Example 1

(One) In the molecule Dehydro Benzooxadine  Preparation of compounds with rings

After mixing 1.7 kg of phenol novolak resin (trade name KPH-F-2001, manufactured by Kolon Chemical Co., Ltd.) with 1.5 kg of aniline and mixing at 60 ° C for 1 hour, formaldehyde 1.6 was added to a 5 L flask equipped with a reflux device. After adding kg to maintain the temperature at 100 ° C., a mixed solution of novolak resin and aniline was added slowly for 30 minutes. Thereafter, the reaction mixture was maintained for 1 hour, and the obtained compound was dried under reduced pressure at 120 ° C. to obtain a compound having a dihydro benzooxadine ring in the molecule. Hereinafter, the obtained resin is abbreviated as 'BE'.

(2) Non-halogen Non turnover  Preparation of Resin Composition

To prepare a non-halogen non-phosphorous resin composition with the composition shown in Table 1, the specific method is as follows.

First, 140 parts by weight of the compound (BE) prepared above was added to a 1000 ml beaker, and 100 parts by weight of methyl cellosolve was added to completely dissolve it, followed by phenol novolac epoxy resin (trade name LER N-690, Bakelite Korea). Company) 60 parts by weight and phenol novolak resin (number average molecular weight = 700, trade name XTW8293, manufactured by HUNTSMAN) 30 parts by weight, cyanate ester resin, 2,2-bis (4-cyanatephenyl) propane prepolymer ( 20 parts by weight of BA230S, manufactured by Lonza, and 0.2 parts by weight of 2-phenyl imidazole were added and completely dissolved. Thereafter, 125 parts by weight of melamine cyanurate (trade name JLS MC-810, manufactured by JLS Corporation), 20 parts by weight of silica (trade name SFP 30M, manufactured by DENKA Japan), and zinc stainate (trade name: Flamtard S, manufactured by Alcan Chemiacls Europe) ) 10 parts by weight of a slurry dispersed in methyl cellosolve was added to a mixed solution, methyl cellosolve was added so that the solid content was 60%, followed by stirring until the slurry was completely mixed with a non-halogen non-phosphorus resin. The composition was prepared.

Example 2

A non-halogen non-phosphorus resin composition was prepared with the composition shown in Table 1 below.

A resin composition was prepared in the same manner as in Example 1, except that 30 parts by weight of a phenol novolak resin (number average molecular weight = 2500, trade name GPX-41, manufactured by GIFU SHELLAC, Japan) was used instead of the phenol novolak resin. Prepared.

Example 3

A non-halogen non-phosphorus resin composition was prepared with the composition shown in Table 1 below.

A resin composition was prepared in the same manner as in Example 1, except that 30 parts by weight of bisphenol A novolak resin (trade name VH4170, manufactured by Gangnam Chemical) was used instead of the phenol novolak resin.

Example 4

A non-halogen non-phosphorus resin composition was prepared with the composition shown in Table 2 below.

A resin composition was prepared in the same manner as in Example 1, except that 60 parts by weight of bisphenol A novolac epoxy resin (trade name LER N865, manufactured by Bakelite Korea) was used instead of the phenol novolac epoxy resin.

Example 5

A non-halogen non-phosphorus resin composition was prepared with the composition shown in Table 2 below.

A resin composition was prepared in the same manner as in Example 1, except that 125 parts by weight of melamine cyanurate (trade name BUDIT 315, manufactured by BUDENHEIM) was used instead of melamine cyanurate.

Example 6

A non-halogen non-phosphorus resin composition was prepared with the composition shown in Table 2 below.

A resin composition was prepared in the same manner as in Example 1, except that 10 parts by weight of zinc borate (trade name Firebrake ZB, manufactured by BORAX) was used instead of zinc stainate.

Comparative Example 1

A non-halogen non-phosphorus resin composition was prepared using the composition shown in Table 3 below.

145 parts by weight of bisphenol A novolac epoxy resin (trade name LER N865, manufactured by Bakelite Korea Inc.) was used in place of the compound (BE) having a dihydrobenzoxadine ring in the molecule and the phenol novolac epoxy resin. Instead of 85 parts by weight of bisphenol A novolac phenol resin (trade name VH4170, manufactured by Kangnam Chemical) and 0.2 parts by weight instead of 2-phenyl imidazole, a resin composition was prepared in the same manner as in Example 1. Was prepared.

