JP2009114377A - Method of preparing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of preparing a uniform resin composition having low viscosity and to provide a prepreg or an insulating resin sheet free from color unevenness or aggregate using the resin composition obtained by the preparing method. <P>SOLUTION: The method of preparing the resin composition includes: a step (1) of dissolving or dispersing a coloring agent (B) in a fluid dispersion prepared by dispersing inorganic filler (A) in a solvent; and after that, a step (2) of dissolving a novolac type epoxy resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing a resin composition.

In recent years, the multilayer printed wiring board is required to have various characteristics as electric and electronic devices become smaller and thinner.
For example, multilayer printed wiring boards used for applications such as semiconductor mounting packages are mainly based on black. As one of techniques for making a multilayer printed wiring board black, a technique of blending a black organic colorant or the like with a resin composition used for manufacturing a multilayer printed wiring board is known.
However, since these organic colorants generally have low solubility in organic solvents, there is a problem that the resin composition used for the production of the multilayer printed wiring board cannot be made into a uniform color.
Therefore, the prepreg or the insulating resin sheet using the resin composition containing the organic colorant has a problem that aggregates and unevenness are generated in appearance.
In addition, with the recent reduction in size and thickness of electric and electronic devices, the prepreg or the insulating resin sheet becomes thinner, and thus aggregates and unevenness appear more noticeably in the appearance.
JP 2001-163969 A

    The present invention provides a method for producing a low-viscosity and uniform resin composition, comprising a resin composition obtained by the production method of the present invention, and a prepreg or insulation having no color unevenness and aggregates. A resin sheet is provided.

Such an object is achieved by the following [1] to [7].
[1] (A) Step (1) of dissolving and / or dispersing (B) colorant in a dispersion in which an inorganic filler is dispersed in a solvent, and then (C) step of dissolving a novolac type epoxy resin. The manufacturing method of the resin composition characterized by including (2).
[2] The method for producing a resin composition according to [1], wherein the step (1) is a step of dispersing by stirring at a peripheral speed of 3 m / sec or more.
[3] The content of the colorant (B) in the resin composition according to [1] or [2] is 0.5 to 6.5 parts by weight with respect to 100 parts by weight of the (A) inorganic filler. Production method.
[4] The method for producing a resin composition according to any one of [1] to [3], wherein the colorant (B) has a weight loss due to sublimation or decomposition at 260 ° C. of 10% or less.
[5] The method for producing a resin composition according to any one of [1] to [4], wherein the (B) colorant is a compound having an anthraquinone structure.
[6] The inorganic filler (A) is at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, silica, talc, calcined talc, and alumina. The manufacturing method of the resin composition in any one.
[7] The content of the solvent used in the step (1) is 25 to 300 parts by weight with respect to 100 parts by weight of the inorganic filler. [1] The resin composition according to any one of [6] Production method.

The resin composition obtained by the production method of the present invention has a low viscosity and is uniform, and the resin composition obtained by the production method of the present invention is a glass fiber substrate, synthetic fiber substrate, organic fiber substrate, or the like. The prepreg impregnated in the base material is an insulating resin sheet that is free from unevenness and agglomerates in appearance, or has an insulating resin layer made of the resin composition formed on a metal foil or film. Also, there are no irregularities or aggregates in the appearance.
Therefore, the multilayer printed wiring board manufactured using the prepreg and / or the insulating resin sheet is excellent in reliability with no color unevenness and aggregates in appearance.

Hereinafter, the manufacturing method of the resin composition of this invention is demonstrated.
The method for producing a resin composition of the present invention comprises (A) a step (1) of dissolving and / or dispersing a colorant in a dispersion obtained by dispersing an inorganic filler in a solvent, and then (C) It includes a step (2) of dissolving a novolac type epoxy resin. By including the steps (1) and (2), the colorant can be uniformly dispersed in the resin composition, and the prepreg produced using the resin composition obtained by the production method of the present invention The insulating resin sheet is free from unevenness and aggregates in appearance. Moreover, since a coloring agent disperse | distributes easily, there exists an advantage which can shorten the manufacturing process time of a resin composition.

