JP2002220435A - Phosphorus-containing epoxy resin composition, prepreg, resin-coated metal foil, adhesive sheet, laminated board and multilayer board, phosphorus-containing epoxy resin varnish for coating, phosphorus-containing epoxy resin sealing material, phosphorus-containing epoxy resin casting material and phosphorus-containing epoxy resin varnish for immersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorus-containing epoxy resin composition which shows excellent flame retardancy without containing a halogen and which can enhance the adhesive strength between each layer in a laminated board or the like. SOLUTION: The composition has a phosphorus-containing epoxy resin, which is obtained by reacting at least one of the organic phosphorus compounds represented by the formulas (1) and (2), R1-R8 of the formula (1) and R'1-R'10 of the formula (2) are a 1-6C hydrocarbon group, a substituted group directly bound to a hetero atom or a hydrogen atom; X and X' are a substituted group represented by the formulas (3) and (4) [in which at least two of R"1-R"5 of the formula (3) are a hydroxyl group; at least two of R"'1-R"'7 of the formula (4) are a hydroxyl group; others are a 1-6C hydrocarbon group, a substituted group directly bound to a hetero atom or a hydrogen atom]} with an epoxy resin containing a novolac type epoxy resin of 20 mass % or more and a curing agent as essential components. The content of a phosphorus is 0.5-4.0 mass % with respect to the total amount of the composition. A triazine-modified novolak resin constitutes a part or all of the agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sealing material, a molding material,
Casting material, adhesive, phosphorus-containing epoxy resin composition used for electronic components as an electrical insulating paint, and prepreg, metal foil with resin, laminated board, multilayer board produced using this,
The present invention relates to a phosphorus-containing epoxy resin varnish for coating, a phosphorus-containing epoxy resin sealing material, a phosphorus-containing epoxy resin casting plate, and a phosphorus-containing epoxy resin varnish for impregnation.

[0002]

2. Description of the Related Art Epoxy resins have been used in a wide range of fields such as electronic parts, electric equipment, automobile parts, FRP, and sports equipment because of their excellent adhesiveness, heat resistance and moldability. Particularly in the above-mentioned fields, for epoxy resin used as a sealing material in electronic parts and electric equipment, halogenated epoxy resin such as brominated epoxy resin is used for the purpose of preventing and delaying fire. ing. That is, such an epoxy resin is synthesized by introducing a halogen typified by bromine into the epoxy resin, and is capable of obtaining a cured product provided with flame retardancy by the halogen in the epoxy resin. It is.

However, when such a cured product is burned,
Environmental problems such as generation of halogen compounds such as hydrogen halides, which are harmful substances, have arisen.

[0004] In order to solve such problems, there has been an increasing demand for epoxy resins having flame retardancy without containing halogen and compositions prepared using the same. Against this background, there is a movement to use a phosphorus-containing epoxy resin instead of a halogen, that is, a phosphorus-containing epoxy resin, and to mix it with a part or the whole of the composition to ensure flame retardancy. Is getting bigger. In fact, Japanese Patent Application Laid-Open
No. 279258 describes, for example, an epoxy resin composition imparted with flame retardancy without using a halogen, a laminate prepared using the same, a sealing material,
Cast material has been obtained.

[0005]

However, in the laminate obtained by the above method, the adhesive strength between the layers is not high enough to be practically used, and therefore, an improvement in the adhesive strength between the layers has been demanded.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent flame retardancy without containing halogen, and can enhance the adhesive strength between layers in a laminate or the like. Resin composition, prepreg produced using this, metal foil with resin, laminated board, multilayer board, phosphorus-containing epoxy resin varnish for coating, phosphorus-containing epoxy resin sealing material, phosphorus-containing epoxy resin casting material, impregnation It is an object to provide a phosphorus-containing epoxy resin varnish for use.

[0007]

Means for Solving the Problems The phosphorus-containing epoxy resin composition according to claim 1 of the present invention comprises at least one of the following organic phosphorus compounds represented by the following formulas (1) and (2):
A phosphorus-containing epoxy resin obtained by reacting a novolak-type epoxy resin with an epoxy resin containing 20% by mass or more, a curing agent as an essential component, and a phosphorus content of 0.5 to 4.0% by mass in the total amount of the composition. And a part or all of the curing agent is a triazine-modified novolak resin.

[0008]

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[0009] The phosphorus-containing epoxy resin composition according to claim 2 contains at least one of the organic phosphorus compounds represented by the above formulas (1) and (2) and 20% by mass or more of a novolak type epoxy resin. Phosphorus-containing epoxy resin obtained by reacting with an epoxy resin to be reacted, average epoxy equivalent 2
Bisphenol A type epoxy resin of 000 or less, a curing agent as an essential component, and a phosphorus content of 0.5 to
4.0% by mass, the content of the bisphenol A type epoxy resin is 2 to 20% by mass of the total epoxy resin, and a part or all of the curing agent is a triazine-modified novolak resin. It is assumed that.

A third aspect of the present invention is the method according to the first or second aspect, further comprising a filler.

A fourth aspect of the present invention is characterized in that, in any one of the first to third aspects, an organic phosphorus compound represented by the following formula (5) is used.

[0012]

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According to a fifth aspect of the present invention, in the third or fourth aspect, the filler is added in an amount of 30 to 1 with respect to 100 parts by mass of the solid content.
It is characterized by containing 20 parts by mass.

According to a sixth aspect of the present invention, in any one of the third to fifth aspects, as the filler, calcium carbonate, silica, kaolin, calcined kaolin, clay, calcined clay,
It is characterized by containing a material selected from talc, calcined talc, hydrotalcite, wollastonite, metal hydroxide, metal oxide, glass powder, silica balloon, and shirasu balloon.

