JP4821059B2 - Resin composition and flame-retardant laminate and printed wiring board using the same - Google Patents

Description

【００４６】
表１の結果より、実施例１〜５で得られた銅張積層板は、難燃性および耐熱性に優れており、かつ耐電食性に優れていた。それに対して、比較例１で得られた積層板は、難燃性が著しく劣り、比較例２で得られた積層板は、難燃性と耐熱性が劣り、比較例３で得られた積層板は、耐熱性が劣るほか、耐電食性が著しく劣っていた。
【００４７】
実施例６
ジメチルジエトキシシラン１４．８部とフェニルトリクロロシラン２１．１部をトルエン３６．０部に溶解して得た溶液を、温度７０℃で激しく撹拌している水１００部に滴下し、ついでトルエンの還流温度で２時間撹拌して、共加水分解および部分縮合を行った。静置して分液し、常法により油層を中和、水洗した後脱水、ろ過し、さらに一部のトルエンを留去して、シロキサンオリゴマーの６０重量％トルエン溶液を得た。得られたシロキサンオリゴマーは、（ＣＨ₃）₂ＳｉＯ単位とＣ₆Ｈ₅ＳｉＯ_3/2単位を等モル含有し、６重量％の水酸基を含有していた。
【００４８】
このようにして得られたシロキサンオリゴマーを、実施例１で用いたのと同じエポキシ樹脂ワニスに、シロキサン分換算で０．５重量％配合し、撹拌して溶解させ、シロキサンオリゴマー含有エポキシ樹脂ワニスを調製した。これを用いて、実施例１と同様にして両面銅張積層板を作製して、実施例１と同様の方法で難燃性および耐熱性を評価したところ、難燃性は９４Ｖ−０、耐熱性は＞３００秒であった。
【００４９】
実施例７
ジメチルジメトキシシラン２０部とジフェニルジメトキシシラン２０部をエチレングリコールモノメチルエーテル５０部に溶解して、混合シラン溶液を調製した。これを撹拌しながら、室温で蒸留水５０部と酢酸０．２８部の溶液を滴下し、ついで５０℃に８時間加熱して、共加水分解および部分縮合を進めた。
【００５０】
このようにして得られたシロキサンオリゴマーを、実施例１で用いたのと同じエポキシ樹脂ワニスに、シロキサン分換算で０．５重量％配合し、撹拌して溶解させ、シロキサンオリゴマー含有エポキシ樹脂ワニスを調製した。これを用いて、実施例１と同様にして両面銅張積層板を作製して、実施例１と同様の方法で難燃性、耐熱性、Ｔｇおよび耐電食性を評価した。その結果は次のとおりであった。
難燃性： ９４Ｖ−０
耐熱性： ＞３００秒
Ｔｇ： １６３℃
耐電食性（５００ｈ）： １×１０¹²
耐電食性（１，０００ｈ）： １×１０¹²
【００５１】
【発明の効果】
本発明の樹脂組成物より作製した積層板は、ハロゲン化合物を含有しない材料でありながら、難燃性、耐熱性および作業性に優れ、かつ耐電食性に優れている。このような積層板から回路を形成して得られたプリント配線板は、信頼性が高く、ワイヤボンディング性が優れている。したがって、本発明の樹脂組成物、ならびにそれを用いた積層板および印刷配線板は、電子機器用の絶縁材料やプリント配線板として、きわめて有用である。[0001]
[Industrial application fields]
The present invention relates to a resin composition that does not contain a bromine compound, and a flame-retardant laminate, particularly a metal-clad laminate, and a printed wiring board, which are used for various electronic materials.
[0002]
[Prior art]
Awareness of environmental destruction is increasing on a global scale. Organohalogen compounds, antimony, lead alloys, lead compounds, and the like that pollute the air and soil and may be harmful to the human body are subject to use restrictions. For this reason, the shift to products that do not contain halogen compounds or lead alloys is progressing mainly in home appliances and various information terminal devices such as personal computers. Printed wiring boards and mounting parts used in such electronic devices are no exception.
