JPH11158352A - Epoxy resin composition, epoxy resin prepreg and epoxy resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition having flame retardancy without using a halogen and having good heat resistance, and to provide an epoxy resin laminate. SOLUTION: This thermosetting resin composition contains an epoxy resin, a thermosetting resin having dihydrobenzoxazine rings, and a phenolic resin composition comprising the reaction product of a phenol compound, a compound having a triazine ring and an aldehyde compound as essential components. The epoxy resin laminate is obtained by impregnating a base material with the epoxy resin composition as a varnish, drying the impregnated base material, and subsequently heating and pressing the obtained epoxy resin prepreg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition, an epoxy resin prepreg, and an epoxy resin laminate.

[0002]

2. Description of the Related Art In recent years, the types of electronic devices have been steadily expanding, and devices using printed wiring boards have been widely used from consumer products such as game machines to industrial products such as computers and control devices. As a substrate of a printed wiring board particularly used for high-performance electronic equipment, an epoxy resin laminate having an epoxy resin as a matrix is frequently used. Various characteristics are required for a substrate of a printed wiring board. Among them, flame retardancy is an important item along with electrical insulation and heat resistance. Generally, a flame retardant is used to make a plastic material having poor self-extinguishing properties flame-retardant. There are two types of flame retardants: an addition type and a reaction type. To make the epoxy resin laminate flame-retardant, a method using a brominated epoxy resin, which is a reaction type flame retardant, has been adopted.

[0003]

However, recently, as the tendency to protect the global environment from various fields has been increasing, when an epoxy resin laminate using a brominated epoxy resin is heated to a high temperature, the brominated epoxy resin is hardly used. There is also a danger that the cured product will produce toxic compounds, and there is also the danger of producing dioxins when burning waste, because bromine is a type of halogen. Therefore, it has been required to impart flame retardancy using a non-halogen flame retardant.
As non-halogen flame retardants, phosphorus flame retardants such as triphenyl phosphate and inorganic flame retardants such as aluminum hydroxide have been used. However, when a phosphorus-based flame retardant such as triphenyl phosphate is blended, there is a disadvantage that heat resistance such as Tg is significantly deteriorated, whereas aluminum hydroxide has a decomposition start temperature of about 2%.
It is 20 ° C., and it is necessary to limit the compounding amount in order to secure the solder heat resistance. The present invention has been made in order to solve such a problem, and has flame retardancy without using a brominated epoxy resin, and has an excellent heat resistance. An object of the present invention is to provide an epoxy resin composition and an epoxy resin prepreg used for manufacturing a board.

[0004]

That is, the present invention provides a phenol resin composition comprising an epoxy resin, a reaction product of a compound having a phenol and a triazine ring as a curing agent and an aldehyde, and a thermosetting resin having a dihydrobenzoxazine ring. The present invention relates to an epoxy resin composition containing a mixture of curable resins as an essential component. Epoxy resin composition according to the present invention,
The base material is impregnated and dried as a varnish to obtain an epoxy resin prepreg. Also, a predetermined number of the epoxy resin prepregs are heated and pressed to form an epoxy resin laminate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The type of epoxy resin is 2
A functional or higher epoxy resin is used. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, polyfunctional phenol There are glycidyl etherified products, diglycidyl etherified products of polyfunctional alcohols, hydrogenated products thereof, and the like, and some of them can be used in combination. The novolak phenol type epoxy resin is preferable because an epoxy resin laminate having more excellent heat resistance can be obtained. The thermosetting resin having a dihydrobenzoxazine ring is not particularly limited as long as the resin has a dihydrobenzoxazine ring and is cured by a ring-opening reaction of the dihydrobenzoxazine ring, and a compound having a phenolic hydroxyl group. , Formalin and primary amines are synthesized by the formula 1.

[0006]

