KR100861645B1 - Flame retardant resin composition, prepreg using the same, and copper clad laminate using the same - Google Patents

Abstract

The present invention relates to a flame retardant resin composition, a prepreg using the same, and a copper foil laminate using the same.

The flame retardant resin composition according to the present invention does not generate a toxic carcinogen such as dioxin during combustion because it does not use a halogen-based flame retardant, and does not use a phosphorus-based epoxy resin. By introducing a compound containing a dihydro benzooxadine ring in the molecule, it improves the flame retardancy of the resin itself than the existing epoxy resin alone, heat resistance and glass transition temperature, lead heat resistance after moisture absorption Excellent property

Therefore, the flame-retardant resin composition which concerns on this invention can be usefully used for prepreg manufacture, A copper foil laminated board can be manufactured using this prepreg.

Description

Flame retardant resin composition, prepreg using the same, and copper clad laminate using the same}

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

Recently, as electronic devices are represented by portable products, miniaturization, light weight, and high functionality are required. In order to cope with this problem, the parts mounted on the printed circuit board may also have pins or pitches from QFP (Quad Flat Package) to TCP (Tape Carrier Package), BGA (Ball Grid Array), and FC (Flip Chip). In Japan, a chip size package (CSP) of the same size as a bare chip is attracting 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. In the conventional resin composition for prepregs or laminates, amine-based curing agents and curing accelerators are generally used 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 is likely to generate toxic gas upon combustion and to generate dioxine, a carcinogen, and thus it is strongly required to regulate the use of halogen-containing substances. Regulation of the use of phosphorus antimony is also strongly required. In addition, phosphorus-containing materials, which are widely used for improving flame retardancy, together 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 Laid-Open Nos. 2003-213077, 2003-206390, 2002-249639, 2001-302879 and the like, and US Patent No. 5,946,222. It is described in.

Japanese Patent Application Laid-Open No. 2003-206390 and US Pat. No. 5,946,222 describe a method of reacting a compound having a dihydro benzooxadine ring and a novolak phenol resin in a molecule. In this case, however, it exhibits high glass transition temperature (Tg) and heat resistance, but it has been found that the flame retardancy of these compositions alone is difficult to achieve 94 V-0 of UL.

Japanese Patent Laid-Open Nos. 2003-213077 and 2001-302879 disclose non-halogen condensed phosphate esters or reactive phosphate esters and inorganic flame retardants in a compound in which a compound having a dihydro benzooxadine ring, an epoxy resin and a phenol resin is reacted in a molecule. The introduced method is described. Japanese Laid-Open Patent Publication No. 2002-249639 discloses a method in which a melamine-modified phenol resin, a non-halogen condensed phosphate ester, and an inorganic flame retardant are introduced as a non-halogen flame retardant to a compound having a dihydro benzooxadine ring in a molecule. However, the non-halogen condensed phosphate esters or reactive phosphate esters used in the aforementioned patent documents contain phosphorus in the molecular structure, have poor heat resistance and high water absorption rate, and greatly reduce the heat resistance of the resin composition and lead heat resistance after moisture absorption. The floating problem occurs, and because it melts at a temperature of 100 ℃ or less, there is a problem that the thickness is difficult to control the flowability when pressing. In particular, reactive phosphate esters have the disadvantage of lowering the glass transition temperature much. In addition, aluminum trihydroxide (ATH), which is an inorganic flame retardant, has a disadvantage in that pyrolysis starts at around 220 ° C., which degrades heat resistance. Magnesium Hydroxide (MH), another inorganic flame retardant, has to be added in large amounts to achieve 94V-0 of UL when it is introduced into a common resin composition, which increases the viscosity and decreases fairness. do.

In Japanese Patent Laid-Open No. 2001-302870, phosphorus or nitrogen is included in an epoxy resin or a phenol resin to improve flame retardancy. In this case, however, the glass transition temperature (Tg) is lowered and heat resistance is lowered.