According to a seventh aspect of the present invention, in any one of the third to fifth aspects, the filler contains one selected from kaolin, calcined kaolin, clay, calcined clay, talc, calcined talc, and metal hydroxide. It is characterized by comprising.

The invention of claim 8 is the invention according to any one of claims 1 to 7, wherein the novolak epoxy resin is
It is characterized by containing a material selected from bisphenol A type novolak type epoxy resin, cresol novolak type epoxy resin and phenol novolak type epoxy resin.

A prepreg according to a ninth aspect is characterized in that the sheet-like substrate is impregnated with the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects and is semi-cured. It is.

Further, the metal foil with resin according to claim 10 is:
The phosphorus-containing epoxy resin composition according to any one of claims 1 to 8 is applied on a metal foil and semi-cured.

An adhesive sheet according to a eleventh aspect is characterized in that the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects is formed into a sheet shape and is semi-cured. is there.

The laminated plate according to claim 12 is the ninth aspect.
Wherein at least one of the prepreg described in (1), the resin-attached metal foil described in (10), and the adhesive sheet described in (11) is laminated and formed.

According to a thirteenth aspect of the present invention, there is provided a multilayer board comprising:
Wherein at least one of the prepreg, the metal foil with resin according to claim 10 and the adhesive sheet according to claim 11 is included in at least one layer in each layer.

According to a fourteenth aspect of the present invention, there is provided a phosphorus-containing epoxy resin varnish for coating, comprising the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects.

[0023] Further, the multilayer board according to claim 15 is characterized in that:
4. A coating comprising the phosphorus-containing epoxy resin varnish for coating according to 4.

According to a sixteenth aspect of the present invention, there is provided a phosphorus-containing epoxy resin sealing material comprising the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects.

According to a seventeenth aspect of the present invention, there is provided a phosphorus-containing epoxy resin casting material comprising the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects.

[0026] A phosphorus-containing epoxy resin varnish for impregnation according to claim 18 is characterized by using the phosphorus-containing epoxy resin composition according to any one of claims 1 to 8.

[0027]

Embodiments of the present invention will be described below.

The present invention is broadly classified into an invention according to claim 1 (hereinafter referred to as a first invention) and an invention according to claim 2 (hereinafter referred to as a second invention). In the first invention, the phosphorus-containing epoxy resin composition has a phosphorus-containing epoxy resin and a curing agent as essential components, whereas in the second invention, the phosphorus-containing epoxy resin composition is the same as the first invention. In addition to the essential components, a bisphenol A type epoxy resin is also an essential component. Hereinafter, each of these components will be described first.

As the phosphorus-containing epoxy resin commonly used in both inventions, a resin synthesized from the organic phosphorus compound represented by the above formula (1) or (2) and an epoxy resin is used. is there. The epoxy resin used in this synthesis is not particularly limited, but it is necessary that the total amount of the phosphorus-containing epoxy resin contains 20% by mass or more of a novolak-type epoxy resin. If the content of the novolak type epoxy resin is less than 20% by mass based on the total amount of the phosphorus-containing epoxy resin, flame retardancy and heat resistance are undesirably reduced. As the novolak type epoxy resin, at least one of bisphenol A type novolak type epoxy resin, cresol novolak type epoxy resin, and phenol novolak type epoxy resin can be surely improved in flame retardancy and heat resistance. Although it is preferable to use those, it is not limited to these, for example, those obtained by reacting a novolak type epoxy resin with phenols, amines or carboxylic acids, and various epoxy resins and novolak A resin obtained by reacting with a type phenol resin can also be used.

On the other hand, the organic phosphorus compounds represented by the formulas (1) and (2) are obtained by starting from compounds in which the substituents X and X 'in these formulas are hydrogen atoms. It can be synthesized by reacting quinones respectively. Hereinafter, this specific example will be described.

That is, a compound in which R1 to R8 and the substituent X in the formula (1) are all hydrogen atoms is, for example,
9.1, commercially available as "HCA" manufactured by Sanko Chemical Co., Ltd.
0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is combined with 1,4-
By reacting with naphthoquinone, an organic phosphorus compound represented by the formula (5) can be synthesized. That is, the formula (5) is a specific example of the organic phosphorus compound represented by the formula (1). This synthesis example is disclosed in JP-A-60-126293, but in order to reduce impurities,
The amount of 1,4-naphthoquinone needs to be reacted in a stoichiometrically smaller amount than "HCA".

Further, as another specific example of the organic phosphorus compound, a compound in which all of R′1 to R′10 and the substituent X ′ in the formula (2) are hydrogen atoms is diphenylphosphine oxide (DPPO). ), And those obtained by reacting this with quinones.

The quinones used for synthesizing the organic phosphorus compounds represented by the above formulas (1) and (2) are not particularly limited, but in addition to the above-mentioned 1,4-naphthoquinone, , 4-benzoquinone, 1,2-benzoquinone,
Tolquinone and the like can also be used. Further, these quinones can be used alone or in combination of two or more.

The synthesis of the phosphorus-containing epoxy resin from the organic phosphorus compound represented by the above formula (1) or (2) and the epoxy resin can be performed by a known method. That is, the reaction temperature is 100 to 20
The temperature is 0 ° C, more preferably 120 to 180 ° C, and the mixture is reacted while stirring in a reaction vessel. If the progress of this reaction is slow, a catalyst can be added as necessary. Specific examples of this catalyst include tertiary amines such as benzyldimethylamine,
Quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, tris (2,6-
Phosphines such as dimethoxyphenyl) phosphine, phosphonium salts such as ethyltriphenylphosphonium bromide, 2-methylimidazole, 2-ethyl-4-
Examples thereof include imidazoles such as methylimidazole.

As described above, the phosphorus-containing epoxy resin can be synthesized, and such a phosphorus-containing epoxy resin may be used alone when preparing the phosphorus-containing epoxy resin composition. Or a mixture of two or more thereof.