[0003]
In general, many of the conventional substrate materials used for printed wiring boards and plastic packages use organic halogen compounds for flame resistance. Moreover, the present condition is using the Sn-Pb type-alloy for the solder connection of mounting components.
[0004]
According to reports on solder materials that do not contain lead, such solders tend to have a higher melting point, and the reflow temperature is likely to increase accordingly. Under such circumstances, the substrate material is required not only to use a halogen compound, but also to have higher heat resistance than ever in order to withstand the melting temperature of the solder.
[0005]
As a flame-retarding method not using an organic halogen compound, conventionally, a phosphorus compound or a nitrogen compound is added, or they are introduced into a resin skeleton. However, in order to ensure flame retardancy with a phosphorus compound or nitrogen compound, it is necessary to add a certain amount, thereby causing an increase in water absorption and a decrease in heat resistance. Therefore, a method of using a metal oxide hydrate in combination for the purpose of reducing the compounding amount of a phosphorus compound or a nitrogen compound has been attempted.
[0006]
However, since the metal oxide hydrate traps a large amount of water that exhibits a cooling effect during combustion, the heat resistance of the resin composition or the laminate is drastically reduced when mixed in a certain amount or more. This is due to the fact that the temperature at which the metal oxide hydrate releases water is lower than the melting temperature of the solder, which is expected to require a higher melting temperature. This is likely to be more noticeable with solders that do not contain lead.
[0007]
The present inventors first processed the substrate and filler of the laminate with a siloxane oligomer having a functional group that reacts with the hydroxyl group, thereby improving the adhesion at the interface between the substrate and the filler and the resin. It has been found that a laminated board and a printed wiring board excellent in drilling workability and insulation characteristics can be manufactured by improving the process (see Patent International Publication No. WO 97/01595). However, the knowledge that this technique can be applied to the flame retardancy of such a laminate has not been obtained so far.
[0008]
[Problems to be solved by the invention]
The present invention has been made on the assumption of such a situation, and is a resin composition that does not contain an organic halogen compound and that is obtained by curing and is excellent in flame retardancy and heat resistance; An object of the present invention is to provide a laminated board excellent in flame retardancy, heat resistance and processability; and a printed wiring board.
[0009]
[Means for Solving the Problems]
As a result of repeated studies to solve the above problems, the present inventors have formulated a metal-functional siloxane oligomer containing a hydrate of a metal oxide as a flame retardant and having reactivity with the hydrate. By blending (C), excellent mechanical properties and workability can be obtained even if a large amount of (C) is blended without impairing the flame retardant effect due to the hydrate of the metal oxide. Thus, the inventors have found that the above object can be achieved, and have completed the present invention.
[0010]
That is, the resin composition of the present invention is
(A) epoxy resin;
(B) a polyfunctional phenol resin having a softening point of 100 ° C. or higher;
(C) a metal oxide hydrate; and (D) a siloxane oligomer having a silicon functional group, wherein the content of (C) is 50 to 200 volumes with respect to the total amount of (A) and (B) % And substantially free of organic halogen compounds. The flame-retardant laminate of the present invention is obtained by laminating and curing a prepreg obtained from the resin composition, and the flame-retardant printed wiring board of the present invention is a metal-clad laminate obtained as described above. Is obtained by forming a circuit.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The epoxy resin as the component (A) may be any compound having two or more epoxy groups in the molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, Phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy Resins, isocyanurate type epoxy resins, hydantoin type epoxy resins, glycidyl ether compounds of polyfunctional phenols, glycidyl ether compounds of bifunctional alcohols, and hydrogenated products thereof It is used alone or in combination of two or more thereof.