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

In order to solve the above problems, the present inventors do not use halogen-based and phosphorus-based flame retardants while studying a resin composition having excellent flame resistance, heat resistance, glass transition temperature, and lead heat resistance after moisture absorption without containing halogen and phosphorus. The flame retardancy without UL meeting the 94V-0 flame retardant grade, improves the electrical properties deterioration for semiconductors, high heat resistance and glass transition temperature, and has found a flame retardant resin composition excellent in lead heat resistance after moisture absorption, and completed the present invention.

The present invention is to provide a flame retardant resin composition, a prepreg using the same, and a copper foil laminate using the same.

The present invention

(A) a compound having a dihydro benzooxadine ring in the molecule,

(B) epoxy resin,

(C) novolac or resol phenolic resin,

(D) cyanate ester resins having two or more cyanate groups in one molecule,

(E) an inorganic metal flame retardant, and

(F) Provides a flame retardant resin composition containing an inorganic filler.

In addition, the present invention provides a prepreg using the flame-retardant resin composition.

Moreover, this invention provides the copper foil laminated board using the said prepreg.

Hereinafter, the present invention will be described in detail.

In the flame retardant resin composition according to the present invention, the (A) compound having a dihydro-benzoxazol Dean ring in the molecule is dihydro-benzoxazol Dean as having a ring if a resin that is curable by ring-opening reaction of dihydro-benzoxazol Dean particularly limited It doesn't work. For example, the compound having a dihydro benzooxadine ring in the molecule (A) can be prepared from a compound having a phenolic hydroxyl group, a primary amine and formaldehyde.

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. The polyfunctional phenols include catechol, hydroquinone, resorcinol, and the like. The bisphenol compounds include bisphenol A, bisphenol F, isomers thereof, and bisphenol S. As said phenol resin, a phenol novolak resin, a resol phenol resin, a phenol modified xylene resin, an alkyl phenol resin, a melamine phenol resin, a phenol modified polybutadiene resin, etc. are mentioned.

Examples of the primary amine include methyl amine; Cyclo hexylamine; Aniline; And aniline substituted with a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ alkoxy group, a cyclohexyl group, or a phenyl group. 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, for the preparation of a compound having a dihydro benzooxadine ring in the molecule (A), the following method can be used, but the scope of the present invention is not limited thereto. To 1 mole of the compound having phenolic hydroxyl groups, 0.5 to 1.5 moles, preferably 0.6 to 1.0 mole, of primary amine are added and the mixture is heated to 50 to 60 ° C. Formaldehyde is added to the mixture in an amount of 1.5 mol to 2.5 mol, preferably 1.9 mol to 2.1 mol, based on 1 mol of the primary amine, and then heated to 60 to 120 캜, preferably 90 to 110 캜, and 60 to 120 After reacting for a minute, the product is dried under reduced pressure at a temperature of 100 ° C. or higher.

The compound having a dihydro benzooxadine ring in the molecule (A) may include a structure represented by the following formula (1).

In Chemical Formula 1, R ₁ is C ₁ ~ C ₆ Alkyl groups; Cyclohexyl group; Phenyl group; Or is a phenyl group substituted with an alkoxy of C ₁ ~ C ₆ alkyl group or a C ₁ ~ C ₆ a.

The content of the compound having a dihydro benzooxadine ring in the molecule (A) is 100 parts by weight in total of the compound having a dihydro benzooxadine ring in the molecule (A) and the epoxy resin (B) [(A) + ( B) = 100] is preferably 50 to 95 parts by weight, more preferably 60 to 90 parts by weight. If the content of the compound having a dihydro benzooxadine ring in the molecule is less than 50 parts by weight, the flame retardant properties of the resin itself is lowered, making it difficult to achieve 94V-0 of UL, lowering the glass transition temperature, and poor heat resistance and hygroscopicity. . 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.

In the flame retardant resin composition according to the present invention, the (B) epoxy resin may be selected from the group consisting of the following compounds, but is not limited thereto.

<Bisphenol A type epoxy>

Wherein R is C ₁ ~ C ₆ Alkyl groups; Cyclohexyl group; Phenyl group; Or a phenyl group substituted with a C ₁ to C ₆ alkyl group or a C ₁ to C ₆ alkoxy group, n is an integer of 1 to 50.

