JP2010248495A - Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate plate and multilayer printed wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting insulating resin composition which has a good balance in all of heat resistance to soldering, heat resistance with copper (T-288), moisture resistance, and a flame retardant property, shows an excellent adhesion strength of plating, and has a low thermal expansion property, and to provide an insulating film with support, a prepreg, a laminate plate and a multilayer printed wiring board using the same. <P>SOLUTION: The thermosetting insulating resin composition includes a curing agent (A) having an N-substituted maleimide group manufactured by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule with an amine compound (b) having an acid substituent and the acid substituent, an epoxy resin (B) having at least two epoxy groups in one molecule, and a phosphorus-containing compound (C) to impart a flame retardant property. The insulating film with support, the prepreg, the laminate plate, and the multilayer printed wiring board use the thermosetting insulating resin composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is for a multilayer printed wiring board that balances solder heat resistance, heat resistance with copper (T-288), moisture resistance and flame resistance, exhibits excellent plating adhesion strength, and has low thermal expansion. The present invention relates to a thermosetting insulating resin composition, and an insulating film with a support, a prepreg, a laminate, and a multilayer printed wiring board using the same.

In recent years, electronic devices have become smaller, lighter, and more functional, and along with this, higher integration of LSIs and chip components has progressed, and the form has rapidly changed to multi-pin and miniaturization. . For this reason, in order to improve the mounting density of electronic components, the development of micro wiring has been advanced for multilayer printed wiring boards.
There is a built-up method as a method for manufacturing a multilayer printed wiring board meeting these requirements, and it is becoming mainstream as a method suitable for weight reduction, miniaturization, and miniaturization.

In addition, there is an active movement to regulate materials including electronic parts that may generate harmful substances during combustion due to increased environmental awareness. In conventional multilayer printed wiring boards, bromo compounds have been used for flame retardancy, but harmful substances may be generated during combustion, so this bromine compound will not be usable in the near future. is expected.
A lead-free solder containing no lead is also being put into practical use as a solder generally used for connecting an electronic component to a multilayer printed wiring board. This lead-free solder has a higher use temperature than conventional eutectic solder by about 20 to 30 ° C. Therefore, the material is required to have higher heat resistance than ever before.

  Furthermore, in the multilayer printed wiring board having the build-up structure, in order to increase the density, the number of layers is increased and the via portion is filled and stacked. However, insulation resin layers that do not contain glass cloth tend to have a large coefficient of thermal expansion for the purpose of reducing the thickness of multilayer printed wiring boards, so the difference in coefficient of thermal expansion with copper in filled and stacked vias It greatly affects reliability and is a concern for reliability. For this reason, a material having a low coefficient of thermal expansion has been required for the insulating resin layer.

In order to reduce the thermal expansion coefficient in the insulating resin layer, generally, a method of filling a large amount of an inorganic filler having a small thermal expansion coefficient and reducing the thermal expansion coefficient of the entire insulating layer has been used (for example, see Patent Document 1). However, such a method tends to cause many problems such as a decrease in fluidity and a decrease in insulation reliability.
In addition, attempts have been made to achieve low thermal expansion by selecting or improving the resin. For example, as an example of an epoxy resin having an aromatic ring, there is a resin composition for low thermal expansion pressure molding using an epoxy resin having a bifunctional naphthalene skeleton or a biphenyl skeleton (see Patent Document 2). 80 to 92.5% by volume. Moreover, conventionally, a method for reducing the thermal expansion coefficient of a resin composition for a wiring board is generally a method in which the thermal expansion coefficient is reduced by increasing the crosslinking density and increasing the glass transition temperature (Tg) (Patent Document 3 and 4). However, increasing the crosslink density requires shortening the molecular chain between the functional groups, but shortening the molecular chain beyond a certain level is difficult in terms of reactivity and resin strength.

  Furthermore, introduction of an imide skeleton, which is considered to be useful for heat resistance and low thermal expansion, has been attempted. For example, a thermosetting composition for build-up using an aromatic diamine having an imide group and an epoxy resin has been proposed. (See Patent Document 5). However, when a low molecular weight polyimide compound is used as a curing agent for an epoxy resin, most of them are not different from the characteristics of the epoxy resin in many cases.

JP 2004-182851 A Japanese Patent Laid-Open No. 5-148543 JP 2000-243864 A JP 2000-114727 A JP 2000-17148 A

  The object of the present invention is to balance solder heat resistance, heat resistance with copper (T-288), moisture resistance and flame retardancy, exhibit excellent plating adhesion strength, and low heat from the above situation. It is an object to provide a thermosetting insulating resin composition for a multilayer printed wiring board that is expandable, and an insulating film with a support, a prepreg, a laminate, and a multilayer printed wiring board using the same.

As a result of diligent research to solve the above problems, the present invention provides an N-substituted maleimide group obtained by reacting a specific maleimide compound and an amine compound in an organic solvent as an insulating resin composition for a multilayer printed wiring board. The inventors have found that the above object can be achieved by using a curing agent having an acidic substituent and a resin composition containing an epoxy resin and a phosphorus-containing compound that imparts flame retardancy, thereby completing the present invention.
That is, the present invention provides the following thermosetting insulating resin composition, insulating film with support, prepreg, laminate and multilayer printed wiring board.