[0012]
The polyfunctional phenol resin as the component (B) is a curing agent as the component (A). Component (B) includes phenol novolak, cresol novolak, bisphenol A novolak, bisphenol F novolak, catechol novolak, and those obtained by substituting these aromatic rings with an alkyl group. You may use together. In the present invention, among these polyfunctional phenol resins, a resin composition having good heat resistance and flame retardancy is obtained by blending those having a softening point of 100 ° C. or higher, preferably 100 to 150 ° C. be able to.
[0013]
Since the blending amount of the component (B) gives excellent heat resistance to the cured resin, the number of hydroxyl groups in the component (B) is 0.8 to 1.2 per epoxy group in the component (A). The amount to be is preferred.
[0014]
The (C) component metal oxide hydrate imparts flame retardancy to the composition of the present invention. Here, the hydrate of a metal oxide is a concept including what is expressed as a metal hydroxide. As the component (C), a hydrate of a metal oxide of Group 2 or 13 of the periodic table is usually used, and aluminum oxide hydrate, magnesium hydroxide and calcium hydroxide are preferable. Aluminum oxide hydrates include what are called aluminum hydroxides, and include monohydrates such as boehmite and diaspore; and trihydrates (aluminum hydroxide) such as gibbsite and bayerite. As the component (C), one type may be used, or two or more types may be used in combination. Gibbsite is particularly preferred because excellent flame retardancy can be obtained with the same blending amount.
[0015]
(C) The compounding quantity of component is 50-200 volume% with respect to the total amount of (A) component and (B) component, Preferably 70-150 volume% is used. When the amount of the component (C) is less than 50% by volume, sufficient flame retardancy cannot be obtained, and when it exceeds 200% by volume, the moldability becomes insufficient.
[0016]
The (D) component siloxane oligomer is a surface treatment agent for an inorganic filler other than the (C) component and optionally the (C) component. The component (D) is not particularly limited as long as it has two or more siloxane units and has at least one silicon functional group that reacts with a hydroxyl group on the substrate surface. The siloxane skeleton may be linear, branched, cyclic, or network-like, and preferably has a branched structure from the compatibility with the component (A) and the component (B). Moreover, since it is easy to handle and processing unevenness does not occur, the number of siloxane units is preferably 2 to 70, and more preferably 5 to 50. Examples of silicon functional groups include hydroxyl groups (also referred to as silanol groups including silicon atoms); alkoxy groups such as methoxy, ethoxy and propoxy; alkoxy-substituted alkoxy groups such as 2-methoxyethoxy; and hydrogen atoms. Are preferable, and a hydroxyl group and a methoxy group are preferable, and a hydroxyl group is particularly preferable. Such a silicon functional group is preferably bonded to a terminal silicon atom when the siloxane skeleton is linear, but may be bonded to any silicon atom in the case of other skeleton structures. Good.
[0017]
In the siloxane oligomer, an unsubstituted or substituted monovalent hydrocarbon group is bonded to a silicon atom. Such groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl; aryl groups such as phenyl; alkenyl groups such as vinyl; and substituted hydrocarbon groups such as 3-methoxypropyl. In order to give excellent heat resistance to the cured resin, it is preferable to have at least one phenyl group in the molecule, and raise the temperature at which the metal oxide hydrate releases water, Since the processing does not cause blistering due to processing such as attaching, and flame retardancy is not impaired, 25 mol% or more of all siloxane units are units having at least one phenyl group. preferable. The other group is preferably a methyl group because it is easy to synthesize and handle.
[0018]
Such a siloxane oligomer includes, for example, silicon functional group-containing silanes such as alkoxysilanes and chlorosilanes and / or partial hydrolysis condensates thereof corresponding to the siloxane units constituting the oligomer. It can be obtained by hydrolysis or (co) alcolysis and partial condensation. For example, the above silanes are dissolved in an alcohol solvent such as methanol, ethanol, 2-methoxyethanol; and / or a hydrocarbon solvent such as toluene, xylene, and weakened with water; an acid such as acetic acid. Acidified water; dripping alcohol or the like, or conversely adding a mixed silane solution in similar water, etc., stirring until the desired degree of polymerization is reached, and separating the oil phase as a siloxane oligomer It can be recovered.