<Phenol novolac epoxy>

<Tetra phenyl ethane epoxy>

<Dicyclopentadiene epoxy>

<Bisphenol A novolac epoxy>

The content of the epoxy resin (B) is from 5 to 100 parts by weight of the total of 100 parts by weight of the compound having a dihydrobenzooxadine ring in the molecule (A) and the epoxy resin (B) ((A) + (B) = 100). It is preferable that it is 50 weight part, and it is more preferable that it is 10-40 weight part. If the content of the epoxy resin is less than 5 parts by weight, the curing reaction time is long, the chemical skeleton of the cured product is hard, so cracks are easily generated during the drilling process, and high temperatures are required for prepreg production, which causes prepregs. Problems with the appearance of the leg worsens. In addition, when the content of the epoxy resin exceeds 50 parts by weight, the flame retardant property of the resin itself is lowered, it is difficult to achieve 94V-0 of UL, the glass transition temperature is lowered, heat resistance and hygroscopicity is greatly reduced.

In addition, in using (B) an epoxy resin, 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 trifunctional, tetrafunctional, and novolak resins. Commonly used multifunctional epoxy resins include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, tetraphenyl ethane epoxy resins, dicyclopentadiene epoxy resins, and poly glycidyl amine epoxy resins. Etc.

In the flame retardant resin composition according to the present invention, examples of the novolak phenol resin in the (C) novolak or resol phenol resin include phenol novolak resin, bisphenol A novolak resin, cresol novolak resin, phenol-modified xylene resin, alkyl Phenol resins, melamine-modified resins, and the like. In addition, examples of the resol phenol resins include phenol type, cresol type, alkyl type, bisphenol A type or copolymers thereof. The general novolak phenol resin has a number average molecular weight of about 600 to 800, and when using a novolak phenol resin that greatly increased it to 2000 or more, copper foil peeling strength tends to be greatly improved.

The content of the (C) phenol resin is from 5 to 100 parts by weight of the total of 100 parts by weight of the compound having a dihydrobenzooxadine ring and the epoxy resin (B) in the molecule (A). It is preferable that it is 40 weight part, and it is more preferable that it is 10-30 weight part. If the content of the phenol resin is less than 5 parts by weight, the curing time is long, the crosslinking density is lowered, and the heat resistance and mechanical properties are deteriorated.If the phenol resin is used in excess of 40 parts by weight, the crosslinking density is also lowered. And glass transition temperature, mechanical properties are lowered, moisture absorption is increased, flame retardant properties are lowered, it is difficult to achieve 94V-0 of UL.

In the flame retardant resin composition according to the present invention, it is preferable to use a compound represented by the following formula (2) for the cyanate ester resin having two or more cyanate groups in the molecule (D) .

또는

이다.In Formula 2, R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or C ₁ ~ C ₆ Alkyl group, R ₆ is

or

to be.

Specifically, the cyanate ester resin having two or more cyanate groups in one molecule includes 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, Or 2,2-bis (4-cyanatephenyl) -1,1,1,3,3,3-hexafluoro propane. The cyanate ester resin having two or more cyanate groups in one molecule is preferably a prepolymerized monomer. In this case, when varnishing with a solvent using a monomer, recrystallization may occur and impregnation may be impossible. Therefore, the monomer change rate of the cyanate compound in the prepolymerized cyanate ester resin is preferably reacted to be 10 to 70 mol%, more preferably 30 to 60 mol%. If the monomer change rate of the cyanate compound is less than 10 mol%, recrystallization may occur. If it exceeds 70 mol%, the viscosity of the varnish becomes too high to impregnate the substrate, and the storage stability of the varnish is also reduced. do.

The content of the cyanate ester resin having two or more cyanate groups in one molecule (D) is 100 parts by weight in total of the compound having a dihydrobenzooxadine ring in the molecule (A) and the epoxy resin (B). A) + (B) = 100] is preferably from 3 to 50 parts by weight, more preferably from 5 to 30 parts by weight. If the content of the cyanate ester resin is less than 3 parts by weight, the adhesive strength 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 the present invention may further include a curing accelerator and a curing retardant. As a hardening accelerator, an imidazole series hardening accelerator is especially preferable, and a hardening retardant is a boric acid type hardening retarder.