1.1 Manufactured by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in the molecule with an amine compound (b) having an acidic substituent represented by the general formula (I) in an organic solvent. Curing agent (A) having N-substituted maleimide group and acidic substituent, epoxy resin (B) having at least two epoxy groups in one molecule, and phosphorus-containing compound (C) imparting flame retardancy A thermosetting insulating resin composition comprising:

（Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を示し、Ｒ₂は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、ハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である）

(R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and R ₂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, (x is an integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5)

2. Furthermore, the said 1 thermosetting insulating resin composition containing the hardening | curing agent and / or hardening accelerator (D) of the said epoxy resin.
3. Furthermore, the said 1 or 2 thermosetting insulating resin composition containing the compound (E) which can be chemically roughened.
4). The phosphorus atom content derived from the phosphorus-containing compound (C) that imparts flame retardancy to 100 parts by mass of the total amount of components (A) to (D) in terms of solids is 0.5 to 2.0 parts by mass. The thermosetting insulation resin composition in any one of said 1-3.
5). The thermosetting insulating resin composition according to any one of the above 1 to 4, comprising 10 to 65 parts by mass of an inorganic filler (F) with respect to 100 parts by mass of the total amount of components (A) to (D) in terms of solid matter. .

6). A semi-cured film of the thermosetting insulating resin composition according to any one of 1 to 5 above is formed on a support surface.
7). A prepreg characterized in that the thermosetting insulating resin composition according to any one of 1 to 5 above is impregnated in a sheet-like reinforcing base material comprising fibers.
8). An insulating resin layer is formed using any one of (1) the thermosetting insulating resin composition of any one of 1 to 5 above, (2) the insulating film with support of 6 above, and (3) the prepreg of 7 above. A laminated board characterized by being made.
9. A multilayer printed wiring board produced by using the laminated board of 8 above.

  The thermosetting insulating resin composition for a multilayer printed wiring board of the present invention is a curing agent having an N-substituted maleimide group and an acidic substituent obtained by reacting a specific maleimide compound and an amine compound in an organic solvent (A ), The epoxy resin (B) and the phosphorus-containing compound (C) that imparts flame retardancy, the glass transition temperature (Tg) is particularly high, so the heat resistance is high, the thermal expansion is low, and the plating is excellent. A thermosetting resin composition capable of forming an insulating resin layer exhibiting adhesion strength is obtained, the thermosetting insulating resin composition, an insulating film with a support using the same, a laminate produced from a prepreg, and a multilayer print The wiring board is balanced with all of solder heat resistance, heat resistance with copper (T-288), moisture resistance and flame retardancy, and has high reliability, so that a product suitable for an electronic component or the like can be obtained.

Hereinafter, the present invention will be described in detail.
The thermosetting insulating resin composition according to the present invention (hereinafter also simply referred to as an insulating resin composition) includes a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule, and a general formula (I And a curing agent (A) having an N-substituted maleimide group and an acidic substituent, which is produced by reacting an amine compound (b) having an acidic substituent shown in FIG. A thermosetting insulating resin composition comprising an epoxy resin (B) having an epoxy group and a phosphorus-containing compound (C) imparting flame retardancy.

（Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を示し、Ｒ₂は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、ハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である）

(R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and R ₂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, (x is an integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5)

Examples of the maleimide compound (a) having at least two N-substituted maleimide groups in one molecule include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-( 1,3-phenylene) bismaleimide, N, N ′-[1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N , N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3-dimethyl-5,5-diethyl-4, 4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) Phenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] Methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimide) Phenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-male Imidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4 -(4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) ) Biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) di Sulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl ] Sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- ( 3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4 -(4-Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl ] Benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide represented by the following general formula (II), and the like. These maleimide compounds may be used alone or in combination of two or more. May be used
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N ′-(1,3-phenylene) bismaleimide, which has a high reaction rate and can have higher heat resistance, 2 , 2-bis (4- (4-maleimidophenoxy) phenyl) propane is preferred, and bis (4-maleimidophenyl) methane and N, N ′-(1,3-phenylene) bismaleimide are more preferred because of their low cost. From the viewpoint of solubility in a solvent, bis (4-maleimidophenyl) methane is particularly preferred.

（式中、ｒは１〜１０の整数である。）

(In the formula, r is an integer of 1 to 10.)

  Examples of the amine compound (b) having an acidic substituent represented by the general formula (I) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o -Aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc., among these, From the viewpoint of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and heat resistant M-Aminophenol and p-aminophenol are more preferable from the viewpoint, and m-aminophenol is particularly preferable from the viewpoint of low toxicity. Preferred.

In producing the curing agent (A), the diamine compound (c) can be used together with the amine compound (b) having an acidic substituent represented by the general formula (I).
Examples of the diamine compound (c) include aromatic amines such as m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenylmethane, and 2,2. '-Bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, bis (3-amino which is a diamine having a sulfur atom in the molecular main chain Phenyl) sulfone, bis (4-aminophenyl) sulfone, 2,2′-diaminodiphenyl sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, bis (2,3,5,6) -Tetrafluoro-4-aminophenyl) sulfide, 2,2'-dithiodianiline, 3,3'-dithiodiani 4,4′-dithiodianiline, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy) Diphenylsulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2′-bis [4- {2- (4-aminophenoxy) ethoxy } Phenyl] sulfone, 3,3′-disulfonic acid-bis {4- (3-aminophenoxy) -phenyl} sulfone, 3,3 ′, 5,5′-tetramethyl-bis {4- (4-aminophenoxy) ) Phenyl} sulfone, 4,4′-bis (6-aminonaphthoxy) diphenylsulfone, 4,4′-bis (3-aminophenoxyphenyl) diphenylsulfone, aliphatic Ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, which are amines, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) Tetramethyldisiloxane, diaminopolysiloxane, 2,5-diamino-1,3,4-oxadiazol, bis (4-aminocyclohexyl) methane, guanamine compounds such as melamine, benzogua Min, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2 , 4-diamino-6-methacryloyloxyethyl-s-triazine and the like.