[0019]
(C) The processing method of the siloxane oligomer with respect to component and other inorganic fillers mix | blended with the case is not specifically limited, The dry method which adds a siloxane oligomer directly, or the process diluted with the organic solvent etc. A wet method using a liquid is suitable.
[0020]
The processing amount of the siloxane oligomer in the component (C) and other inorganic fillers is not particularly limited, but is sufficiently dispersed in the system and effective for the treatment of the object, and the component (C) and as required Forming a moderately thick polysiloxane layer on the surface of other inorganic fillers to be blended to produce excellent interfacial adhesion with the component (A) and reducing residual stress And since it gives the resin the outstanding heat resistance, 0.01 to 5.0 weight% is suitable with respect to the total amount of (C) component and another inorganic filler.
[0021]
In addition to the above components (A) to (D), various components can be arbitrarily blended in the resin composition of the present invention.
[0022]
In order to accelerate the curing of the component (A), a curing accelerator can be blended as necessary. The type and blending amount of the curing accelerator are not particularly limited. For example, imidazole compounds, tertiary amines, onium salts and the like are used, and one type may be used or two or more types may be used in combination. .
[0023]
Furthermore, in order to improve heat resistance, flame retardancy, etc., and to give appropriate mechanical properties to the resin composition and / or its cured product, an inorganic filler other than the component (C) may be used in combination. Good. As such inorganic filler, alumina, silica, titanium oxide, clay, calcium carbonate, aluminum carbonate, magnesium silicate, aluminum silicate, mica, short glass fiber, etc. are used, and aluminum borate, silicon carbide, etc. Various whiskers are used. These may be used alone or in combination of two or more.
[0024]
In order to increase the affinity between the metal oxide hydrate and the resin, various coupling agents may be used in combination with the surface treatment in addition to the siloxane oligomer. As the coupling agent, a silane coupling agent, a titanate coupling agent, or the like is used. As the silane coupling agent, carbon functional silane is used, and 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 2- (2,3-epoxycyclohexyl) ethyltri Epoxy group-containing silane such as methoxysilane; 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl (methyl) ) Amino group-containing silane such as dimethoxysilane; Cationic silane such as 3- (trimethoxylyl) propyltetramethylammonium chloride; Vinyl group-containing silane such as vinyltriethoxysilane; 3-Methacryloxypropyltrimethoxysilane Acrylic group-containing silane such as Mercapto group-containing silane such as beauty 3-mercaptopropyltrimethoxysilane and the like. Examples of titanate coupling agents include alkyl titanates such as titanium propoxide and titanium butoxide. Such a coupling agent may use 1 type, or may use 2 or more types together, and the compounding quantity does not have a restriction | limiting in particular.
[0025]
A solvent is used in order to dilute or disperse | distribute each component of a resin composition, the inorganic filler etc. which are mix | blended arbitrarily, or to form a varnish. Examples of the solvent include hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate; ether alcohols such as ethylene glycol monomethyl ether; methanol, ethanol , Alcohols such as isopropanol and butanol; and aprotic polar solvents such as N, N-dimethylformamide are exemplified, and one kind or a mixture of two or more kinds may be used. Moreover, you may mix | blend the reactive diluent which has one epoxy group in a molecule | numerator.
[0026]
The solid content concentration of the varnish is not particularly limited and can be appropriately changed depending on the resin composition and the type and blending amount of the inorganic filler. However, the resin content of the prepreg is sufficient to maintain the insulation of each layer, and the varnish Since the workability is not impaired by the increase in the apparent viscosity, and the appearance of the prepreg is not impaired, the range of 50 to 80% by weight is preferable.
[0027]
If necessary, the composition of the present invention may further contain a colorant, an antioxidant, a reducing agent, an ultraviolet blocking agent and the like. However, the resin composition of the present invention has an aromatic bromine compound, a brominated epoxy resin and a terminal group derivative thereof, brominated alcohol, brominated pentaerythritol, brominated benzyl acrylate, brominated alkyl isocyanurate due to its problems. Organic bromine compounds such as: Organic halogen compounds such as chlorinated paraffin and chlorinated polyethylene are not substantially contained.