Although the said process (1) is not specifically limited, For example, it can disperse | distribute with various stirring apparatuses, such as a three roll, a ball mill, an ultrasonic disperser, a disperser stirrer, and a vacuum defoaming kneading apparatus. Among these, it is preferable to use a disperser stirrer.

In the step (1), stirring is preferably performed at a peripheral speed of 3 m / sec or more. If it is performed at a speed lower than the above, dispersion may be insufficient.
The peripheral speed can be obtained by ((stirring blade width × 3.14 (circumferential ratio)) / (time required for the blade to make one round).

Although the said process (2) is not specifically limited, For example, it can carry out with apparatuses, such as a three roll, a ball mill, an ultrasonic disperser, and various mixers. Among these, it is preferable to use a disperser stirrer.

The solvent used in the method for producing the resin composition is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, amide solvents such as dimethylacetamide, dimethylformamide, toluene, ethyl acetate, cyclohexane , Heptane, cyclohexane, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, and anisole. Among these, ketone solvents and amide solvents can disperse the colorant (B) more uniformly. Moreover, it is preferable at the point that there is little reactivity with a thermosetting resin. Also, one of these can be used alone, or two or more can be used in combination.

The content of the solvent is preferably 25 to 300 parts by weight, more preferably 40 to 100 parts by weight with respect to 100 parts by weight of the (A) inorganic filler. When it is lower than the above range, the dispersibility of the resin and the inorganic filler may be deteriorated, and when it is higher than the above range, appearance unevenness may be generated when an insulating resin sheet or prepreg is produced.

The (A) inorganic filler used in the present invention is not particularly limited, and examples thereof include silicates such as talc, fired talc, fired clay, unfired clay, mica, and glass, titanium oxide, alumina, silica, and fused silica. Oxides, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, Borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride, carbon nitride, strontium titanate, barium titanate, etc. A titanate etc. can be mentioned. As the inorganic filler, one of these can be used alone, or two or more can be used in combination. Among these, magnesium hydroxide, aluminum hydroxide, silica, fused silica, talc, calcined talc, and alumina are preferable, and fused silica is particularly preferable in terms of excellent low thermal expansion. Although the shape is crushed or spherical, it is preferable to use spherical silica in order to lower the melt viscosity of the resin composition in order to ensure the impregnation of the base material during prepreg production.

  The inorganic filler (A) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can be used, and an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination.

The average particle diameter of the (A) inorganic filler is not particularly limited, but is preferably 0.005 to 10 μm, particularly preferably 0.01 to 2 μm. If the particle size of the inorganic filler is less than the lower limit, the viscosity of the varnish becomes high, which may affect the workability during prepreg production. When the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the varnish.
Furthermore, spherical silica having an average particle diameter of 5.0 μm or less is preferable, and spherical fused silica having an average particle diameter of 0.01 to 2 μm is particularly preferable. Thereby, the filling property of an inorganic filler can be improved. The average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by HORIBA, LA-500).

Although content of the said (A) inorganic filler is not specifically limited, 20 to 80 weight% of the whole resin composition is preferable, and 30 to 75 weight% is especially preferable. When the content is within the above range, particularly low thermal expansion and low water absorption can be achieved.

Next, the colorant (B) used in the method for producing the resin composition will be described.

(B) The colorant is not particularly limited, and examples thereof include carbon pigments such as carbon black and split black, azo metal complex black dyes, and organic black dyes. As the colorant, one of these can be used alone, or two or more can be used in combination.

Among these, organic black dyes are preferable in terms of reliability tests such as insulation reliability tests and ionic impurities, and those having a weight loss of 10% or less due to sublimation or decomposition at 260 ° C. are particularly heat resistant. It is preferable in terms. Thereby, it becomes excellent in moisture absorption solder heat resistance. Specific examples include Kayset Black A-N (manufactured by Nippon Kayaku Co., Ltd.), Kayase Black G (manufactured by Nippon Kayaku Co., Ltd.), and the like. The weight decrease at 260 ° C. can be confirmed by measuring the weight decrease at 260 ° C. when the sample is heated at 10 ° C./min using a TGA (thermogravimetric measuring device).