Examples of the imidazole series curing accelerators include 1-methyl imidazole, 2-methyl imidazole, 2-ethyl 4-methyl imidazole, and 2-ethyl 4-methyl imidazole. ), 2-phenyl imidazole, 2-cyclohexyl 4-methyl imidazole, 4-butyl 5-ethyl imidazole , 2-methyl 5-ethyl imidazole, 2-octyl 4-hexyl imidazole, 2,5-dichloro-4-ethyl imidazole (2 Imidazoles such as, 5-dichloro-4-ethyl imidazole), 2-butoxy 4-allyl imidazole, and imidazole derivatives, and the like, particularly due to excellent reaction stability and low cost. Preference is given to 2-methyl imidazole or 2-phenyl imidazole. The content of the imidazole is preferably 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 composition. If the content of imidazole is less than 0.01 part by weight, the curing time may be long, and the glass transition temperature may not come out sufficiently. If the content of the imidazole is more than 0.15 part, the storage stability of varnish is reduced.

It is preferable that it is 0.01-0.2 weight part with respect to 100 weight part of total resin compositions, and, as for the content of boric acid which can be used as the said curing retardant, it is more preferable that it is 0.05-0.15 weight part. If the content of boric acid is less than 0.01 parts by weight, it is difficult to realize a high glass transition temperature because the curing temperature and the curing density cannot be sufficiently increased. If the content of the boric acid is more than 0.2 parts by weight, the curing temperature is too high and uncured at the time of press, resulting in poor heat resistance.

In the flame retardant resin composition according to the present invention, the inorganic metal flame retardant (E) preferably uses magnesium hydroxide (MH). Conventionally, the content of (B) epoxy resins and (C) novolac or resol phenol resins having relatively low flame retardancy and poor flame retardant properties of the compound having (A) dihydrobenzooxadine ring having excellent flame retardant properties. In order to achieve a UL 94V-0 standard by introducing a large amount of magnesium hydroxide, there was a disadvantage in that the viscosity of the varnish rapidly rises and the processability is very poor. However, in the present invention, the content of the compound having the (A) dihydro benzooxadine ring having excellent flame retardant properties is greatly increased than in the prior art, and the resin in the varnish [(A) + (B) + (C) + ( D)] It is introduced to occupy more than 50 parts by weight of 100 parts by weight, by introducing a large amount of inorganic fillers, non-combustible materials to improve the flexural modulus, to minimize the content of magnesium hydroxide to maintain fairness while maintaining UL 94V-0 The specification was achieved.

The content of magnesium hydroxide in the inorganic metal flame retardant (E) is preferably 10 to 40 parts by weight based on 100 parts by weight of the resin [(A) + (B) + (C) + (D)] in the varnish, 15 More preferably, it is 30 weight part. If the content of magnesium hydroxide is less than 10 parts by weight, it is difficult to achieve UL's 94V-0 specification, and if it exceeds 40 parts by weight, the processability is very poor and the copper foil peel strength is weak.

In a high flexural modulus in accordance with the present invention for non-halogen-based and non-phosphorus-retardant resin composition, wherein (F) an inorganic The filler is preferably a silica filler. Since the silica filler 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.

The content of the inorganic filler (F) is preferably 50 to 100 parts by weight, more preferably 60 to 80, based on 100 parts by weight of the resin [(A) + (B) + (C) + (D)] in the varnish. Parts by weight. If the content of the inorganic filler is less than 50 parts by weight, it is difficult to implement high flexural modulus and lower the flame retardant properties. If the content is more than 100 parts by weight, filler dispersion may be difficult, the viscosity of the resin composition may increase rapidly, and the adhesion may be degraded. .

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 flame retardant resin composition according to the present invention may further include a mixture of a naphthol dye and a metal complex salt acid dye in the (G) azo dye.

The mixture of the naphthol dye and the metal complex salt acid dye in the azo dye (G) is used to make the color of the prepreg and the laminate black and to facilitate the product inspection in the printed circuit board manufacturing process. Conventionally, only one of naphthol dyes and metal complex acid dyes is used, but varnish formulations have a disadvantage in that color is difficult to realize with only one dye or that heat resistance is weak. Therefore, in the present invention, by appropriately mixing the naphthol dye and the metal complex salt acid dye in the azo dye, it is possible to suppress implementation of black and weakness of heat resistance.