[0028]
A resin composition obtained by blending each of the above components, particularly a varnish prepared by further blending a solvent and / or a reactive diluent, is impregnated into a substrate, air-dried as necessary, and then in a drying furnace. By semi-curing, a printed wiring board prepreg is obtained. The treatment conditions are usually 80 to 200 ° C., preferably 100 to 180 ° C. for 3 to 30 minutes, preferably 5 to 15 minutes. The substrate is not particularly limited as long as it is used when producing a metal-clad laminate or a multilayer printed wiring board, but a fiber substrate such as a woven fabric or a nonwoven fabric is usually used. Examples of the fiber substrate include inorganic fibers such as glass, silica glass, silica alumina glass, alumina, zirconia, asbestos, tyrano, silicon carbide, silicon nitride, and boron carbide; carbon fibers; aromatic polyamide, polyether ether ketone, There are organic fibers such as polyetherimide, polyethersulfone, and cellulose, and mixed papers thereof. In particular, a woven fabric of glass fibers is preferably used.
[0029]
The prepreg used in the present invention is cured by heating and pressing at a temperature of 150 to 200 ° C. and a pressure of about 1.0 to 8.0 MPa, and a laminated sheet, particularly a metal-clad laminated sheet such as a copper-clad laminated sheet, It is used to manufacture a multilayer printed wiring board on which a circuit is formed.
[0030]
[Action]
In the resin composition of the present invention, by adding 50 to 200% by volume of the metal oxide hydrate in the resin component, hydration water is released upon combustion, and thus obtained by curing the composition. Flame retardancy can be imparted to the laminate.
[0031]
Furthermore, by blending the silicon functional siloxane oligomer, the dispersibility of the hydrate in the system can be improved, the deterioration of insulation due to the aggregation can be prevented, and good processability can be maintained. In particular, when the siloxane oligomer has at least one phenyl group and 25 mol% or more of all siloxane units are used, the temperature at which the metal oxide hydrate releases water can be increased. Accordingly, since water is not released at the temperature during processing such as soldering, the resin does not bulge. Further, by using a polyfunctional epoxy resin and a polyfunctional phenol resin having a softening point of 100 ° C. or higher, it is possible to prevent a decrease in heat resistance due to the release of water from the hydrate.
[0032]
【Example】
Hereinafter, the present invention will be described by way of examples. The present invention is not limited by these examples. In Examples and Comparative Examples, parts represent parts by weight.
[0033]
Example 1
A solution was prepared by blending 20 parts of dimethyldimethoxysilane and 25 parts of tetramethoxysilane with 105 parts of methanol. While stirring this, a solution of 17.8 parts of distilled water and 0.60 part of acetic acid was added dropwise, and then heated to 50 ° C. for 8 hours to proceed the cohydrolysis and partial condensation. Liquid separation was performed to obtain an oil phase as a silanol group-containing siloxane oligomer.
[0034]
This siloxane oligomer was dissolved in methyl ethyl ketone to obtain a solution having a solid content of 1% by weight. A varnish composed of the following resin and inorganic filler was prepared, and 0.5 parts of the siloxane oligomer solution was added to the siloxane oligomer solution while stirring.
Bisphenol A type epoxy resin (epoxy equivalent: 245) 10 parts bisphenol A novolak type epoxy resin (epoxy equivalent: 205) 90 parts phenol novolak resin (hydroxyl equivalent: 108, softening point: 108 ° C.) 52 parts 2-ethyl-4- Methylimidazole 0.5 part Aluminum hydroxide (Gibsite) 90 parts Calcined clay 30 parts Methyl ethyl ketone was further added to prepare a varnish having a solid content of 70% by weight.