The content of the colorant (B) is not particularly limited, but is preferably 0.5 to 6.5 parts by weight, more preferably 0.7 to 5.0 parts by weight with respect to 100 parts by weight of the inorganic filler. It is to contain part. If it is less than the above-mentioned parts by weight, unevenness may occur in the appearance of the resulting multilayer printed wiring board, and if it exceeds the above-mentioned parts by weight, the curability may be lowered.

The (C) novolac type epoxy resin is not particularly limited. For example, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenyl aralkyl type novolac epoxy resin, a naphthalene aralkyl type novolak epoxy resin, a dicyclopentadiene type novolac epoxy resin. Etc. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more and those prepolymers can be used in combination. . Among these, novolak type epoxy having a methylene bond such as biphenyl aralkyl type novolak epoxy resin and naphthalene aralkyl type novolak epoxy resin is excellent in heat resistance, flame retardancy and water absorption, and among them, biphenyl aralkyl type novolak epoxy. Resins are preferred. Thereby, moisture absorption solder heat resistance and a flame retardance improve.

The biphenyl aralkyl type novolak epoxy resin refers to an epoxy resin having one or more biphenyl alkylene groups in a repeating unit. For example, a xylylene type epoxy resin, a biphenyl dimethylene type epoxy resin, etc. are mentioned. Among these, a biphenyl dimethylene type epoxy resin is preferable. The biphenyl dimethylene type epoxy resin can be represented by, for example, the formula (I).

The average repeating unit n of the biphenyldimethylene type epoxy resin represented by the formula (1) is not particularly limited, but is preferably 1 to 10, and particularly preferably 2 to 5. When the average repeating unit n is less than the lower limit, the biphenyldimethylene type epoxy resin is easily crystallized, and the solubility in a general-purpose solvent is relatively lowered, which may make handling difficult. On the other hand, if the average repeating unit n exceeds the upper limit, the fluidity of the resin is lowered, which may cause molding defects.

The content of the (C) novolac type epoxy resin is not particularly limited, but is preferably 1 to 65% by weight, and particularly preferably 5 to 40% by weight, based on the entire first resin composition. If the content is less than the lower limit, the moisture resistance of the resulting product may be reduced, and if it exceeds the upper limit, the heat resistance may be reduced.

Although the weight average molecular weight of the (C) novolac type epoxy resin is not particularly limited, the weight average molecular weight is preferably 5.0 × 10 ^{2 to} 2.0 × 10 ⁴ , particularly 8.0 × 10 ^{2 to} 1.5 ×. 10 ⁴ is preferred. When the weight average molecular weight is less than the lower limit value, tackiness may occur in the prepreg, and when the upper limit value is exceeded, the impregnation property to the base material may be reduced during preparation of the prepreg, and a uniform product may not be obtained. is there.
In addition, the weight average molecular weight of the said (C) novolak-type epoxy resin can be measured by GPC, for example.

The resin composition preferably further disperses a thermosetting resin (substantially free of halogen) in addition to (C) the novolac type epoxy resin. The thermosetting resin is, for example, a resin having a triazine ring such as a urea (urea) resin, a melamine resin, an unsaturated polyester resin, a bismaleimide resin, a polyurethane resin, a diallyl phthalate resin, a silicone resin, a resin having a benzoxazine ring, Examples include cyanate resins.
One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more and those prepolymers can be used in combination. .

Of these, cyanate resins (including prepolymers of cyanate resins) are particularly preferable. Thereby, the thermal expansion coefficient of a prepreg can be made small. Furthermore, the electrical properties (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the prepreg are also excellent.

The cyanate resin can be obtained by, for example, reacting a halogenated cyanide compound with a phenol and prepolymerizing it by a method such as heating as necessary. Specifically, novolak type cyanate resin, cresol novolak type cyanate resin, novolak type cyanate resin such as dicyclopentadiene aralkyl novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin And bisphenol type cyanate resin. Among these, novolak type cyanate resins such as novolak type cyanate resin, cresol novolak type cyanate resin, and dicyclopentadiene aralkyl novolak type cyanate resin are preferable, and novolak type cyanate resin is particularly preferable.