The naphthol dye is preferably a compound represented by the following Chemical Formula 3, and the metal complex acid dye is preferably a compound represented by the following Chemical Formula 4.

The naphthol dye represented by Chemical Formula 3 has excellent heat resistance, and the metal complex salt acid dye represented by Chemical Formula 4 has excellent color development to black.

The content of the naphthol dye and the metal complex salt acid dye in the (G) azo dye was 0.4 to 1.0 parts by weight based on 100 parts by weight of the resin [(A) + (B) + (C) + (D)] in the varnish. It is preferable that it is preferable that it is 0.6-0.8 weight part, respectively. If the content of the naphthol dye in the azo dye is less than 0.4 parts by weight, it is difficult to exert the effect, if it exceeds 1.0 parts by weight may reduce the dispersibility and adhesion of the dye. In addition, when the content of the metal complex salt acid dye in the azo dye is less than 0.4 parts by weight, it is difficult to exert the effect, when it exceeds 1.0 parts by weight may lower the heat resistance.

The present invention also provides a prepreg comprising the flame retardant resin composition according to the present invention in a glass fiber.

The prepreg is preferably 30 to 60% by weight of the flame retardant resin composition according to the present invention in 30 to 60% by weight of glass fiber.

The present invention also provides an integrated copper foil laminate by heating and pressurizing at least one or more laminates of the prepreg and an outer layer of copper foil located outside of the laminate.

In one embodiment of the present invention, by using one to eight sheets of the prepreg, a conductive sheet (for example, copper foil) is heated and integrated on both sides to provide a copper foil laminate. At this time, the reaction conditions are preferably heated and pressurized for 80 to 100 minutes at a temperature of 200 ~ 250 ℃ temperature, 40 ~ 50 kg / ㎠.

The flame retardant resin composition according to the present invention does not generate a toxic carcinogen such as dioxin during combustion because it does not use a halogen-based flame retardant, and does not use a phosphorus-based epoxy resin. By introducing a compound containing a dihydro benzooxadine ring in the molecule, it improves the flame retardancy of the resin itself than the existing epoxy resin alone, heat resistance and glass transition temperature, lead heat resistance after moisture absorption Excellent property

Therefore, the flame-retardant resin composition which concerns on this invention can be usefully used for prepreg manufacture, A copper foil laminated board can be manufactured using this prepreg.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Example  One  :

1. in a molecule Dehydro Benzooxadine  Preparation of compounds with rings

After mixing 1.7 kg of phenol novolac resin (trade name KPH-F-2001, manufactured by Kolon Emulsion Co., Ltd.) with 1.5 kg of aniline and mixing at 60 ° C for 1 hour, 1.6 kg of formaldehyde in a 5 L flask equipped with a reflux device. After adding to maintain the temperature at 100 ° C., a mixed solution of novolak resin and aniline was slowly added 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 (A) having a dihydro benzooxadine ring in the molecule.

2. Preparation of Flame Retardant Resin Composition

First, 80 parts by weight of the compound (A) prepared in 1 above was added to a 1000 ml beaker, and 100 parts by weight of methyl cellosolve was added thereto to completely dissolve. (B) 20 parts by weight of bisphenol A novolac epoxy resin ( C) 10 parts by weight of a cresol novolak resin (number average molecular weight = 2500), (D) 7 parts by weight of a 2,2-bis (4-cyanatephenyl) propane prepolymer (BA230S, manufactured by Lonza) with a cyanate ester resin , 0.1 parts by weight of 2-phenyl imidazole, 0.1 parts by weight of boric acid, 0.7 parts by weight of (G) azo naphthol dye, and 0.7 parts by weight of azo metal complex salt acid dye were completely dissolved. Then, (E) 25 parts by weight of magnesium hydroxide (trade name Magnifin, manufactured by ALBEMARLE), and (F) 75 parts by weight of silica (trade name SFP 30M, manufactured by DENKA, Japan) were dispersed in a methyl cellosolve. Into the mixed solution, methylcellosolve was added so that the solid content was 50%, followed by stirring until the slurry was completely mixed to prepare a flame retardant resin composition.