Comparative Example 2

A non-halogen non-phosphorus resin composition was prepared using the composition shown in Table 3 below.

The same procedure as in Example 1 was carried out except that 160 parts by weight of the compound (BE) having a dihydro benzooxadine ring in the molecule was used and no cyanate ester resin having two or more cyanate groups in one molecule was used. The resin composition was prepared by the method.

Comparative Example 3

A non-halogen non-phosphorus resin composition was prepared using the composition shown in Table 3 below.

Example 1 except that 250 parts by weight of aluminum trihydroxide (ATH, trade name Arafil 73, manufactured by HUNTSMAN) was used instead of melamine cyanurate (trade name JLS MC-810, manufactured by JLS, China). In the same manner as the resin composition was prepared.

[Comparative Example 4]

A non-halogen non-phosphorus resin composition was prepared using the composition shown in Table 3 below.

Example 1 except that 280 parts by weight of magnesium hydroxide (MH, trade name FLAMDANT, manufactured by Shinwon Chemical Co., Ltd.) was used instead of melamine cyanurate (trade name JLS MC-810, manufactured by JLS, China). In the same manner as the resin composition was prepared.

Experimental Example 1

(One) Copper foil Laminate  Produce

The resin composition prepared in Examples and Comparative Examples was impregnated into glass fibers (2116 manufactured by Nittobo Co., Ltd.), followed by hot air drying, to prepare a glass fiber prepreg having a resin content of 45% by weight.

Four glass fiber prepregs were laminated and placed together by placing 12 μm copper foil (manufactured by Furukawa) on both sides, followed by heating at 210 ° C. and a pressure of 45 kg / cm 2 for 90 minutes using a press. It was pressed and the copper foil laminated board of thickness 0.4mm was manufactured.

(2) Copper foil Laminate  evaluation

The physical properties of the copper foil laminate were evaluated by the following methods, and the results are shown in Tables 1 to 3 below.

(a) Glass transition temperature: The copper foil layer of the copper foil laminated sheet was removed by etching, and the glass transition temperature was measured by TMA (thermo mechanical analysis).

(b) Copper foil peeling strength: The copper foil of 1 cm in width was peeled off from the copper foil laminated board surface, and peeling strength of copper foil was measured with the tensile strength analyzer (texture analyzer).

(c) Lead heat resistance: The time to withstand after placing a 0.4 mm thick sample cut into 5 cm × 5 cm in a bath at 288 ℃.

(d) Lead heat resistance after moisture absorption: A 0.4 mm thick sample cut to a size of 5 cm × 5 cm was treated for 2 hours in an underwater tank at 120 ° C. and 2 atmospheres, and then immersed in a lead bath at 288 ° C. for 10 seconds, and then expanded. Was observed and evaluated based on the following criteria.

◎: does not expand at all

○: partially expanded

△: Mostly expanded

X: Inflate to the front side.

(e) Flame retardancy: The rod-shaped specimens were prepared from copper foil-laminated laminates and measured by UL94 test method, which is a standard method for evaluating flame retardancy divided into V-0, V-1 and V-2 grades by the vertical combustion test method. .

As shown in Table 1 and 2, when using the melamine cyanurate (JLS MC-810) flame retardant in Examples 1 to 3 according to the present invention showed good flame retardancy and excellent heat resistance and lead heat resistance after moisture absorption, phenol furnace In the case of Example 1 using a volac resin (number average molecular weight = 700), a particularly high glass transition temperature was shown, and in Example 2 using a phenol novolac resin (number average molecular weight = 2500), particularly a high copper foil peel strength Indicated. In Example 3 using bisphenol A novolak resin, the physical properties of Examples 1 and 2 were shown at the glass transition temperature and the copper foil peel strength. In the case of Example 4 using bisphenol A novolac epoxy resin, the glass transition temperature was further increased, and in Example 5 using another kind of melamine cyanurate (BUDIT 315, no surface treatment), Example 1 Slightly lacking but overall excellent properties. Example 6 using zinc borate (Firebrake ZB) also exhibited a high glass transition temperature, excellent copper foil peel strength, excellent heat resistance and flame resistance.