However, the phosphorus content is 0.5 to 4.0% by mass based on the total amount of the phosphorus-containing epoxy resin composition, since the flame retardancy can be enhanced while maintaining the heat resistance.
It is set so that If the phosphorus content is less than 0.5% by mass, it is difficult to ensure flame retardancy, and if it exceeds 4.0% by mass, the heat resistance deteriorates.

As a curing agent commonly used in both inventions, a triazine-modified novolak resin is used alone or in combination with another curing agent. Specific examples of the resin include Dainippon Ink and Chemicals, Inc .; product number “LA-7054” and product number “LA-7055”. On the other hand, the other curing agent is not particularly limited as long as it is a commonly used one such as various phenolic resins, acid anhydrides, amines, hydrazides, and acidic polyesters. When the phosphorus-containing epoxy resin containing the above-mentioned curing agent is used, the adhesive strength between layers in a laminated board or the like can be increased.

The bisphenol A type epoxy resin used in the second invention has an average epoxy equivalent of 20.
It is necessary to use those having a value of 00 or less. Such bisphenol A type epoxy resin is bisphenol A
Glycidyl ether as a basic skeleton, and is not particularly limited as long as the average epoxy equivalent is 2000 or less. However, even if the basic skeleton is glycidyl ether of bisphenol A, if the average epoxy equivalent exceeds 2,000, the glass transition temperature (Tg) of the cured product may be lowered, and the heat resistance may be deteriorated. Absent. The substantial lower limit of the average epoxy equivalent is 160.

Further, the above average epoxy equivalent of 2000
The content of the following bisphenol A type epoxy resin is 2 to 20% by mass in the total epoxy resin in that the adhesive strength between the layers in the laminated board or the like can be further increased.
It is set so that If the content is less than 2% by mass, sufficient adhesiveness may not be obtained, and if it exceeds 20% by mass, the flame retardancy may be reduced.

As the epoxy resin other than the above-mentioned phosphorus-containing epoxy resin and bisphenol A type epoxy resin, any epoxy resin containing no halogen or phosphorus, that is, non-halogen non-phosphorus, can be used in combination.

In both inventions, a curing accelerator can be used. For example, tertiary amines, quaternary ammonium salts, phosphines, imidazoles, etc. may be mentioned as the same as the catalyst added as needed when synthesizing the phosphorus-containing epoxy resin as described above. However, the present invention is not limited to these.

In both the inventions, it is preferable to include a filler in the phosphorus-containing epoxy resin composition from the viewpoint that the storage stability of the semi-cured product can be improved. At this time, 30 parts by mass of the filler was
When it is contained in an amount of up to 120 parts by mass, the storage stability of the semi-cured product can be surely enhanced, which is preferable. When the amount of the filler is less than 30 parts by mass, the storage stability of the semi-cured product may not be sufficiently improved. Conversely, when the amount exceeds 120 parts by mass, there is no problem regarding the storage stability of the semi-cured product. Adhesion may be reduced. It should be noted that the solid content serving as a reference when compounding the filler does not include a liquid material such as a solvent, and also does not include the filler itself.

The filler is not particularly limited. For example, as the inorganic filler, calcium carbonate, silica, kaolin, calcined kaolin, clay,
Calcined clay, talc, calcined talc, hydrotalcite, wollastonite, metal hydroxide, metal oxide, glass powder, silica balloon, shirasu balloon, and the like can be used. Pulp fibers, synthetic fibers, ceramic fibers, and the like can be used, and fine particle rubber, thermoplastic elastomer, and the like can be used as the organic filler. It is preferable to use the above-mentioned inorganic filler, but among the listed kaolin, calcined kaolin, clay, calcined clay, talc, calcined talc, metal hydroxide, heat resistance after the laminate and the like absorb moisture Is more preferable. The above-mentioned fillers can be used alone or as a mixture of two or more.

The phosphorus-containing epoxy resin composition according to the present invention comprises the above-described phosphorus-containing epoxy resin, a curing agent, and, if necessary, known additives and other components in the first invention. In the second invention, in addition to the components of the first invention, a bisphenol A type epoxy resin having an average epoxy equivalent of 2000 or less is blended, and the mixture is uniformly mixed with a mixer, a blender or the like, and then heated and kneaded with a kneader or a roll. Can be prepared.

Here, a semiconductor device can be manufactured by sealing and molding the phosphorus-containing epoxy resin composition prepared as described above as a phosphorus-containing epoxy resin sealing material. For example, a semiconductor device in which a semiconductor element such as an IC is mounted in a transfer mold and a transfer molding is performed, and the semiconductor element is sealed with a sealing material of a phosphorus-containing epoxy resin composition is manufactured. Is what you can do.

Further, a semiconductor device can be manufactured by sealingly molding the phosphorus-containing epoxy resin composition prepared as described above using a phosphorus-containing epoxy resin casting material. For example, the C mounted on the wiring board
By molding a semiconductor element such as OB by a potting method, a semiconductor device in which the semiconductor element is sealed with a casting material of a phosphorus-containing epoxy resin composition can be manufactured.

In the semiconductor device thus obtained, since the semiconductor element is sealed by the cured product of the above-mentioned phosphorus-containing epoxy resin composition, it can exhibit excellent flame retardancy. In addition, no harmful substances are generated even when the fuel burns. Moreover, the adhesive strength between the sealing material or the casting material and the semiconductor element is
Triazine-modified novolak resin and average epoxy equivalent of 20
It is enhanced by a bisphenol A type epoxy resin of 00 or less.