Example  2  :

A flame-retardant resin composition was prepared in the same manner as in Example 1 2, except that 20 parts by weight of a phenol novolac epoxy resin was used instead of the bisphenol A novolac epoxy resin in Example 1 2.

Example  3  :

Example 2, except that 25 parts by weight of magnesium hydroxide (trade name Magshield, manufactured by MARTIN MARIETTA) instead of magnesium hydroxide (trade name Magnifin, manufactured by ALBEMARLE), the same as in Example 1 2 A flame retardant resin composition was prepared by the method.

Comparative example  One  :

100 parts by weight of bisphenol A novolac epoxy resin was used in place of the compound having a dihydro benzooxadine ring in the molecule in Example 2, and 50 parts by weight of cresol novolac resin was used instead of 10 parts by weight of cresol novolac resin. , A flame retardant resin composition was prepared in the same manner as in Example 1 2, except that the filler composition was added in the same manner as in Example 1 to the resin composition weight.

Comparative example  2  :

Except that in Example 1 2, except that the cyanate ester resin having two or more cyanate groups in one molecule is not used and the filler composition is added in the same manner as in Example 1 relative to the weight of the resin composition, A flame retardant resin composition was prepared in the same manner as in Example 2.

Comparative example  3  :

Example 2 2 and 2 except that aluminum trihydroxide (ATH, trade name Arafil 73, manufactured by HUNTSMAN) was used instead of magnesium hydroxide (trade name Magnifin, manufactured by ALBEMARLE). In the same manner, a resin flame retardant composition was prepared.

Comparative example  4  :

In Example 1 2, except that 0.7 parts by weight of azo-based naphthol dyes and 0.7 parts by weight of azo metal complex salt acid dyes, 1.4 parts by weight of only azo-based naphthol dyes were used. Flame retardant resin composition was prepared in the same manner as.

Comparative example  5  :

Example 1 Example 2, except that 0.7 parts by weight of the azo-based naphthol dye and 0.7 parts by weight of the azo metal complex salt acid dye, except that only 1.4 parts by weight of the azo metal complex salt acid dye was used, Example 1 Flame-retardant resin composition was prepared in the same manner as in 2.

Comparative example  6  :

A flame retardant resin composition was prepared in the same manner as in Example 1 2, except that silica (SFP 30M) was not used in Example 2 2.

Experimental Example  Physical property evaluation

Copper foil Laminate  Produce

After impregnating the resin composition prepared in Examples 1 to 3 and Comparative Examples 1 to 6 into glass fibers (2116 manufactured by Nittobo), and hot air dried to prepare a glass fiber prepreg having a resin content of 45% by weight. It was. Four glass fiber prepregs were laminated, and then placed together by placing 12 µm copper foil (manufactured by Furukawa) on both sides, followed by heating at a temperature of 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. Property evaluation

Physical properties of the copper foil laminate prepared by using the resin composition prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were evaluated in the following manner.

(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 peel strength

After peeling off the copper foil of width 1cm from the copper foil laminated board surface, the peeling strength of the copper foil was measured with the tensile strength analyzer (texture analyzer).

(c) lead heat resistance

The endurance time was measured after raising a 0.4 mm thick sample cut to a size of 5 cm × 5 cm in a bath at 288 ℃.

(d) lead heat resistance after moisture absorption

A 0.4 mm-thick sample cut into 5 cm x 5 cm size was treated for 2 hours in an underwater tank at 120 ° C and 2 atmospheres, and then immersed in a bath at 288 ° C for 10 seconds, and then observed for expansion and the following criteria. Evaluated.

※ ◎: No expansion at all

   ○: partly inflated,

   △: most of the expansion,

   X: Inflate to the front side.