As shown in Table 3, in Comparative Example 1 using a bisphenol A novolac epoxy resin instead of using a compound having a dihydro benzooxadine ring in the molecule, the heat resistance and lead heat resistance after moisture absorption is excellent, but the glass The transition temperature was low, the flame retardancy did not achieve UL 94V-0, and copper foil peeling strength fell. In addition, in Comparative Example 2 without using a cyanate ester resin, flame retardancy was good, but the glass transition temperature was low, the copper foil peel strength was low, and the lead heat resistance after moisture absorption was insufficient. In Comparative Example 3 using an excessive amount of aluminum trihydroxide (ATH) and Comparative Example 4 using an excessive amount of magnesium hydroxide (MH), the flame retardancy is good, but the copper foil peel strength was very poor due to the excess flame retardant, comparison In the case of Example 3, the lead heat resistance and the lead heat property after moisture absorption also fell very much.

The non-halogen-based non-phosphorus resin composition of the present invention does not generate toxic carcinogens such as dioxins during combustion, and improves flame retardant properties and heat resistance properties of the resin itself by introducing a compound having a dihydrobenzoxadine ring in the molecule. By using a non-phosphorus melamine-based flame retardant having a pyrolysis temperature of 300 ° C. or more and a zinc-based flame retardant as appropriately mixed, there is an effect of having good flame retardancy, excellent heat resistance, and heat resistance after moisture absorption without lowering the glass transition temperature.

Those skilled in the art will be able to make various applications and modifications within the scope of the present invention based on the above contents.

Claims (14)

(A) a compound having a dihydro benzoxadine ring in a molecule, (B) an epoxy resin, (C) a novolak or a resol phenol resin, (D) a cyanate ester resin having two or more cyanate groups in one molecule, (E) a non-phosphorus melamine flame retardant, (F) zinc flame retardant aid and (G) inorganic filler; To 100 parts by weight of the total of the compound (A) and the epoxy resin (B), The compound (A) is 20 to 95 parts by weight, the epoxy resin (B) is 5 to 80 parts by weight, the novolak or resol phenol resin (C) is 5 to 80 parts by weight, at least two of the cyan Cyanate ester resin (D) having an nate group is included in an amount of 3 to 50 parts by weight; Based on 100 parts by weight of the total resin composition, The non-phosphorus melamine-based flame retardant (E) is included so that the nitrogen content of the melamine-based flame retardant is 5 to 25%, the non-phosphorus zinc-based flame retardant (F) is included in an amount of 2 to 20 parts by weight, The inorganic filler (G) is included in an amount of 3 to 50 parts by weight; A non-halogen-based non-phosphorus-based flame retardant resin composition for a copper foil laminate comprising a compound having a dihydro benzooxadine ring in a molecule of the compound (A):

(One) Wherein R ₁ is an alkyl group, a cyclohexyl group, a phenyl group, or a phenyl group substituted from an alkyl group or an alkoxy group. The method of claim 1, wherein the compound (A) is reacted with 0.5 to 1.5 mol of the primary amine with respect to 1 mol of the compound having a phenolic hydroxyl group, and formaldehyde is 1.5 to 2.5 mol with respect to 1 mol of the primary amine. A non-halogen type non-phosphorus flame-retardant resin composition which is added and obtained by ring-opening reaction of dihydro benzooxadine. delete delete delete delete delete The non-halogen non-phosphorous flame-retardant resin composition of claim 1, wherein the non-phosphorus melamine flame retardant (E) has a pyrolysis temperature (5% weight loss temperature) of at least 300 ° C. by thermogravimetric analysis (TGA). The non-halogen-based non-phosphorous flame-retardant resin composition according to claim 1, wherein the non-phosphorus melamine-based flame retardant (E) contains 30 to 80% of nitrogen in a molecule and has a particle diameter of 0.1 to 15 µm. delete delete delete A prepreg in which the resin composition according to any one of claims 1, 2, 8 and 9 is impregnated into glass fibers, wherein the resin composition is 40 to 70% by weight, and the glass fiber is 30 to 60% by weight. Prepreg in% by weight. A copper foil laminated sheet which is integrated by heating and pressing at least one or more laminates of the prepreg of claim 13 and a copper foil outer layer located outside of the laminate.