The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, aprotic compounds such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide May be used, and one or two or more may be used in combination.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility. Cyclohexanone and propylene are low toxicity and high volatility and hardly remain as a residual solvent. Glycol monomethyl ether and dimethylacetamide are particularly preferred.

Here, the use amount of the maleimide compound (a), the amine compound (b) having an acidic substituent and the diamine compound (c) is determined based on the maleimide compound (a) relative to the equivalent (T _b ) of the —NH ₂ group of the amine compound (b). ) Equivalent ratio (T _a / T _b ) of equivalents (T _a ) of maleimide groups in the range of 1.0 <(T _a / T _b ) ≦ 10.0, and the corresponding amount ratio (T _a / T _b ) is more preferably in the range of 2.0 ≦ (T _a / T _b ) ≦ 10.0. Appropriate amount ratio (T _a / T _b) without gelation and heat resistance is decreased by a larger than 1.0, solubility in an organic solvent by a 10.0, plating adhesion strength, And heat resistance does not fall.
Moreover, it is preferable to set it as 10-1000 mass parts per 100 mass parts of total amounts of (a), (b), (c) component, and, as for the usage-amount of an organic solvent, it is more preferable to set it as 100-500 mass parts. Preferably, it is particularly preferably 200 to 500 parts by mass. When the blending amount of the organic solvent is 10 parts by mass or more, sufficient solubility of the curing agent in the organic solvent can be obtained, and when it is 1000 parts by mass or less, a long reaction time is not caused.
The reaction temperature of the components (a), (b), and (c) is preferably 50 to 200 ° C, more preferably 70 to 160 ° C. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
Moreover, a reaction catalyst can be arbitrarily used for this reaction, and it is not specifically limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be used.

  Next, the component (B) is not particularly limited as long as it is an epoxy resin having at least two epoxy groups in one molecule. For example, bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol Examples thereof include glycidyl ethers, glycidyl ethers, glycidyl amines, glycidyl esters, and the like such as naphthyl, naphthalene, alicyclic, and alcohols, which can be used alone or in combination. Specifically, in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, Biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. are preferable, and naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type from the viewpoint of having good low thermal expansion and high glass transition temperature An epoxy resin, a biphenyl aralkyl type epoxy resin, and a phenol novolac type epoxy resin are more preferable.

  The mass ratio of the (A) component and the (B) component in terms of solid content in the insulating resin composition of the present invention is preferably such that the total amount is 100 parts by mass and the (A) component is 20 to 95 parts by mass. 40 to 90 parts by mass is more preferable. By setting the component (A) to 20 parts by mass or more, flame retardancy, heat resistance, adhesiveness and dielectric properties are improved. Moreover, the thermosetting insulating resin composition which has high reliability can be obtained by setting it as 95 mass parts or less.

In the present invention, in addition to the components (A) and (B), the phosphorus-containing compound (C) imparting flame retardancy is used, and it is preferable to use a compound having a reactive functional group containing a phosphorus atom. This reactive functional group is any one of an acidic substituent of the curing agent (A), an epoxy group of the epoxy resin (B), and a functional group of an epoxy resin curing agent and / or a curing accelerator (D) described later. Reacts with the above.
Examples of the phosphorus-containing compound (C) that imparts flame retardancy include phosphorus-containing epoxy resins, phosphorus-containing phenol resins, phenoxyphosphazene compounds, condensed phosphate compounds, and diphosphinates. It is particularly effective to use these in combination.
An example of a commercially available phosphorus-containing compound that does not have a reactive functional group is Exolit OP930 [manufactured by Clariant Japan Co., Ltd., product name, phosphorus content 23 mass%]. Examples of the phosphorus-containing compound having a reactive functional group include phosphorus-containing phenols such as FX-305 (product name, phosphorus content: about 3% by mass) manufactured by Toto Kasei Co., Ltd., which is a phosphorus-containing epoxy compound. The compound HCA-HQ [manufactured by Sanko Co., Ltd., product name, phosphorus content: about 9% by mass] and phosphorus-containing phenol produced by a known method can also be used. As the phosphorus-containing phenol compound, for example, the phosphorus-containing phenol produced by the method described in US 2007/0221890 is soluble in a solvent, and aggregates are hardly formed, which is preferable in terms of forming fine wiring. .

An epoxy resin curing agent and / or a curing accelerator (D) can be optionally used in combination with the insulating resin composition of the present invention.
The epoxy resin curing agent is not particularly limited as long as it has a curing action of epoxy resin, but examples include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyandiamide, Examples thereof include phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac resin. Among these, dicyandiamide, cresol novolak, and aminotriazine novolak are preferable from the viewpoints of curability and low thermal expansion, and dicyandiamide and aminotriazine novolak resin are particularly preferable because flame retardancy and adhesion are improved. The epoxy resin curing agent can be used alone or in combination of two or more.
Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.

  The insulating resin composition of the present invention can further contain a compound (E) that can be chemically roughened. The chemical roughening compound (E) is not particularly limited as long as it is a compound that forms a fine roughened shape on the surface of the insulating resin layer to be described later by desmear treatment, but is preferably a crosslinked rubber particle or a polyvinyl acetal resin. Preferably, it is a crosslinked rubber particle.

Examples of the crosslinked rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles.
The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).

Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N [above, trade name, manufactured by Ganz Kasei Co., Ltd.], Metabrene KW-4426 [trade name, manufactured by Mitsubishi Rayon Co., Ltd.], EXL-2655 [Product Name: manufactured by Rohm and Haas Co., Ltd.).
Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation).
Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 [average particle size 0.5 μm, manufactured by JSR Corporation].
Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) [manufactured by Mitsubishi Rayon Co., Ltd.].
The crosslinked rubber particles may be used alone or in combination of two or more.