[0035]
Example 2
A varnish having a solid content of 70% by weight was prepared in the same manner as in Example 1 except that 52 parts of a phenol novolak resin having a hydroxyl equivalent weight of 108 and a softening point of 120 ° C. was used instead of the phenol novolak resin of Example 1.
[0036]
Example 3
A varnish having a solid content of 70% by weight was obtained in the same manner as in Example 1 except that 52 parts of cresol novolak resin (hydroxylation equivalent: 108, softening point: 121 ° C.) was used instead of the phenol novolak resin of Example 1. Was prepared.
[0037]
Example 4
A varnish having a solid content of 70% by weight was prepared in the same manner as in Example 1 except that the blending amount of aluminum hydroxide in Example 1 was changed to 150 parts.
[0038]
Example 5
A varnish having a solid content of 70% by weight was prepared in the same manner as in Example 1 except that 0.5 part of 3-glycidoxypropyltrimethoxysilane was added to the varnish of Example 1.
[0039]
Comparative Example 1
A varnish having a solid content of 70% by weight was prepared without adding aluminum hydroxide to the varnish of Example 1.
[0040]
Comparative Example 2
A varnish having a solid content of 70% by weight was prepared in the same manner as in Example 1 except that 52 parts by weight of a phenol novolak resin having a hydroxylation equivalent of 108 and a softening point of 84 ° C. was blended in place of the phenol novolac resin of Example 1. did.
[0041]
Comparative Example 3
A varnish having a solid content of 70% by weight was prepared in the same manner as in Example 1 except that the siloxane oligomer of Example 1 was not added.
[0042]
Each varnish prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was impregnated into a glass cloth (# 2116, E-glass) having a thickness of about 0.1 mm, and then dried by heating at 150 ° C. for 3 to 10 minutes. Thus, a prepreg having a resin content of 48% by weight was obtained. Four prepregs were stacked, a copper foil having a thickness of 18 μm was stacked on both sides thereof, and pressed for 90 minutes under a pressing condition of 170 ° C. and 3.0 MPa to prepare a double-sided copper-clad laminate.
[0043]
The obtained double-sided copper clad laminate was evaluated for flame retardancy, glass transition temperature, heat resistance and electric corrosion resistance. The results were as shown in Table 1.
[0044]
The test method was as follows.
Flame retardancy, glass transition temperature (Tg): Measured according to JIS C 6481.
Heat resistance: A double-sided copper-clad laminate was cut into 50 mm x 50 mm, floated on solder at 288 ° C, and the time until blistering was measured.
Electric corrosion resistance: Double-sided copper-clad laminate was processed with a drill with a diameter of 0.4 mm to a hole interval of 0.3 mm, a voltage of 50 V was applied between the holes, and the conditions were 85 ° C. and 85% RH for 500 hours. The insulation resistance after leaving for 1,000 hours was measured.
[0045]
[Table 1]

[0046]
From the result of Table 1, the copper clad laminated board obtained in Examples 1-5 was excellent in the flame retardance and heat resistance, and was excellent in the electrical corrosion resistance. On the other hand, the laminate obtained in Comparative Example 1 is significantly inferior in flame retardancy, and the laminate obtained in Comparative Example 2 is inferior in flame retardancy and heat resistance, and the laminate obtained in Comparative Example 3 is used. In addition to being inferior in heat resistance, the plate was inferior in electric corrosion resistance.
[0047]
Example 6
A solution obtained by dissolving 14.8 parts of dimethyldiethoxysilane and 21.1 parts of phenyltrichlorosilane in 36.0 parts of toluene was added dropwise to 100 parts of water which was vigorously stirred at a temperature of 70 ° C. The mixture was stirred at reflux temperature for 2 hours to carry out cohydrolysis and partial condensation. The mixture was allowed to stand and separated, and the oil layer was neutralized and washed with water by a conventional method, followed by dehydration and filtration. A part of toluene was distilled off to obtain a 60 wt% toluene solution of a siloxane oligomer. The obtained siloxane oligomer contained equimolar amounts of (CH ₃ ) ₂ SiO units and C ₆ H ₅ SiO _3/2 units, and contained 6% by weight of hydroxyl groups.