Thereby, a crosslinking density increases and the heat resistance of a multilayer printed wiring board manufactured using the said resin composition and a flame retardance improve. This is because the novolak type cyanate resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate resin has a high benzene ring ratio due to its structure and is easily carbonized. Furthermore, even when the thickness of the prepreg is 0.5 mm or less, excellent rigidity can be imparted to a laminate produced by curing the prepreg. In particular, since the rigidity during heating is excellent, the reliability when mounting a semiconductor element is also excellent.

As the novolac-type cyanate resin, for example, one represented by the formula (2) can be used.

The average repeating unit n of the novolak cyanate resin represented by the formula (2) is not particularly limited, but is preferably 1 to 10, and particularly preferably 2 to 7. When the average repeating unit n is less than the lower limit, the novolac cyanate resin has low heat resistance, and low molecular weight components may be desorbed and volatilized during heating. Moreover, when average repeating unit n exceeds the said upper limit, melt viscosity will become high too much and the moldability of a prepreg may fall.

Although the weight average molecular weight of the cyanate resin is not particularly limited, the weight average molecular weight is preferably 5.0 × 10 ^{2 to} 4.5 × 10 ³ , and particularly preferably 6.0 × 10 ^{2 to} 3.0 × 10 ³ . When the prepreg is produced when the weight average molecular weight is less than the lower limit, tackiness may occur, and when the prepregs come into contact with each other, they may adhere to each other or transfer of the resin may occur. Moreover, when the weight average molecular weight exceeds the above upper limit, the reaction becomes too fast, and when used in the production of a multilayer printed wiring board, molding defects may occur or the interlayer peel strength may be lowered.

The weight average molecular weight of the cyanate resin or the like can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).
In addition, the cyanate resin is not particularly limited, but one kind can be used alone, or two or more kinds having different weight average molecular weights can be used in combination, or one kind or two kinds or more and prepolymers thereof can be used. It can also be used together.

Although content of the said cyanate resin is not specifically limited, 5-42 weight% of the whole said resin composition is preferable, and 10-40 weight% is especially preferable. If the content is less than the lower limit, the coefficient of thermal expansion may increase, and if the content exceeds the upper limit, the moisture resistance may be reduced.

The resin composition preferably further uses a curing agent as necessary. The curing agent is not particularly limited. For example, the compound that reacts with an epoxy group of (C) novolac type epoxy resin such as a phenol resin, the reaction between epoxy groups such as imidazole, or the reaction of a compound that reacts with an epoxy group is promoted. A curing accelerator can be used.

The phenol resin is not particularly limited. For example, a phenol novolak resin, a cresol novolac resin, a bisphenol A novolak resin, an arylalkylene type novolak resin or the like novolak type phenol resin, an unmodified resole phenol resin, tung oil, linseed oil, walnut Examples include resol-type phenol resins such as oil-modified resol phenol resins modified with oil. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination. Among these, arylalkylene type phenol resins are particularly preferable. This further improves the hygroscopic solder heat resistance.

The curing accelerator is not particularly limited, and examples thereof include organic metals such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III). Salt, triethylamine, tributylamine, tertiary amines such as diazabicyclo [2,2,2] octane, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl -5 Imidazoles such as loxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzoic acid Examples thereof include acids, organic acids such as salicylic acid and p-toluenesulfonic acid, and mixtures thereof. One of these can be used alone, including derivatives thereof, or two or more of these can be used in combination.

The resin composition preferably further contains a coupling agent. The coupling agent (C) can improve the wettability of the interface between a resin such as a novolac type epoxy resin and an inorganic filler, and can improve the heat resistance of a multilayer printed wiring board produced from the resin composition, particularly moisture absorption. Later solder heat resistance can be improved.

Although the coupling agent is not particularly limited, for example, one kind selected from an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and a silicone oil type coupling agent. It is preferable to use the above coupling agent. Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.