Embedded image (In the formula, R1 is a methyl group, a phenyl group, or a phenyl group substituted with at least one alkyl group having 1 to 3 carbon atoms or an alkoxyl group.) As a compound having a phenolic hydroxyl group, polyfunctional phenol, biphenol Compounds, bisphenol compounds,
Trisphenol compounds, tetraphenol compounds and phenol resins are exemplified. Polyfunctional phenols include catechol, hydroquinone and resorquinol. Examples of the bisphenol compound include bisphenol A, bisphenol F and its positional isomer, bisphenol S, and tetrafluorobisphenol A. As the phenolic resin, a resole resin, a phenol novolak resin, a phenol-modified xylene resin,
Examples thereof include an alkylphenol resin, a melamine phenol resin, and a phenol-modified polybutadiene. Specific examples of the primary amine include methylamine, cyclohexylamine, aniline, and substituted aniline. In the present invention, a mixture of a compound having a phenolic hydroxyl group and a primary amine is added to an aldehyde heated to 70 ° C or higher, and the mixture is added at 70 to 110 ° C, preferably 90 to 100 ° C.
For 20 to 120 minutes, and then dried under reduced pressure at a temperature of 120 ° C. or lower to synthesize. The phenols for obtaining the phenolic resin composition in the present invention are not particularly limited, for example, phenol, or cresol, xylenol,
Examples include alkylphenols such as ethylphenol and butylphenol, polyphenols such as bisphenol A, bisphenol F, bisphenol S, resorcin, and catechol, phenylphenol, and aminophenol. The use of these phenols is not limited to only one type, and two or more types can be used in combination. The phenols for obtaining the phenol resin composition are not particularly limited, and include, for example, phenol or alkylphenols such as cresol, xylenol, ethylphenol, butylphenol, bisphenol A, bisphenol F, bisphenol S, resorcinol, Examples include polyhydric phenols such as catechol, phenylphenol, aminophenol and the like. The use of these phenols is not limited to only one type, and two or more types can be used in combination. Further, the compound containing a triazine ring for obtaining the phenol resin composition of the present invention is not particularly limited, but is preferably the following general formula (I) and / or general formula (II) .

[0007]

Embedded image (Wherein R1, R2, and R3 are an amino group, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group,
Ether group, ester group, acid group, unsaturated group, cyano group,
Represents one of

[0008]

Embedded image (Wherein R4, R5, and R6 are an amino group, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group,
Ether group, ester group, acid group, unsaturated group, cyano group,
In general formula (I), at least one of R1, R2, and R3
One is preferably an amino group. As the compound represented by the general formula (I), specifically, for example, melamine,
Alternatively, guanamine derivatives such as acetoguanamine and benzoguanamine, and cyanuric acid, and cyanuric acid derivatives such as methyl cyanurate, ethyl cyanurate, acetyl cyanurate, and cyanuric chloride are exemplified. Among these, any two or three of R1, R2, and R3
Guanamine derivatives such as melamine, acetoguanamine and benzoguanamine each having an amino group are more preferred. Specific examples of the compound represented by the general formula (II) include, for example, isocyanuric acid, or methyl isocyanurate, ethyl isocyanurate, allyl isocyanurate, 2-hydroxyethyl isocyanurate, 2-carboxylethyl isocyanurate, chlorinated And isocyanuric acid derivatives such as isocyanuric acid. Of these, isocyanuric acid in which all of R4, R5, and R6 are hydrogen atoms is most preferable. In addition, cyanuric acid, which is a compound represented by the general formula (I) which is a tautomer, is also a preferable compound.

When these compounds are used, they are not limited to one kind alone, and two or more kinds can be used in combination. Aldehydes for obtaining the phenolic resin composition of the present invention are not limited, but formaldehyde is preferred from the viewpoint of easy handling. The formaldehyde source is not limited, but typical sources include formalin, paraformaldehyde and the like.

A typical method for obtaining the phenolic resin composition of the present invention will be described below. First, the above-mentioned phenols, aldehydes, and compounds having a triazine ring are reacted under basic or acidic catalysis. At this time, the pH of the system is not particularly limited, but since many of the compounds containing a triazine ring are easily dissolved in a basic solution, the reaction is preferably performed by basic catalysis. Use is preferred. Also, the reaction order of each raw material is not particularly limited, and phenols and aldehydes are first reacted, and then, even if a compound having a triazine ring is added, conversely, the compound having a triazine ring is reacted with the aldehyde. Even if phenols are added, all the raw materials may be added and reacted at the same time. At this time,
Although the molar ratio of the aldehyde to the phenol is not particularly limited, it is 0.2 to 1.5, preferably 0.4 to 0.8. The weight ratio of the compound having a triazine ring to the phenol is 10 to 98:
90-2, preferably 50-95: 50-5. When the weight ratio of phenols is 10% or less, it is difficult to convert the resin into a resin. Further, although not particularly limited as a catalyst, typical examples include sodium hydroxide,
Hydroxides of alkali metals and alkaline earth metals such as potassium hydroxide and barium hydroxide, and their oxides, ammonia, primary to tertiary amines, hexamethylenetetramine, sodium carbonate, etc., and hydrochloric acid, sulfuric acid, and sulfone Examples include inorganic acids such as acids, organic acids such as oxalic acid and acetic acid, Lewis acids, and divalent metal salts such as zinc acetate.