  The average particle size of the crosslinked rubber particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the crosslinked rubber particles can be measured using a dynamic light scattering method. For example, the crosslinked rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, and the particle size distribution of the rubber particles is measured on a mass basis using a concentrated particle size analyzer [FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.]. It is measured by making the median diameter as an average particle diameter.

  As a polyvinyl acetal resin, the kind, the amount of hydroxyl groups, and the amount of acetyl groups are not particularly limited, but those having a number average polymerization degree of 1000 to 2500 are preferred. Within this range, solder heat resistance can be secured, and the viscosity and handling properties of the varnish are good. Here, the number average degree of polymerization of the polyvinyl acetal resin can be determined, for example, from the number average molecular weight of polyvinyl acetate as a raw material (measured using a standard polystyrene calibration curve by gel permeation chromatography). Moreover, a carboxylic acid modified product etc. can also be used.

As a polyvinyl acetal resin, for example, Sekisui Chemical Co., Ltd. trade name, ESREC BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z , KS-5, KS-5Z, KS-8, KS-23Z, trade names manufactured by Denki Kagaku Kogyo Co., Ltd., and electrified butyral 4000-2, 5000A, 6000C, 6000EP.
Polyvinyl acetal resins can be used alone or in admixture of two or more.

The insulating resin composition according to the present invention has the following mass parts per 100 mass parts of the total amount of components (A) to (D) in terms of solid content (hereinafter, these components are also referred to as resin components). It is preferable.
The content of the curing agent (A) is preferably 20 to 95 parts by mass, and more preferably 40 to 90 parts by mass. By setting the component (A) to 20 parts by mass or more, flame retardancy, heat resistance, adhesiveness and dielectric properties are improved.
The content of the epoxy resin (B) is preferably 5 to 80 parts by mass, and more preferably 5 to 60 parts by mass. When the component (B) is 5 parts by mass or more, heat resistance and adhesiveness are improved, and when it is 80 parts by mass or less, a low thermal expansion coefficient is satisfied.

  The phosphorus atom content derived from the phosphorus-containing compound (C) is preferably 0.5 to 2.0 parts by mass per 100 parts by mass of the resin component. When the phosphorus atom content is 0.5 parts by mass or more, flame retardancy is improved. When the content is 2.0% by mass or less, it is possible to obtain an improvement in glass transition temperature (Tg) due to the characteristics of the flame retardant, a reduction in thermal expansion coefficient, and an improvement in adhesive strength with the conductor layer. From the viewpoint of thermal expansion coefficient and heat resistance, the phosphorus atom content is more preferably 0.7 to 1.5 parts by mass.

  The content of the epoxy resin curing agent and / or curing accelerator (D) is preferably 0 to 50 parts by mass, and more preferably 0 to 30 parts by mass. By adding the component (D), the heat resistance becomes high with low thermal expansion, and when it is 50 parts by mass or less, a thermosetting insulating resin composition having high reliability can be obtained.

  The content of the compound (E) that can be chemically roughened is preferably 0.5 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass. By setting the content of the compound capable of chemical roughening to 0.5 parts by mass or more, the adhesive strength between the insulating resin layer and the conductor layer is increased, and by setting the content to 5 parts by mass or less, the insulation reliability between wirings is increased. It will not be insufficient.

  In the insulating resin composition of the present invention, it is preferable to contain an inorganic filler (F) in order to reduce the thermal expansion coefficient of the insulating resin layer. Examples of the inorganic filler (F) include silica, mica, talc, short glass fiber or fine powder and hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, magnesium hydroxide, and the like. Among these, silica, aluminum hydroxide, and magnesium hydroxide are preferable from the viewpoint of dielectric properties, heat resistance, and flame retardancy, and silica and aluminum hydroxide are more preferable because of low thermal expansion. Moreover, in order to embed a lower wiring layer, the insulating film with a support for a multilayer printed wiring board is required to have high fluidity. Therefore, it is desirable from the viewpoint of fluidity that the inorganic filler is spherical.

It is preferable that content of an inorganic filler (F) is 10-65 mass parts with respect to 100 mass parts of resin component total amount, More preferably, it is 20-55 mass parts. By making the inorganic filler 10 parts by mass or more, the low thermal expansion coefficient of the insulating resin layer after curing is lowered. In addition, by setting the inorganic filler to 65 parts by mass or less, the insulating resin layer does not become brittle and cracks do not occur in a temperature cycle test or the like.
These inorganic fillers can be treated with a coupling agent in order to increase dispersibility, and the inorganic filler can be dispersed by a known kneading method such as a kneader, a ball mill, a bead mill, or a three roll.
The average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.5 μm or less, considering that the miniaturization of wiring is advanced. By setting the thickness to 1 μm or less, the surface unevenness after the desmear process described later is reduced, so that no etching residue occurs and the insulating property is not insufficient. The average particle diameter is a 50% cumulative diameter (Median diameter) measured by using a particle size distribution measuring device (MT3300EXII manufactured by Nikkiso).

Furthermore, in the insulating resin composition of the present invention, any known thermoplastic resin, elastomer, flame retardant, filler, etc. can be used in combination as long as the effects of the present invention are not impaired.
Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin. .
Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.
Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide.
Examples of the filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  Arbitrary addition of an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightening agent, an adhesion improver and the like is also possible with respect to the insulating resin composition of the present invention, and is not particularly limited. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.

  In the insulating resin composition used for the insulating film with support and the prepreg of the present invention, an organic solvent can be arbitrarily used as a diluting solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, and aromatic solvents such as toluene, xylene, and mesitylene. Examples of the solvent include one type or a mixture of two or more types.