On the other hand, a phosphorus-containing epoxy resin varnish can be prepared by mixing the phosphorus-containing epoxy resin composition prepared as described above with an organic solvent to adjust the viscosity. The organic solvent used at this time is not particularly limited, but for example, N, N-
Amides such as dimethylformamide (DMF), ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, methanol,
Examples thereof include alcohols such as ethanol, and aromatic hydrocarbons such as benzene and toluene. One of these organic solvents may be used alone,
A mixture of more than one species can be used. In addition,
The content of the phosphorus-containing epoxy resin composition is preferably from 30 to 80% by mass based on the total amount of the phosphorus-containing epoxy resin varnish.

A prepreg can be prepared using the phosphorus-containing epoxy resin varnish prepared as described above as a phosphorus-containing epoxy resin varnish for impregnation, and can be used as a phosphorus-containing epoxy resin varnish for coating. , A resin-attached metal foil, an adhesive sheet, a laminated board, a multilayer board, and the like. Hereinafter, a method for manufacturing these will be described.

In preparing a prepreg, the above-described phosphorus-containing epoxy resin varnish for impregnation is impregnated into a sheet-like substrate, and then heated and dried at 100 to 200 ° C. for 1 to 40 minutes to semi-cur the resin component (B). Stage). At this time, the amount of the resin in the prepreg is preferably 30 to 80% by mass based on the total amount of the prepreg. In addition, as the sheet-like base material,
Although not particularly limited, for example, a woven or nonwoven fabric of inorganic fibers such as glass, or a woven or nonwoven fabric of organic fibers such as polyester, polyamine, polyacryl, polyimide, and Kevlar can be used.

In preparing a metal foil with a resin, the above-mentioned phosphorus-containing epoxy resin varnish for coating is applied to one surface of the metal foil using a roll coater or the like.
It can be carried out by heating and drying at 100 to 200 ° C. for 1 to 40 minutes and semi-curing (B-stage) the resin component. At this time, the thickness of the resin portion of the metal foil with resin is preferably 5 to 80 μm. In addition, as the metal foil, although not particularly limited, for example,
A metal such as copper, aluminum, brass, and nickel can be used alone, or a composite material such as an alloy can be used. The thickness of such a metal foil is 0.012 to 0.07
It is preferably 0 mm.

In producing the adhesive sheet, a method generally called a casting method can be used. That is, the above-mentioned phosphorus-containing epoxy resin varnish for coating is coated on one surface of the carrier film by 5 to 1 μm.
After coating to a thickness of 00 μm, 100 to 20
This is carried out by heating and drying at 0 ° C. for 1 to 40 minutes, semi-curing (B-stage) the resin component, and forming it into a sheet. At this time, the thickness of the adhesive sheet is 5 to 80 μm.
m is preferable. In the above method, if the surface of the carrier film is previously treated with a release material,
The molded adhesive sheet can be easily peeled off from the carrier film, thereby improving workability. The carrier film is not particularly limited as long as it does not dissolve in the phosphorus-containing epoxy resin varnish for coating. For example, a polyester film, a polyimide film, or the like can be used.

As described above, when a filler is contained in the phosphorus-containing epoxy resin varnish for impregnation or the phosphorus-containing epoxy resin varnish for coating, the storage stability of the prepreg, the resin-coated metal foil, and the adhesive sheet is improved. It is possible to enhance the nature.

The production of the laminate can be carried out as follows. That is, a required number of at least one of the above-described prepreg, resin-coated metal foil, and adhesive sheet are stacked, and heated and pressed to form a laminate. At this time, a metal foil-clad laminate for processing into a printed wiring board can be manufactured by laminating and forming a metal foil on one side or both sides. The metal foil is not particularly limited. For example, the same metal foil as used for producing the metal foil with resin can be used. In the case of manufacturing a laminate using a metal foil with a resin, the metal foil of the metal foil with a resin is arranged and laminated so that the metal foil is on the outside. The heating and pressing conditions are not particularly limited as long as the phosphorus-containing epoxy resin composition can be cured.However, if the pressure is too low, air bubbles remain inside the obtained laminate and the electrical Because the characteristics may be reduced,
For example, a temperature of 160 to 220 ° C. and a pressure of 49.0 to 4
It is preferable to set 90.3 N / cm ² (5 to 50 kgf / cm ² ) and the time to 40 to 240 minutes.

In producing a multilayer board, the above-mentioned laminated board can be used. That is, a circuit for the inner layer is formed in advance on one or both sides of the laminate by an additive method, a subtractive method, or the like, and the surface of the circuit is subjected to a blackening treatment using an acid solution or the like, thereby producing an inner layer material. Keep it. Then, on one or both sides of the inner layer material, a required number of at least one of the above-described prepreg, resin-coated metal foil, and adhesive sheet are stacked to form an insulating layer, and a metal foil or the like is disposed outside the insulating layer. By forming the conductor layer by using this method, a multilayer board for processing into a multilayer printed wiring board can be manufactured. When a multilayer board is manufactured using a resin-attached metal foil, the resin-attached metal foil is arranged and laminated so that the metal foil is on the outside.

In forming the insulating layer using the prepreg, a required number of prepregs are stacked on one side or both sides of the inner layer material, and a metal foil is disposed outside the prepreg. It can be performed by laminating. That is, the cured product of the prepreg becomes the insulating layer, and the metal foil disposed outside the insulating layer becomes the conductor layer. Note that the same metal foil as described above can be used as the metal foil, and the conditions for heating and pressing can be the same as those for producing a laminate.

In forming the insulating layer using the metal foil with resin, the metal foil with resin is laminated on one or both sides of the inner layer material with the metal foil facing outward, and this is heated and pressed to form a laminate. Can be done by doing That is, the cured product of the resin portion of the resin-attached metal foil becomes the insulating layer, and the outer metal foil becomes the conductor layer. The conditions for the heating and pressurizing can be the same as the conditions for producing the laminate.