(e) flame retardant

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

Physical property measurement results are shown in Table 1.

division Example Comparative example One 2 3 One 2 3 4 5 6 Resin composition Compounds with dihydrobenzoxadine rings in the molecule 80 80 80 - 80 80 80 80 80 Bisphenol A Novolak Epoxy Resin 20 - 20 100 20 20 20 20 20 Phenolic Novolak Epoxy Resin - 20 - - - - - - - Cresol Novolak Resin (Mn = 2500) 10 10 10 50 10 10 10 10 10 Cyanate Ester Resin 7 7 7 10 - 7 7 7 7 2-phenyl imidazole (2PI) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Boric acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Azo Naphthol Dye 0.7 0.7 0.7 0.7 0.7 0.7 1.4 - 1.4 Azo metal complex salt acid dye 0.7 0.7 0.7 0.7 0.7 0.7 - 1.4 1.4 Filler composition Magnesium Hydroxide (Magnifin) 25 25 - 34 24 - 25 25 25 Magnesium Hydroxide (Magshield) - - 25 - - - - - - ATH (Arafil73) - - - - - 25 - - - Silica (SFP 30M) 75 75 75 102 72 75 75 75 - Properties Varnish gel time (seconds) @ 160 ° C 360 380 362 420 430 365 358 357 380 Glass transition temperature (℃) 175 171 175 167 165 175 176 174 178 Copper Foil Peeling Strength (kgf / cm) 1.05 1.10 1.02 0.98 0.78 1.08 1.04 1.03 1.25 Lead Heat Resistance (sec) @ 288 ℃ 900 820 850 1050 520 31 1210 61 650 Lead heat resistance after moisture absorption @ 288 ℃ ◎◎◎ ◎◎◎ ◎◎◎ ◎◎◎ ○○○ × △△ ◎◎◎ × ○○ ◎◎◎ Flexural modulus (Gpa) 28 27 28 27 27 28 28 28 15 Black implementation OK OK OK OK OK OK NG OK OK Flame Retardant (UL94) V-0 V-0 V-0 V-1 V-0 V-0 V-0 V-0 V-1

As shown in Table 1, the flame-retardant resin composition (Examples 1 to 3) according to the present invention uses a large amount of a compound having a dihydro benzooxadine ring excellent in flame retardant properties, and introduces a large amount of silica filler which is a non-combustible material. At the same time, some magnesium hydroxide was introduced to show good flame retardancy, excellent heat resistance, heat resistance after moisture absorption, and high flexural modulus. In Example 1 using a bisphenol A novolac epoxy resin, glass transition temperature and heat resistance were superior to those of Example 2 using a phenol novolac epoxy resin, and the copper foil peeling strength of Example 2 was better. In the case of Example 1 and Example 3 in which the manufacturer used different magnesium hydroxide, the overall physical properties were similar, but the heat resistance was slightly superior in Example 1 using magnesium hydroxide.

On the other hand, in Comparative Example 1 using bisphenol A novolac epoxy resin instead of using a compound having a dihydro benzooxadine ring in the molecule, the glass transition temperature is excellent in heat resistance, lead heat resistance after moisture absorption, and flexural modulus. Was low, the flame retardancy did not achieve UL 94V-0, and copper foil peeling strength was inferior. 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 peeling strength was low, and the lead heat resistance after moisture absorption was insufficient. In Comparative Example 3 using aluminum trihydroxide (ATH) instead of magnesium hydroxide, flame retardancy was good, but lead heat resistance and lead heat resistance after moisture absorption became very weak. In Comparative Example 4 using only azo-naphthol dye alone instead of mixing azo-naphthol dye and azo-metal complex salt acid dye, the heat resistance was excellent but failed to realize black color, and only azo-based metal complex salt acid dye was used. In the case of Comparative Example 5 used alone, black was realized but the heat resistance was very weak. In Comparative Example 6, in which the silica filler was not introduced, the copper foil peeling strength was very high, but the flexural modulus was very weak and UL 94 V-0 was not implemented.

The flame retardant resin composition according to the present invention does not generate a toxic carcinogen such as dioxin during combustion because it does not use a halogen-based flame retardant, and does not use a phosphorus-based epoxy resin. By introducing a compound containing a dihydro benzooxadine ring in the molecule, it improves the flame retardancy of the resin itself than the existing epoxy resin alone, heat resistance and glass transition temperature, lead heat resistance after moisture absorption Excellent property

Therefore, the flame-retardant resin composition which concerns on this invention can be usefully used for prepreg manufacture, A copper foil laminated board can be manufactured using this prepreg.