Since it is not preferable that inorganic substances such as metals remain as catalyst residues, it is preferable to use amines as basic catalysts and organic acids as acidic catalysts. The reaction may be performed in the presence of various solvents from the viewpoint of controlling the reaction. Next, if necessary, impurities such as salts are removed by neutralization and washing with water. However, when amines are used as the catalyst, it is preferable not to perform the reaction. After the completion of the reaction, unreacted aldehydes, phenols, solvents and the like are removed according to ordinary methods such as atmospheric distillation and vacuum distillation. At this time, it is preferable to remove unreacted aldehydes and methylols,
In order to obtain a resin composition substantially free of unreacted aldehydes and methylols, a heat treatment at 120 ° C. or higher is required. At this time, when a novolak resin is obtained, it is preferable to sufficiently heat and distill according to a conventional method. Although not particularly limited, the unreacted monofunctional phenol monomer is preferably 2% or less at this time, as described above. The product thus obtained is a phenol resin composition comprising a mixture or condensate of a phenol, a compound having a triazine ring and an aldehyde. Although not particularly limited, it is preferable that the mixture or the condensate does not contain an unreacted aldehyde and does not substantially contain a methylol substrate.

Further, in the resin composition of the present invention, ordinary inorganic and organic fillers and reinforcing fibers can be used as fillers. For example, staple fiber, yarn, cotton cloth, glass cloth, glass mat, glass fiber, carbon fiber, quartz fiber, flame-retardant synthetic fiber, silica powder, calcium carbonate,
Magnesium hydroxide, aluminum hydroxide and the like. If these fillers are treated with a coupling agent in advance, the interfacial adhesion with the resin can be improved. On this occasion,
Adding a coupling agent is also effective in improving the interfacial adhesion between the filler and the resin. The method for producing a copper-clad laminate, a prepreg, a sealing material, and a molding material from these resin compositions is not particularly limited. Normally,
These resin compositions are formed into a solution by using an organic solvent, and then applied to a substrate and dried. The thus-prepared prepregs are laminated, copper foils are formed on both sides thereof, and then pressed, whereby a copper-clad laminate can be produced. In addition, a sealing material, a molding material, and the like can be manufactured by melt-kneading the resin composition and the filler. Epoxy resin (A)
The optimum blending ratio of the phenolic resin composition (B) comprising a reaction product of a phenol and a compound having a triazine ring with an aldehyde and the compound (C) having a dihydrobenzoxazine ring is not particularly limited ( A) 40 to 60, (B) 10 to 20 (C) 30 to
40 (parts by weight).

[0013]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples. Examples 1 to 5 and Comparative Examples 1 to 3 [1] Synthesis of dihydrobenzoxazine ring (I) (1) Synthesis of phenol novolak Phenol 1.9 kg, formalin (37% aqueous solution)
1.15 kg and 4 g of oxalic acid were charged into a 5-liter flask and reacted at a reflux temperature for 6 hours. Subsequently, the internal pressure was reduced to 6666.1 Pa or less to remove unreacted phenol and water. The obtained resin had a softening point of 89 ° C. (ring and ball method) and a 3 to polynuclear / binuclear ratio of 89/11 (peak area ratio by gel permeation chromatography). (2) Introduction of dihydrobenzoxazine ring 1.7 k of phenol novolak resin synthesized above
g (equivalent to 10 mol of hydroxyl groups) to aniline 1.
49 kg (corresponding to 16 mol) was stirred at 80 ° C. for 5 hours to prepare a uniform mixed solution. In a 5 liter flask, 1.62 kg of formalin was charged and heated to 90 ° C.
To this, a novolak / airin mixed solution was added little by little over 30 minutes. 30 minutes after the completion of the addition, the mixture was kept at the reflux temperature, and then decompressed to 6666.1 Pa or less at 100 ° C. for 2 hours to remove the condensed water, and heat cured in which 95% of the reactive hydroxyl groups were converted to dihydrobenzoxazine. A water-soluble resin was obtained. Hereinafter, the obtained resin is abbreviated as (M1).

[2] Synthesis of dihydrobenzoxazine ring (II) (1) Synthesis of phenol novolak 1.9 kg of phenol, formalin (37% aqueous solution)
1.10 kg and 4 g of oxalic acid were charged into a 5-liter flask and reacted at a reflux temperature for 6 hours. Subsequently, the internal pressure was reduced to 6666.1 Pa or less to remove unreacted phenol and water. The obtained resin had a softening point of 84 ° C. (ring and ball method), and a 3 to polynuclear / binuclear ratio of 82/18 (peak area ratio by gel permeation chromatography). (2) Introduction of a dihydrobenzoxazine ring A dihydrobenzoxazine ring was introduced in the same manner as in the synthesis (I) of a thermosetting resin having a dihydrobenzoxazine ring. The resulting thermosetting resin has 90% of the reactive hydroxyl groups of the phenol novolak resin.
Into which a dihydrobenzoxazine ring was introduced. Hereinafter, the obtained resin is abbreviated as (M2).