In forming the insulating layer using the adhesive sheet, a plurality of inner layer materials and the adhesive sheet may be alternately overlapped, or the adhesive sheet may be overlapped on one side or both sides of the inner layer material and formed on the outer side. This can be performed by arranging a metal foil and heating and pressurizing the metal foil to form a laminate. That is, the cured product of the adhesive sheet serves as an insulating layer, and the metal foil disposed outside serves as a conductor layer. Note that the same metal foil as described above can be used as the metal foil, and the conditions for heating and pressing can be the same as those for producing a laminate.

In forming the insulating layer, the above-described phosphorus-containing epoxy resin varnish for coating may be used. That is, after applying a phosphorus-containing epoxy resin varnish for coating on one or both sides of the above-mentioned laminated board or multilayer board, a metal foil or the like is arranged on this surface, and this is heated and pressed to form a laminate. be able to. In this case, the cured product of the phosphorus-containing epoxy resin varnish for coating serves as an insulating layer, and the metal foil disposed outside serves as a conductor layer. Then, after forming a circuit on the metal foil by a known method, a multilayer board having a larger number of layers can be produced by forming an insulating layer and a conductor layer one by one in the same manner as described above. It is. When using the above-mentioned phosphorus-containing epoxy resin varnish for coating, if necessary, the dilution concentration with an organic solvent, the type of the organic solvent,
Additives and the like can be appropriately changed, and for example, an organic solvent having a lower boiling point can be used.

Then, a circuit is formed on one or both sides of the laminated board or multilayer board manufactured as described above by an additive method, a subtractive method, or the like, and a hole is formed by laser processing, drilling, or the like. A printed wiring board or a multilayer printed wiring board can be manufactured by plating a hole to form a via hole or a through hole to establish conduction between layers. Further, by forming the insulating layer and the conductor layer one by one as described above, a multilayer printed wiring board having a larger number of layers can be formed.

In the thus obtained laminated board or multilayer board, the insulating layer is formed of a cured product of the above-mentioned phosphorus-containing epoxy resin composition without containing halogen, so that excellent flame retardancy is obtained. That can show
Even if it burns, it will not produce harmful substances. In addition, the adhesive strength between the prepregs forming the insulating layer and between the insulating layer and the conductive layer is determined by a triazine-modified novolak resin or a bisphenol A type epoxy having an average epoxy equivalent of 2000 or less to the phosphorus-containing epoxy resin composition. It is enhanced by the blending of the resin. When the insulating layer is formed using a resin-attached metal foil or an adhesive sheet, since the sheet-like base material of inorganic fibers such as glass does not exist in the layer, the adhesive strength between the respective layers is reduced as in the case of the prepreg. Although it cannot be directly measured, it is easily presumed from the results obtained when prepreg is used that the adhesive strength between the layers is improved.

[0062]

The present invention will be specifically described below with reference to examples.

The phosphorus-containing epoxy resin was synthesized as shown in the following synthesis examples (1) to (6). here,
"HCA" refers to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd .; product number "HCA"), "DPP
"O" is diphenylphosphine oxide,
"1,4-NQ" means 1,4-naphthoquinone,
“1,4-BQ” means 1,4-benzoquinone,
"YDPN-638" is a phenol novolak type epoxy resin (manufactured by Toto Kasei Co., Ltd .;
-638 ") and" YD-128 "are bisphenol A type novolak type epoxy resins (manufactured by Toto Kasei Co., Ltd .; product number" YD-128 "), and" YDCN-701 "is cresol novolak type epoxy resin (Manufactured by Toto Kasei Co., Ltd .; product number “YDCN-701”).

Synthesis Example (1) In a four-necked glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device, 16 HCA was added.
0.5 g and 400 g of toluene were charged, and "HCA" was dissolved by heating. Thereafter, 109.0 g of “1,4-NQ”
While paying attention to the heat of reaction, the mixture was added in small portions. After the completion of the reaction, 730 g of “YDPN-638” was charged, the mixture was stirred while introducing nitrogen gas, and heated to 120 ° C. to dissolve. Further, 0.25 g of triphenylphosphine was added and reacted at 150 ° C. for 4 hours. The epoxy equivalent of the obtained phosphorus-containing epoxy resin is 385 g.
/ Eq, phosphorus content was 2.3% by mass.

Synthesis Example (2) 209.5 g of “HCA”, 400 g of toluene,
142.5 g of “1,4-NQ”, “YDPN-63”
650 g of 8 "and 0.25 g of triphenylphosphine
The same operation as in Synthesis Example (1) was performed except that. The epoxy equivalent of the obtained phosphorus-containing epoxy resin is 580 g /
The eq and phosphorus contents were 3.0% by mass.

Synthesis Example (3) 153.5 g of “HCA”, 400 g of toluene,
104.5 g of “1,4-NQ”, “YDCN-70”
1 "is 750 g, and triphenylphosphine is 0.25 g.
The same operation as in Synthesis Example (1) was performed except that. The epoxy equivalent of the obtained phosphorus-containing epoxy resin is 455 g /
The eq and phosphorus contents were 2.2% by mass.

Synthesis Example (4) 124.0 g of “DPPO”, 400 g of toluene,
90.0 g of “1,4-NQ”, “YDCN-701”
Was performed in the same manner as in Synthesis Example (1), except that 790 g of triphenylphosphine and 0.25 g of triphenylphosphine were used. The epoxy equivalent of the obtained phosphorus-containing epoxy resin is 390 g / e.
q, phosphorus content was 1.9% by mass.

Synthesis Example (5) 160.5 g of “HCA”, 400 g of toluene,
75.0 g of "1,4-BQ", "YDPN-638"
Was carried out in the same manner as in Synthesis Example (1), except that 770 g of triphenylphosphine and 0.25 g of triphenylphosphine were used. The epoxy equivalent of the obtained phosphorus-containing epoxy resin is 360 g / e.
q, phosphorus content was 2.3% by mass.