[0048]
The siloxane oligomer thus obtained was blended in the same epoxy resin varnish used in Example 1 in an amount of 0.5% by weight in terms of siloxane, and dissolved by stirring to obtain a siloxane oligomer-containing epoxy resin varnish. Prepared. Using this, a double-sided copper clad laminate was prepared in the same manner as in Example 1, and the flame retardancy and heat resistance were evaluated in the same manner as in Example 1. The flame retardancy was 94 V-0, Sex was> 300 seconds.
[0049]
Example 7
20 parts of dimethyldimethoxysilane and 20 parts of diphenyldimethoxysilane were dissolved in 50 parts of ethylene glycol monomethyl ether to prepare a mixed silane solution. While stirring this, a solution of 50 parts of distilled water and 0.28 part of acetic acid was added dropwise at room temperature, and then heated to 50 ° C. for 8 hours to proceed co-hydrolysis and partial condensation.
[0050]
The siloxane oligomer thus obtained was blended in the same epoxy resin varnish used in Example 1 in an amount of 0.5% by weight in terms of siloxane, and dissolved by stirring to obtain a siloxane oligomer-containing epoxy resin varnish. Prepared. Using this, a double-sided copper-clad laminate was prepared in the same manner as in Example 1, and the flame retardancy, heat resistance, Tg and electric corrosion resistance were evaluated in the same manner as in Example 1. The results were as follows.
Flame retardancy: 94V-0
Heat resistance:> 300 seconds Tg: 163 ° C
Electric corrosion resistance (500h): 1 × 10 ¹²
Electric corrosion resistance (1,000h): 1 × 10 ¹²
[0051]
【The invention's effect】
The laminate produced from the resin composition of the present invention is a material that does not contain a halogen compound, but has excellent flame retardancy, heat resistance, workability, and excellent electric corrosion resistance. A printed wiring board obtained by forming a circuit from such a laminate has high reliability and excellent wire bonding. Therefore, the resin composition of the present invention, and a laminate and a printed wiring board using the resin composition are extremely useful as an insulating material for electronic equipment and a printed wiring board.

Claims (7)

A resin composition for a flame-retardant printed wiring board in which a mounted component is soldered with a solder material that does not have lead,
(A) epoxy resin;
(B) a polyfunctional phenol resin having a softening point of 100 to 150 ° C;
(C) a hydrate of a metal oxide; and (D) a siloxane oligomer having a silicon functional group,
(B) is at least one multifunctional phenol resin selected from the group consisting of phenol novolak, cresol novolak, bisphenol A novolak, bisphenol F novolak, catechol novolak and those aromatic rings substituted with alkyl groups. ,
(C) is one or more selected from the group consisting of aluminum oxide hydrate, magnesium hydroxide and calcium hydroxide,
25% or more of the total siloxane units of (D) have at least one phenyl group,
The blending amount of (B) is such that the number of hydroxyl groups of (B) is 0.8 to 1.2 per epoxy group of (A),
(D) is the surface treatment agent of (C) or (E) when the surface treatment agent of (C) or (E) other inorganic filler is included,
The resin composition, wherein the treatment amount of (D) is 0.01 to 5.0% by weight with respect to the total weight of (C) and (E).   The resin composition according to claim 1, wherein the softening point of (B) is 100 to 121 ° C.   The resin composition according to claim 1 or 2, wherein the silicon functional group (D) is a hydroxyl group.   The resin composition according to any one of claims 1 to 3, wherein the number of the siloxane units (D) is 2 to 70.   The flame-retardant laminated board obtained by laminating | stacking and hardening the prepreg obtained from the resin composition of any one of Claims 1-4.   The flame-retardant laminate according to claim 5, which is a metal laminate.   A flame-retardant printed wiring board obtained by forming a circuit from the metal laminate according to claim 6.