[3] Synthesis of dihydrobenzoxazine ring (I) 41.4 parts of phenol and 9.4 parts of benzoguanamine were used.
51 parts of 5% formalin and 0.47 parts of oxalic acid were added, and the temperature was gradually raised to 100 ° C. while paying attention to heat generation.
After reacting at 100 ° C. for 5 hours, the temperature was raised to 180 ° C. while removing water under normal pressure, and unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 103 ° C. Was. Hereinafter, this composition is abbreviated as “N1”. Weight ratio of phenol and compound having a triazine ring, unreacted formaldehyde amount, presence or absence of methylol group,
And the amount of unreacted phenol monomer was determined, and the results are summarized in Table 1.

[4] Synthesis example of phenolic resin composition (I
I) 29 parts of 41.5% formalin and 0.47 parts of triethylamine were added to 94 parts of phenol and reacted at 80 ° C. for 3 hours. After adding 19 parts of melamine and further reacting for 1 hour, the temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was performed for 2 hours while maintaining the temperature. Next, the temperature was raised to 180 ° C. while removing water at normal temperature, and unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 136 ° C. The weight ratio of phenol to melamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, and the amount of unreacted phenol monomer were determined. The results are summarized in Table 1. Hereinafter, this composition is referred to as “N2”.
Abbreviated.

[0017]

[Table 1]

[5] Other Compounds The phenol novolak type epoxy resin used in this study had an epoxy equivalent of 179 and a softening point of 40 ° C. As aluminum hydroxide, it is assumed that there are few residual ions and the like generally used for electronic materials,
Particles having a particle diameter of 3 to 5 μm were used.

[6] Preparation of Laminated Plate Each of the resin compositions shown in Table 2 was prepared by adding methyl ethyl ketone /
Dimethylformamide was dissolved in a mixed solvent of 50/50 parts by weight, and the solution was adjusted with methyl ethyl ketone so that the nonvolatile content was 60 to 70%. Thereafter, each mixed solution was impregnated into a glass cloth (0.2 mm), and
It dried at 60 degreeC for 4 minutes, and obtained the prepreg. Eight prepregs are stacked, and copper foil of 18 μm is stacked on both surfaces thereof.
It was heated and pressed at 85 ° C. under a pressure of 40 kgf / cm 2 for 100 minutes to obtain a 1.6 mm-thick double-sided copper-clad laminate. Next, the laminate was subjected to an etching treatment to remove the copper foil and then subjected to physical property tests. As a result, the results shown in Table 2 were obtained.

[0020]

[Table 2] * 1: Moisture-absorbing solder heat resistance test is 26 hours after pressure cooker (PCT) treatment (121 ° C, under steam) for a predetermined time.
The evaluation was performed by immersing in a 0 ° C. solder bath for 20 seconds. The evaluation was performed by visual judgment of the appearance of the test piece, the occurrence of measling or swelling. ○: Above nothing
△: Mesling, ×: Swelling * 2: Heat resistance test was performed according to UL-94. When a phenol resin composition is used alone as a curing agent, the moisture absorption solder heat resistance is all swollen by PCT2h treatment, but the phenol resin composition and a dihydrobenzoxazine compound are used in combination as a curing agent. It can be seen that the heat resistance of the moisture-absorbing solder is greatly improved.

[0021]

The phenol resin composition (B) comprising a reaction product of the epoxy resin (A) of the present invention, a phenol, a compound having a triazine ring and an aldehyde, and a dihydrobenzoxazine compound (C) are used. ,
It has become possible to provide an epoxy resin laminate excellent in moisture absorption solder heat resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08J 5/24 CFC C08J 5/24 CFC C09D 163/00 C09D 163/00 // B29K 105: 06 (72) Inventor Teruki Aizawa Ibaraki 1500, Ogawa, Shimodate, Hitachi, Japan Inside the Shimodate Plant of Hitachi Chemical Co., Ltd. (72) Inventor Yasuyuki Hirai 1500, Oji, Shimodate, Ibaraki Prefecture, Shimodate Plant of Hitachi Chemical Co., Ltd. 1500 Ogawa, Hitachi Chemical Industry Co., Ltd., Shimodate Plant (72) Inventor Shinichi Kamoshida 1500, Oji, Shimodate City, Ibaraki Prefecture, Hitachi Chemical Co., Ltd., Shimodate Plant

Claims (3)

[Claims] An essential component is a phenol resin composition (B) comprising an epoxy resin (A), a reaction product of a compound having a phenol or triazine ring and an aldehyde, and a compound (C) having a dihydrobenzoxazine ring. An epoxy resin composition characterized by the following. 2. An epoxy resin prepreg obtained by using the epoxy resin composition according to claim 1 as a varnish and impregnating and drying the varnish on a substrate. 3. An epoxy resin laminate obtained by heating and pressing the epoxy resin prepreg according to claim 2.