  The insulating resin composition of the present invention can be suitably used for forming an insulating resin layer in the production of a multilayer printed wiring board. Although the insulating resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating resin layer, it is generally industrially in the form of a sheet-like laminated material such as an insulating film with a support, a prepreg, etc. Is preferably used.

  The insulating film with a support of the present invention is such that a semi-cured film of an insulating resin composition is formed on the surface of the support. (A), (B) and an insulating resin composition in which (C) components are blended, or further an insulating resin composition to which components (D) to (F) are added is applied to a support film, and dried in a varnish. The insulating resin composition layer can be formed by volatilizing the solvent and semi-curing (B-stage). However, this semi-cured state is a state in which the adhesive strength between the insulating resin layer and the circuit pattern substrate forming the insulating resin layer is ensured when the insulating resin composition is cured, and the embedding property (fluidity) of the circuit pattern substrate is ensured. ) Is desirable. As a coating method (coating machine), a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and it is appropriately used depending on the thickness of the insulating resin layer. As a drying method, heating, hot air blowing, or the like can be used.

  The drying conditions after applying the insulating resin composition to the support film are not particularly limited, but the content of the organic solvent in the insulating resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Let dry. Depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, the insulating resin composition layer becomes It is formed. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  The thickness of the insulating resin composition layer formed in the insulating film with support is usually not less than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer is preferably 5 to 70 μm, more preferably 5 to 50 μm, and most preferably 5 to 30 μm in order to reduce the thickness of the printed wiring board.

  The support in the insulating film with the support is made of polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and the like. Examples of the film include metal foil such as release paper, copper foil, and aluminum foil. In addition, you may give a mold release process to a support body and the protective film mentioned later other than a mat | matte process and a corona treatment.

Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable, More preferably, it is 25-50 micrometers. A protective film according to the support can be further laminated on the surface of the insulating resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, foreign matter can be prevented from being mixed.
The insulating film with a support can be wound and stored in a roll shape.

  As a form of the method of forming a laminated board using the insulating film with a support of the present invention and producing a multilayer printed wiring board, for example, the insulating film with a support is used on one side or both sides of a circuit board using a vacuum laminator. Laminate. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Further, in a laminated board obtained by alternately laminating conductor layers and insulating layers, and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned ( Circuits) are also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

  In the above laminate, when the insulating film with a support has a protective film, after removing the protective film, the insulating film with a support and the circuit board are preheated as necessary, Crimp to circuit board while pressing and heating. In the insulating film with a support of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the air pressure is 20 mmHg (26.7 hPa). Lamination is preferably performed under the following reduced pressure. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the insulating film with the support on the circuit board, after cooling to near room temperature, the support can be peeled off and then thermally cured to form an insulating resin layer on the circuit board. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the insulating resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to It is selected in the range of 30 to 120 minutes at 200 ° C.

  If the support is not peeled off after the insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

  Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin composition layer is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid. Roughening treatment is performed with an oxidizing agent such as to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.

  The prepreg of the present invention is a fiber sheet-like reinforcing base impregnated with an insulating resin composition, and the fiber sheet-like reinforcing base is impregnated with a hot melt method or a solvent method. After that, it is manufactured by heating to B stage.

  As the fiber sheet reinforcing substrate, for example, known materials used for various types of laminated sheets for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof. These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.

  The above hot-melt method is a method in which the resin is once coated on a coated paper having good releasability from the resin without dissolving the resin in the organic solvent, and then laminated on the sheet-like reinforcing substrate, or the resin is added to the organic solvent. In this method, the prepreg is produced by, for example, coating directly on a sheet-like reinforcing substrate with a die coater without being dissolved in the substrate. In the solvent method, the resin is dissolved in an organic solvent in the same manner as the insulating film with a support to prepare a resin varnish, the sheet-like reinforcing base material is immersed in the varnish, and the sheet-like reinforcing base material is impregnated with the resin varnish. And then drying.

  Next, as a method for producing a laminate using the prepreg produced as described above, for example, one or several prepregs of the present invention are laminated on a circuit board, and a metal plate is interposed through a release film. Press and laminate under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 0.5 to 4 MPa and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the insulating film with support, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. The obtained laminate can then be used to produce a multilayer printed wiring board by roughening the cured prepreg surface in the same manner as described above, and then forming a conductor layer by plating.

Next, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these descriptions.
In addition, the performance of the insulating resin layer and the copper-clad laminate of the insulating film with support obtained in each Example and Comparative Example was measured and evaluated by the following method.

(1) Glass transition temperature (Tg) and coefficient of thermal expansion The insulating resin layer of the insulating film with support is laminated facing the copper foil [F3-WS-18, trade name, manufactured by Furukawa Circuit Foil Co., Ltd.]. The PET film was peeled off and cured at 180 ° C. for 90 minutes. Thereafter, the entire surface of the copper foil was etched to prepare a sample for evaluating the thermal expansion coefficient of the cured insulating resin layer.
The obtained sheet-like cured product was cut into a length of 20 mm and a width of 3 mm, and using a TMA test apparatus [manufactured by DuPont, TMA2940], the heating rate was 10 ° C./min, the measurement length was 15 mm, and the weight was 5 g. The measurement was performed twice in succession by the tensile load method. The glass transition temperature (Tg) in the second measurement and the average linear thermal expansion coefficient from 30 to 120 ° C. were calculated.