Synthesis Example (6) 125.5 g of “HCA”, 400 g of toluene,
85.5 g of “1,4-NQ” and 7 of “YD-128”
The same operation as in Synthesis Example (1) was performed, except that 90 g and 0.25 g of triphenylphosphine were used. The obtained phosphorus-containing epoxy resin had an epoxy equivalent of 330 g / eq and a phosphorus content of 1.8% by mass.

(Examples 1 to 21 and Comparative Examples 1 to 22) (Preparation of Prepreg) Examples 1 to 21 and Comparative Examples 1 and 2
For No. 2, a phosphorus-containing epoxy resin varnish having the composition shown in Tables 1 to 6 was prepared and impregnated with a glass cloth (manufactured by Nitto Boseki Co., Ltd .; type 7628; product number "H258"). The prepreg was dried by heating for minutes.

Tables 1 and 4 show Examples and Comparative Examples respectively corresponding to the second invention (Examples 1 and 2).
Tables 2 and 3 and Tables 5 and 6 are Examples and Comparative Examples respectively corresponding to the first invention.

In Tables 1 to 6, "Dicy" means dicyandiamide (manufactured by Nippon Carbide Co., Ltd.),
"EPICLON 2055" means a bisphenol A type novolak type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc .; product number "EPICLON 2055"), "L
“A-7054” and “LA-7055” are triazine-modified novolak resins (manufactured by Dainippon Ink and Chemicals, Inc.), and “PSM4357” is phenol novolak (manufactured by Gunei Chemical Co., Ltd .; product number “PSM4357”). ,
“2E4Mz” means 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd .; product number “2E4M”
z ")," talc "is manufactured by Fuji Talc Kogyo Co., Ltd .; product number" PKP-53 ", and" baked talc "is manufactured by Fuji Talc Kogyo Co., Ltd .; product number" LMS-100 "at 800 ° C. “Aluminum hydroxide” is manufactured by Sumitomo Chemical Co., Ltd .; part number “CL-310”; “Kaolin” is manufactured by Fuji Talc Corporation; part number “ASP-07”, “baked” "Kaolin" is made by Fuji Talc Industries Co., Ltd .; product number "SATINTONE No."
5 "and" Alumina "are manufactured by Sumitomo Chemical Co., Ltd .; Part No." AL-41 ", and" Glass powder "are manufactured by Nippon Frit Co .; Part No." GF-2-10 "," Wallast ""Knight" is Kinsei Matech Co., Ltd .; product number "FPW800".

(Preparation of Laminated Plate) Three prepregs prepared as described above were laminated, and a copper foil having a thickness of 18 μm was placed on both sides of the prepreg, and this was placed at 170 ° C. and 392 N / cm ² (4
A laminate for an inner layer material was prepared by performing heat and pressure molding under the conditions of 0 kgf / cm ² ) for 120 minutes. Then, after forming circuits on both sides of the laminate by a subtractive method, through holes were formed, and the circuit surface was subjected to a blackening treatment with an acidic solution to prepare a printed wiring board for an inner layer material.

(Preparation of Multilayer Board) On each side of the printed wiring board for the inner layer material, one prepreg is laminated, and a copper foil having a thickness of 18 μm is arranged outside the prepreg.
Heat and pressure molding was performed at 70 ° C. and 392 N / cm ² (40 kgf / cm ² ) for 120 minutes to prepare a multilayer board for evaluating flame retardancy.

(Evaluation of Interlayer Adhesion Strength) JIS C 648
1 In accordance with 5.7, the prepreg 1
Peeling was performed between the sheet and the remaining two sheets, and the strength was measured.

(Evaluation of Life of Semi-cured Product) For the semi-cured products of the phosphorus-containing epoxy resin varnishes of Examples and Comparative Examples, the minimum melt viscosity at 130 ° C. was measured using a falling flow tester. At this time, the initial melt viscosity and 40
The melt viscosity after storage in a thermostat at ± 3 ° C. for 3 days was measured, and from each measurement result, the degree of change in the melt viscosity was calculated by the following formula, and the life was evaluated.

Degree of change in melt viscosity (times) = (melt viscosity after 3 days) / (initial melt viscosity) (Evaluation of heat resistance to moisture absorption)
cut into square meters at 121 ° C and 2 atmospheres under a saturated steam pressure of 2 atm.
After moisture absorption for 3 hours, this is placed in a solder bath at 260 ± 5 ° C for 3 hours.
It was charged for 0 seconds, and the presence or absence of blistering was observed. The situation of the blister at this time was determined as follows.

Level 1: No measling on the glass cloth surface is recognized (pass level).

Level 2: Measuring on the glass cloth surface is observed, but no blistering occurs (pass level).

Level 3: Swelling has occurred (failure level).

(Evaluation of Flame Retardancy) The entire surface of the multilayer plate was etched, and the flame retardancy was evaluated according to the UL94-1993 20 mm vertical test method.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

As can be seen from Tables 1 to 6, it was confirmed that the triazine-modified novolak resin was used as a curing agent in each of the examples, so that the interlayer adhesion strength was improved. Moreover, it is confirmed that when a bisphenol A type epoxy resin having an average epoxy equivalent of 2000 or less is used in combination, the interlayer adhesive strength is further improved.

It is presumed that the use of the filler reduces the degree of change in the melt viscosity and increases the storage stability of the semi-cured product. However, if the filler is used excessively, the interlayer adhesion strength decreases. Is confirmed. On the other hand, in Examples 1, 3, and 6 to 8 in which no filler was used, the degree of change in the melt viscosity was larger than that in which the filler was used, and the storage stability of the semi-cured product was estimated to be lower. .