Claims (17)

(A) a compound having a dihydro benzooxadine ring in the molecule, (B) epoxy resin, (C) novolac or resol phenolic resin, (D) cyanate ester resins having two or more cyanate groups in one molecule, (E) Magnesium Hydroxide (MH), and (F) Flame retardant resin composition containing a silica filler. The flame retardant resin composition according to claim 1, wherein the compound having a dihydro benzooxadine ring in the molecule (A) is a compound represented by the following general formula (1). <Formula 1>

In Chemical Formula 1, R ₁ is C ₁ ~ C ₆ Alkyl groups; Cyclohexyl group; Phenyl group; Or is a phenyl group substituted with an alkoxy of C ₁ ~ C ₆ alkyl group or a C ₁ ~ C ₆ a. The compound content according to claim 1, wherein the compound content having a dihydro benzooxadine ring in the molecule (A) is 100 parts by weight in total of the compound having a dihydro benzooxadine ring in the molecule (A) and the epoxy resin (B). (A) + (B) = 100] 50 to 95 parts by weight based on the flame retardant resin composition. The flame retardant resin composition of claim 1, wherein the epoxy resin (B) is selected from the group consisting of the following compounds. <Bisphenol A type epoxy>

Wherein R is C ₁ ~ C ₆ Alkyl groups; Cyclohexyl group; Phenyl group; Or a phenyl group substituted with a C ₁ to C ₆ alkyl group or a C ₁ to C ₆ alkoxy group, n is an integer of 1 to 50. <Phenol novolac epoxy>

<Tetra phenyl ethane epoxy>

<Dicyclopentadiene epoxy>

<Bisphenol A novolac epoxy>

The content of the epoxy resin (B) is a total of 100 parts by weight of the compound having a dihydro benzooxadine ring in the molecule (A) and the epoxy resin (B) [(A) + (B) = 100 to 5 to 50 parts by weight, based on the flame retardant resin composition. The content of the (C) novolak or resol phenol resin is 100 parts by weight in total of the compound having a dihydro benzooxadine ring and the (B) epoxy resin in the molecule (A). (B) = 100] non-halogen-based and non-phosphorous flame-retardant resin composition for high flex modulus, characterized by containing 5 to 40 parts by weight. The flame retardant resin composition according to claim 1, wherein the cyanate ester resin having two or more cyanate groups in one molecule (D) is a compound represented by the following general formula (2). <Formula 2>

In Chemical Formula 2, R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen or an alkyl group of C ₁ to C ₆ , and R ₆ is

or

to be. delete The flame retardant resin composition according to claim 1, wherein the content of the magnesium hydroxide (E) is 10 to 40 parts by weight based on 100 parts by weight of the total of the components (A) to (D). delete The flame retardant resin composition according to claim 1, wherein the content of the silica filler (F) is 50 to 100 parts by weight based on 100 parts by weight of the total of the components (A) to (D). The flame retardant resin composition according to claim 1, further comprising a mixture of a naphthol dye and a metal complex salt acid dye in the (G) azo dye. The mixture of the naphthol dye and the metal complex salt acid dye of the (G) azo dye is a mixture of the naphthol dye represented by the following formula (3) and the metal complex salt represented by the following formula (4). Flame retardant resin composition. <Formula 3>

<Formula 4>

The content of the naphthol dye and the metal complex salt acid dye in the (G) azo dye includes 0.4 to 1.0 parts by weight based on 100 parts by weight of the total of the components (A) to (D), respectively. Flame retardant resin composition, characterized in that. The prepreg comprising 40 to 70% by weight of the flame retardant resin composition of any one of claims 1 to 7, 9 and 11 to 14 in 30 to 60% by weight of the glass fiber. A copper foil laminated plate which is integrated by heating and pressing at least one or more laminates of the prepreg of claim 15 and an outer layer of copper foil located outside of the laminate. The copper foil laminate according to claim 16, wherein the reaction conditions are heated and pressurized for 80 to 100 minutes at a temperature of 200 to 250 ° C and a pressure of 40 to 50 kg / cm 2.