(2) Plating adhesion strength Both sides of glass cloth base epoxy resin double-sided copper-clad laminate [manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-679F, copper foil thickness: 12 μm] made by MEC The roughening process was performed using "CZ8100" (brand name).
The insulating film with a support was laminated on both surfaces of the circuit board that had been roughened as described above. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at a pressure of 0.5 MPa for 30 seconds.
The PET film was peeled from the laminated insulating film with a support, and the insulating resin composition layer was cured under curing conditions at 180 ° C. for 60 minutes to form an insulating resin layer.
Next, fine irregularities were formed on the surface of the insulating resin layer by immersing the laminate in a desmear treatment liquid. Plating by a semi-additive method, and immersing the laminate in a copper etchant to form a 3 mm wide plated copper foil to produce an evaluation board, autograph [Shimadzu Corporation, AG-100C] The plating adhesion strength was measured.

(3) Solder heat resistance A 5 cm square evaluation board from which the copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared and 121 ° C. using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. After performing the pressure-cooker treatment for up to 4 hours under the condition of 2 atm, the evaluation substrate was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance.

(4) Heat resistance with copper (T-288)
By producing a 5 mm square evaluation substrate from a copper clad laminate and measuring the time until the evaluation substrate bulges at 288 ° C. by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). evaluated.

(5) Hygroscopicity (water absorption rate)
A copper-clad laminate was immersed in a copper etching solution to produce an evaluation substrate from which the copper foil was removed, and pressure was applied for up to 4 hours under the conditions of 121 ° C. and 2 atm using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. -After the cooker treatment, the water absorption rate of the evaluation substrate was measured.

(6) Flame Retardancy Evaluation A test piece cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).

Production Example 1: Production of curing agent (A-1) In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, o-tolidine: 35.80 g Bis (4-maleimidophenyl) methane: 469.50 g, p-aminophenol: 35.70 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours to form a biphenyl skeleton in the molecular main chain. And a solution of a curing agent (A-1) having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 2: Production of curing agent (A-2) 3,3′-dihydroxy-4 was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. , 4′-diaminobiphenyl: 23.10 g, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane: 463.60 g, aniline: 20.30 g, and dimethylacetamide: 360.00 g The solution was reacted at 100 ° C. for 2 hours to obtain a solution of a curing agent (A-2) having an acidic substituent and an unsaturated N-substituted maleimide group.

Production Example 3: Production of curing agent (A-3) 3,3′-dihydroxy-4 was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. , 4′-diaminobiphenyl: 42.90 g, bis (4-maleimidophenyl) sulfone: 453.90 g, p-aminophenol: 43.20 g, and dimethylacetamide: 360.00 g were added at 100 ° C. for 2 hours. By reacting, a solution of a curing agent (A-3) having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 4: Production of Curing Agent (A-4) In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, o-tolidine: 45.20 g , M-phenylenebismaleimide: 449.10 g, p-aminophenol: 45.70 g, and dimethylacetamide: 360.00 g were reacted at 100 ° C. for 2 hours to react with an acidic substituent and an unsaturated N-substituted maleimide. A solution of a curing agent (A-4) having a group was obtained.

Production Example 5 Production of Curing Agent (A-5) In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 4,4′-bis (4 -Aminophenoxy) biphenyl: 38.60 g, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane: 478.50 g, p-aminophenol: 22.90 g, and propylene glycol monomethyl ether: 360.00 g was added and reacted at reflux temperature for 2 hours to obtain a solution of a curing agent (A-5) having an acidic substituent and an unsaturated N-substituted maleimide group.

Production Example 6 Production of Curing Agent (A-6) In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 4,4′-bis (4 -Aminophenoxy) biphenyl: 69.10 g, bis (4-maleimidophenyl) sulfone: 429.90 g, p-aminophenol: 41.00 g, and propylene glycol monomethyl ether: 360.00 g were added at reflux temperature. It was made to react for time, and the solution of the hardening | curing agent (A-6) which has an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 7: Production of curing agent (A-7)
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 2,2′-dimethyl-4,4′-diaminobiphenyl: 32.20 g, 3 , 3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide: 475.20 g, p-aminophenol: 32.60 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours. Thus, a solution of a curing agent (A-7) having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 8: Production of curing agent (A-8)
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, o-dianisidine: 36.70 g and 3,3-dimethyl-5,5-diethyl- 4,4-Diphenylmethane bismaleimide: 471.10 g, p-aminophenol: 32.20 g, and dimethylacetamide: 360.00 g were added, and reacted at 100 ° C. for 2 hours to give an acidic substituent and an unsaturated N-substitution. A solution of a curing agent (A-8) having a maleimide group was obtained.

Production Example 9: Production of curing agent (A-9) Bis (4-aminophenyl) sulfone was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 26.40 g, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g, It was made to react at 140 degreeC for 5 hours, and the solution of the hardening | curing agent (A-9) which has an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 10: Production of curing agent (A-10)
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, bis (4-aminophenyl) sulfone: 40.20 g and bis (4-maleimidophenyl) Methane: 464.40 g, p-aminophenol: 35.40 g, and dimethylacetamide: 360.00 g are added and reacted at 100 ° C. for 4 hours to have an acidic substituent and an unsaturated N-substituted maleimide group. A solution of (A-10) was obtained.

Production Example 11 Production of Curing Agent (A-11) Bis (4-aminophenyl) sulfide was added to a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 43.40 g, 4-methyl-1,3-phenylenebismaleimide: 452.90 g, p-aminophenol: 43.70 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours. A solution of a curing agent (A-11) having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 12 Production of Curing Agent (A-12) In a reaction vessel having a thermometer, a stirrer, a moisture meter with a reflux condenser and a heat-coolable volume of 2 liters, bis [4- (4-amino] Phenoxy) phenyl] sulfone: 44.80 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 472.60 g, p-aminophenol: 22.60 g, and propylene glycol monomethyl ether: 360 0.000 g was added and reacted at reflux temperature for 2 hours to obtain a solution of a curing agent (A-12) having an acidic substituent and an unsaturated N-substituted maleimide group.