Further, as in Examples 9 to 12, 16 to 21, it was confirmed that the use of a specific filler improved the heat resistance to moisture absorption.

[0091]

As described above, the phosphorus-containing epoxy resin composition according to claim 1 of the present invention comprises at least one of the organic phosphorus compounds represented by the above formulas (1) and (2),
A phosphorus-containing epoxy resin obtained by reacting a novolak-type epoxy resin with an epoxy resin containing 20% by mass or more, a curing agent as an essential component, and a phosphorus content of 0.5 to 4.0% by mass in the total amount of the composition. In addition, since part or all of the curing agent is a triazine-modified novolak resin, by blending a phosphorus-containing epoxy resin, it is possible to ensure flame retardancy without containing a halogen that causes generation of harmful substances. In addition, by blending a triazine-modified novolak resin as a curing agent, the adhesive strength between the layers in a laminated board or the like can be increased.

Further, the phosphorus-containing epoxy resin composition according to claim 2 contains at least one of the organic phosphorus compounds represented by the above formulas (1) and (2) and at least 20% by mass of a novolak type epoxy resin. Phosphorus-containing epoxy resin obtained by reacting with an epoxy resin to be reacted, average epoxy equivalent 2
Bisphenol A type epoxy resin of 000 or less, a curing agent as an essential component, and a phosphorus content of 0.5 to
4.0% by mass, the content of the bisphenol A type epoxy resin is 2 to 20% by mass of the total epoxy resin, and a part or all of the curing agent is a triazine-modified novolak resin. By blending the epoxy resin containing, it is possible to ensure flame retardancy without containing a halogen that causes the generation of harmful substances, and by blending a triazine-modified novolak resin as a curing agent, it can be used in laminated boards and the like. The adhesive strength between the layers can be increased. In addition, by blending a bisphenol A type epoxy resin having an average epoxy equivalent of 2000 or less, the adhesive strength between the layers can be further increased, and the heat resistance can be increased.

The third aspect of the present invention is to improve the storage stability of the semi-cured product because it contains a filler in the first or second aspect.

The invention of claim 4 uses the phosphorus-containing epoxy resin because the compound represented by the above formula (5) is used as the organic phosphorus compound in any one of claims 1 to 3. By doing so, it is possible to ensure flame retardancy without containing a halogen that causes the generation of harmful substances, and by blending a triazine-modified novolak resin as a curing agent, the adhesive strength between layers in a laminated board or the like can be improved. It can be enhanced.

The invention of claim 5 is characterized in that in claim 3 or 4, the filler is added in an amount of 30 to 1 with respect to 100 parts by mass of the solid content.
Since it contains 20 parts by mass, the storage stability of the semi-cured product can be surely enhanced.

The invention according to claim 6 is the invention according to any one of claims 3 to 5, wherein the filler is calcium carbonate, silica, kaolin, calcined kaolin, clay, calcined clay.
Since it contains talc, calcined talc, hydrotalcite, wollastonite, metal hydroxide, metal oxide, glass powder, silica balloon, and shirasu balloon, the storage stability of the semi-cured product is further improved. It can be enhanced.

[0097] The invention according to claim 7 includes the filler according to any one of claims 3 to 5, wherein the filler is selected from kaolin, calcined kaolin, clay, calcined clay, talc, calcined talc, and metal hydroxide. As a result, the storage stability of the semi-cured product can be further improved, and the heat resistance of the laminated board or the like after moisture absorption can be improved.

The invention of claim 8 is the invention according to any one of claims 1 to 7, wherein the novolak epoxy resin is
Since it contains a bisphenol A type novolak type epoxy resin, a cresol novolak type epoxy resin, or a phenol novolak type epoxy resin,
Flame retardancy and heat resistance can be reliably improved.

In the prepreg according to the ninth aspect, since the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects is impregnated into a sheet-like substrate and is semi-cured, it is possible to reduce the generation of harmful substances. Flame retardancy can be ensured without containing halogen causing the problem, and the adhesive strength between the layers can be increased when a laminate or the like is manufactured.

The resin-attached metal foil according to claim 10 is
Since the phosphorus-containing epoxy resin composition according to any one of claims 1 to 8 is applied on a metal foil and is semi-cured, it does not contain a halogen that causes generation of a harmful substance, and thus has flame retardancy. In addition to the above, it is possible to increase the adhesive strength between the layers when a laminate or the like is manufactured.

In the adhesive sheet according to the eleventh aspect, since the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects is formed into a sheet and is semi-cured, it causes the generation of harmful substances. This makes it possible to ensure flame retardancy without containing halogen, and to increase the adhesive strength between the layers when a laminate or the like is produced.

Further, the laminated plate according to claim 12 is the ninth aspect.
Since at least one of the prepreg, the metal foil with resin according to claim 10 and the adhesive sheet according to claim 11 is laminated and formed, it contains a halogen that causes generation of harmful substances. Thus, the flame retardancy can be ensured without increasing the adhesive strength between the layers.

The multilayer board according to the thirteenth aspect is the ninth aspect.
Since at least one of the prepreg described in (1), the metal foil with resin described in (10), and the adhesive sheet described in (11) is included in at least one layer in each layer, it causes generation of harmful substances. Flame retardancy can be ensured without containing halogen, and the adhesive strength between the layers is enhanced.

The phosphorus-containing epoxy resin varnish for coating according to the fourteenth aspect uses the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects. In addition to the above, it is possible to ensure flame retardancy without containing and to increase the adhesive strength between the layers.

The multilayer board according to claim 15 is characterized in that:
Since the phosphorus-containing epoxy resin varnish for coating according to 4 is coated, flame retardancy can be secured without containing a halogen that causes generation of harmful substances,
The adhesive strength between the layers is increased.