Production Example 13 Production of Curing Agent (A-13) Bis [4- (4-amino] was placed in a 2 liter reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser and capable of heating and cooling. Phenoxy) phenyl] sulfone: 66.30 g, polyphenylmethanemaleimide: 440.30 g, p-aminophenol: 33.40 g, and propylene glycol monomethyl ether: 360.00 g were allowed to react at reflux temperature for 2 hours. A solution of a curing agent (A-13) having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 14 Production of Curing Agent (A-14) A reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, was charged with bis [4- (4-amino]. Phenoxy) phenyl] sulfone: 79.40 g, bis (4-maleimidophenyl) sulfone: 420.50 g, p-aminophenol: 40.10 g, and propylene glycol monomethyl ether: 360.00 g were added at reflux temperature. By reacting for a time, a solution of a curing agent (A-14) having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 15: Production of curing agent (A-15) In a reaction vessel with a volume of 2 liters capable of being heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, o-tolidine sulfone: 44.10 g And bis (4-maleimidophenyl) methane: 460.80 g, p-aminophenol: 35.10 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours to give an acidic substituent and unsaturated group A solution of a curing agent (A-15) having an N-substituted maleimide group was obtained.

Production Example 16: Production of curing agent (A-16) Bis (4-maleimidophenyl) methane was placed in a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 358.00 g, m-aminophenol: 54.50 g, and propylene glycol monomethyl ether: 412.50 g were added and reacted for 5 hours while refluxing to obtain a solution of the curing agent (A-16).

Production Example 17 Production of Curing Agent (A-17) Bis (4-maleimidophenyl) methane was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 358.00 g, p-aminophenol: 54.50 g, and propylene glycol monomethyl ether: 412.50 g were added and reacted for 5 hours while refluxing to obtain a solution of a curing agent (A-17).

Production Example 18: Production of curing agent (A-18) 2,2′-bis [4] was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. -(4-Maleimidophenoxy) phenyl] propane: 358.00 g, p-aminophenol: 34.23 g, and propylene glycol monomethyl ether: 392.23 g were added and reacted for 5 hours while refluxing to cure the curing agent (A- 18) was obtained.

Production Example 19 Production of Curing Agent (A-19) Polyphenylmethanemaleimide: 358.0 g in a reaction vessel with a volume of 2 liters that can be heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. And p-aminophenol: 54.50 g and propylene glycol monomethyl ether: 412.50 g were added and reacted for 5 hours under reflux to obtain a solution of a curing agent (A-19).

Production Example 20 Production of Curing Agent (A-20) Bis (4-maleimidophenyl) sulfone was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 408.00 g, p-aminophenol: 54.50 g, and dimethylacetamide: 462.50 g were added and reacted at 100 ° C. for 2 hours to obtain a solution of a curing agent (A-20).

Production Example 21 Production of Curing Agent (A-21) Bis (4-maleimidophenyl) ether was added to a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 360.00 g, p-aminophenol: 54.50 g, and dimethylacetamide: 414.50 g were added and reacted at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-21).

Production Comparative Example 1 Production of Curing Agent (A-22) With reference to the example of JP-B 63-34899, a kneader having a volume of 1 liter equipped with a steam heating device was charged with bis (4-maleimidophenyl) methane: 358. 0.000 g and m-aminophenol: 54.50 g, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled and pulverized to have a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A-22 ) Was obtained.

Production Comparative Example 2: Production of Curing Agent (A-23) With reference to the example of JP-B-6-8342, a kneader having a volume of 1 liter equipped with a steam heating device, bis (4-maleimidophenyl) methane: 358 0.000 g and m-aminobenzoic acid: 68.50 g, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, pulverized, and a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A- 23) powder was obtained.

Production Comparative Example 3: Production of Curing Agent (A-24) Diaminodiphenylmethane: 32.60 g and bis (4 -Maleimidophenyl) Methane: 471.50 g, p-aminophenol: 35.90 g, and dimethylacetamide: 360.00 g were added and reacted at 100 ° C. for 2 hours to convert acidic substituents and unsaturated N-substituted maleimide groups. A solution of the curing agent (A-24) was obtained.

Production Comparative Example 4: Production of Curing Agent (A-25) 2,2′-Bis [4- (4) was added to a 2 liter reaction vessel with a thermometer, a stirrer, and a reflux condenser and a heatable and coolable reaction vessel. -Aminophenoxy) phenyl] propane: 63.40 g, bis (4-maleimidophenyl) methane: 471.20 g, p-aminophenol: 33.70 g, and dimethylacetamide: 360.00 g. It was made to react for time, and the solution of the hardening | curing agent (A-25) which has an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Comparative Example 5: Production of curing agent (A-26) Bis (4-maleimidophenyl) methane: 358.00 g and m-aminophenol: 54.50 g were placed in a 1 liter kneader equipped with a steam heating device. Then, the mixture was heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, and pulverized to obtain a powder of a curing agent (A-26) having an N-substituted maleimide group and an acidic substituent.

Production Comparative Example 6: Production of curing agent (A-27) Bis (4-maleimidophenyl) methane: 358.00 g and m-aminobenzoic acid: 68.50 g were added to a 1 liter kneader equipped with a steam heating device. The mixture was heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, and pulverized to obtain a powder of a curing agent (A-27) having an N-substituted maleimide group and an acidic substituent.