Further, since the phosphorus-containing epoxy resin sealing material according to claim 16 uses the phosphorus-containing epoxy resin composition according to any one of claims 1 to 8, halogens that cause generation of harmful substances are eliminated. It is possible to ensure flame retardancy without containing the same and to increase the adhesive strength between the semiconductor element and the sealing material in the semiconductor device.

The phosphorus-containing epoxy resin casting material according to the seventeenth aspect uses the phosphorus-containing epoxy resin composition according to any one of the first to eighth aspects, and thus contains a halogen that causes generation of harmful substances. It is possible to ensure flame retardancy without performing the process and to increase the adhesive strength between the semiconductor element and the casting material in the semiconductor device.

Further, since the phosphorus-containing epoxy resin varnish for impregnation according to claim 18 uses the phosphorus-containing epoxy resin composition according to any one of claims 1 to 8, halogens which cause generation of harmful substances are eliminated. Flame retardancy can be ensured without containing, and the adhesive strength between the layers is enhanced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 63/00 C08L 63/00 A C09K 21/14 C09K 21/14 F-term (Reference) 4F072 AB04 AB05 AB06 AB07 AB09 AB28 AB29 AD28 AD32 AD33 AE01 AF01 AG03 AH02 AH21 AJ04 AK05 AL09 4H028 AA46 BA01 BA04 4J002 CC073 CC183 CD052 CD111 CD201 DE096 DE236 DE286 DJ006 DJ016 DJ036 DJ046 DL006 FA106 FD016 FD143 4J036 AD08 AF02 DC02 DC01 JA05 JA08 JA11 (54) [Title of the Invention] Phosphorus-containing epoxy resin composition, prepreg, metal foil with resin, adhesive sheet, laminate, multilayer board, phosphorus-containing epoxy resin varnish for coating, phosphorus-containing epoxy resin sealing material , Phosphorus-containing epoxy resin casting material, phosphorus-containing epoxy resin varnish

Claims (18)

[Claims] 1. A phosphorus-containing compound obtained by reacting at least one of the organic phosphorus compounds represented by the following formulas (1) and (2) with an epoxy resin containing 20% by mass or more of a novolak type epoxy resin. An epoxy resin and a curing agent are essential components, the phosphorus content is 0.5 to 4.0% by mass of the total amount of the composition, and a part or all of the curing agent is a triazine-modified novolak resin. A phosphorus-containing epoxy resin composition. Embedded image 2. A phosphorus-containing compound obtained by reacting at least one of the organic phosphorus compounds represented by the above formulas (1) and (2) with an epoxy resin containing 20% by mass or more of a novolak type epoxy resin. An epoxy resin, a bisphenol A type epoxy resin having an average epoxy equivalent of 2,000 or less, and a curing agent are essential components, and the phosphorus content is 0.1% in the total amount of the composition.
5 to 4.0% by mass, and the content of the bisphenol A type epoxy resin is 2 to 20% by mass in the total epoxy resin.
And a phosphorus-containing epoxy resin composition, wherein part or all of the curing agent is a triazine-modified novolak resin. 3. The phosphorus-containing epoxy resin composition according to claim 1, further comprising a filler. 4. An organic phosphorus compound represented by the following formula (5):
2. The method according to claim 1, wherein the method comprises:
4. The phosphorus-containing epoxy resin composition according to any one of claims 1 to 3. Embedded image 5. The filler is added in an amount of 3 parts per 100 parts by mass of the solid content.
The phosphorus-containing epoxy resin composition according to claim 3, comprising 0 to 120 parts by mass. 6. As a filler, calcium carbonate, silica, kaolin, calcined kaolin, clay, calcined clay, talc, calcined talc, hydrotalcite, wollastonite, metal hydroxide, metal oxide, glass powder, silica The phosphorus-containing epoxy resin composition according to any one of claims 3 to 5, wherein the phosphorus-containing epoxy resin composition contains a material selected from a balloon and a shirasu balloon. 7. The filler according to claim 3, wherein the filler contains one selected from kaolin, calcined kaolin, clay, calcined clay, talc, calcined talc, and metal hydroxide. 3. The phosphorus-containing epoxy resin composition according to item 1. 8. The method according to claim 1, wherein the novolak type epoxy resin is selected from bisphenol A type novolak type epoxy resin, cresol novolak type epoxy resin and phenol novolak type epoxy resin. The phosphorus-containing epoxy resin composition according to any one of the above. 9. A prepreg, wherein the phosphorus-containing epoxy resin composition according to claim 1 is impregnated in a sheet-like substrate and is semi-cured. 10. A metal foil with resin, wherein the phosphorus-containing epoxy resin composition according to any one of claims 1 to 8 is applied on a metal foil and semi-cured. 11. An adhesive sheet, wherein the phosphorus-containing epoxy resin composition according to claim 1 is formed into a sheet and semi-cured. 12. The prepreg according to claim 9, at least one of the metal foil with resin according to claim 10, and the adhesive sheet according to claim 11, which is formed by lamination molding. Laminated board. 13. A layer comprising at least one of the prepreg according to claim 9, the metal foil with resin according to claim 10, and the adhesive sheet according to claim 11. A multilayer board characterized by the above. 14. A phosphorus-containing epoxy resin varnish for coating, comprising the phosphorus-containing epoxy resin composition according to claim 1. Description: 15. A multilayer board, which is coated with the phosphorus-containing epoxy resin varnish for coating according to claim 14. 16. A phosphorus-containing epoxy resin sealing material comprising the phosphorus-containing epoxy resin composition according to claim 1. Description: 17. A phosphorus-containing epoxy resin casting material comprising the phosphorus-containing epoxy resin composition according to claim 1. Description: 18. A phosphorus-containing epoxy resin varnish for impregnation, comprising the phosphorus-containing epoxy resin composition according to any one of claims 1 to 8.