Examples 1-31 and Comparative Examples 1-12
Using methyl ethyl ketone as a diluent solvent, the following components were mixed in the blending ratios (parts by mass) shown in Tables 1 to 7 to prepare a uniform insulating resin composition varnish having a resin content of 65% by mass.
That is,
(1) As the compound A having an acidic substituent and an unsaturated N-substituted maleimide group, Examples 1 to 31 used the curing agents obtained in Production Examples 1 to 21. Moreover, in the comparative examples 1-10, the hardening | curing agent which has the acidic substituent obtained by manufacture comparative examples 1-6 and the unsaturated N-substituted maleimide group was used.
(2) As epoxy resin (B), bifunctional naphthalene type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name, HP-4032D], naphthol aralkyl type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name : ESN-175] bifunctional naphthalene aralkyl type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: ESN-375], biphenyl type epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade name: YX-4000], Biphenyl aralkyl type epoxy resin [Nippon Kayaku Co., Ltd., brand name: NC-3000H], anthracene type epoxy resin [Japan Epoxy Resin Co., Ltd., brand name: YX-8800] were used.
(3) As phosphorus-containing compound (C) that imparts flame retardancy, phosphorus-containing epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: Epototo ZX-1548-3, phosphorus content 3 mass%], phosphorus-containing phenol Resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content 9.6% by mass], condensed phosphate compound [Eighth Chemical Industry Co., Ltd., trade name: PX-200, containing phosphorus Amount 9% by mass], aluminum dialkylphosphinic acid [manufactured by Clariant Co., Ltd., trade name: OP-930, phosphorus content 3.5% by mass].
(4) As an epoxy resin curing agent of component (D), aminotriazine novolak resin [Dainippon Ink Chemical Co., Ltd., trade name: LA-3018], benzoguanamine [manufactured by Nippon Shokubai Co., Ltd.], dicyandiamide [Daiei] Chemical Industry Co., Ltd.] was used. As a curing accelerator, an imidazole derivative [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L] was used.
(5) Cross-linked acrylonitrile butadiene rubber (NBR) particles: XER-91 [manufactured by JSR Co., Ltd.], core-shell type rubber particles: Staphyloid AC3832 [trade name, Gantz Kasei Co., Ltd.] )] And polyvinyl acetal resin: KS-23Z [trade name, manufactured by Sekisui Chemical Co., Ltd.].
(6) As the inorganic filler (F), fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC], aluminum hydroxide [manufactured by Showa Denko KK, trade name: HP-360] was used.

Next, the insulating resin composition varnish was uniformly coated on a polyethylene terephthalate film (thickness 38 μm, hereinafter referred to as PET film) with a die coater so that the thickness of the insulating resin composition layer after drying was 40 μm. And dried at 100 ° C. for 6 minutes. Subsequently, it wound up in roll shape, bonding the 15-micrometer-thick polypropylene film on the surface of the insulating resin composition layer. The obtained roll-shaped film was slit to a width of 507 mm to produce a sheet-like insulating film with a support having a size of 507 × 336 mm.
Moreover, the insulating resin composition varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 50% by mass. Next, four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
With respect to the insulating resin layer and the copper-clad laminate of the insulating film with support thus produced, the performance was measured and evaluated by the method described above. The results are shown in Tables 1-7.

As is apparent from Tables 1 to 5, the insulating resin compositions of the examples according to the present invention have a low thermal expansion coefficient of 25 to 40 ppm / ° C. and a glass transition temperature (Tg). The heat resistance is high as 210 to 270 ° C., and the plating adhesion strength is also higher than that of the comparative example. Moreover, it is excellent in all of heat resistance with copper (T-288), moisture resistance, and flame retardancy, is well balanced, and has high reliability.
On the other hand, as is apparent from Tables 6 to 7, the insulating resin composition of the comparative example has a glass transition temperature (Tg) of 140 to 210 ° C and a thermal expansion coefficient of 39 to 52 ppm / ° C. Moreover, it is inferior to any one of plating adhesion strength, solder heat resistance, heat resistance with copper (T-288), moisture resistance, and flame retardancy, and its reliability is low.

Claims (9)

It is produced by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule and an amine compound (b) having an acidic substituent represented by the general formula (I) in an organic solvent. A curing agent (A) having an N-substituted maleimide group and an acidic substituent, an epoxy resin (B) having at least two epoxy groups in one molecule, and a phosphorus-containing compound (C) imparting flame retardancy The thermosetting insulating resin composition characterized by the above-mentioned.

(R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and R ₂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, (x is an integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5)   Furthermore, the thermosetting insulating resin composition of Claim 1 containing the hardening | curing agent and / or hardening accelerator (D) of the said epoxy resin.   Furthermore, the thermosetting insulating resin composition of Claim 1 or 2 containing the compound (E) which can be chemically roughened.   The phosphorus atom content derived from the phosphorus-containing compound (C) that imparts flame retardancy to 100 parts by mass of the total amount of components (A) to (D) in terms of solids is 0.5 to 2.0 parts by mass. The thermosetting insulating resin composition according to any one of claims 1 to 3.   Thermosetting insulation in any one of Claims 1-4 containing 10-65 mass parts inorganic filler (F) with respect to 100 mass parts of total amounts of (A)-(D) component of solid substance conversion. Resin composition.   A semi-cured film of the thermosetting insulating resin composition according to any one of claims 1 to 5 is formed on the surface of the support.   A prepreg characterized in that the thermosetting insulating resin composition according to any one of claims 1 to 5 is impregnated in a sheet-like reinforcing base material comprising fibers.   The insulating resin layer is (1) the thermosetting insulating resin composition according to any one of claims 1 to 5, (2) the insulating film with a support according to claim 6, and (3) the claim 7. A laminate formed by using any of the prepregs.   A multilayer printed wiring board produced by using the laminated board according to claim 8.