Although the addition amount of the coupling agent is not particularly limited, it is preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the inorganic filler. If the content is less than the lower limit, the inorganic filler cannot be sufficiently coated, and thus the effect of improving the heat resistance may be reduced. If the content exceeds the upper limit, the reaction is affected, and the bending strength is reduced. There is a case.

The resin composition may further contain a component that improves the adhesion to the conductor circuit layer in the multilayer printed board manufacturing process. For example, a phenoxy resin, a polyvinyl alcohol-based resin, and a coupling agent that improves the adhesion with the metal constituting the conductor layer, and the like are mentioned. Among these, the adhesion is particularly excellent, and the influence on the curing reaction rate is small. A phenoxy resin is preferable at this point. Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a novolak skeleton, a phenoxy resin having a naphthalene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.

Further, the resin composition may further contain additives other than the above components such as an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion scavenger as necessary. good.

(Example)
EXAMPLES Hereinafter, although the manufacturing method of the resin composition of this invention is demonstrated in detail by an Example, this invention is not limited to the following examples, unless the summary is exceeded.

The colorant (B) used in the examples of the present invention is as follows.
B1: Perinone and anthraquinone dyes (trade name Kayase Black A-N (manufactured by Nippon Kayaku Co., Ltd.))
Weight reduction rate at 260 ° C 1.5%
B2: Methine and anthraquinone dye (trade name Kayase Black G (manufactured by Nippon Kayaku Co., Ltd.))
Weight reduction rate at 260 ° C 1.5%
B3: Organic colorant (trade name Sudan Black 141 (manufactured by Chuo Synthetic Chemical))
Weight reduction rate at 260 ° C 4.4%

The weight reduction rate at 260 ° C. of the (B) colorant used was determined by increasing the temperature of the sample from 30 ° C. to 500 ° C. at 10 ° C./min by TG-DTA (simultaneous differential thermothermal weight measurement). The weight change was followed, and a value obtained by ((30 ° C. sample weight) − (300 ° C. sample weight)) / (30 ° C. sample weight) × 100 was obtained.

Example 1
Process (1)
(A) As an inorganic filler, 49.8 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 49.8 parts by weight of methyl ethyl ketone are mixed, and vacuum demulsification kneading is performed. Dispersed with a stirrer. Next, (B) B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight are mixed as a colorant, and a peripheral speed of 4 m / sec is used using a disperser stirrer. Stir for 60 minutes.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 14.0 parts by weight as a (C) novolak type epoxy resin in the dispersion liquid in which (A) inorganic filler and (B) colorant are dispersed. In addition, 24.6 parts by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, and biphenyldimethylene type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851HHH) as a curing agent 10.8 parts by weight and 0.2 parts by weight of a coupling agent (manufactured by Nihon Unicar Co., A187) were added and stirred for 120 minutes using a disperser stirrer to produce a resin composition.

(Example 2)
Process (1)
(A) As an inorganic filler, 59.7 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 59.7 parts by weight of methyl ethyl ketone are mixed, and vacuum demulsion kneading stirring is performed. Dispersed by equipment. Next, (B) B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight are mixed as a colorant, and stirred for 60 minutes with a disperser stirrer at a peripheral speed of 4 m / sec. did.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 11.2 parts by weight as a (C) novolak type epoxy resin in a dispersion in which (A) inorganic filler and (B) colorant are dispersed. 19.6 parts by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, biphenyldimethylene type phenolic resin (MEH-7851HHH, manufactured by Meiwa Kasei Co., Ltd.) as a curing agent 8.6 parts by weight and 0.3 part by weight of a coupling agent (manufactured by Nippon Unicar Company, A187) were added and stirred for 120 minutes using a disperser stirrer to produce a resin composition.

(Example 3)
Process (1)
(A) As an inorganic filler, 49.8 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 49.8 parts by weight of methyl ethyl ketone are mixed, and vacuum demulsification kneading is performed. Dispersed with a stirrer. Next, (B) B2: Methine and 0.6 parts by weight of an anthraquinone organic dye (Kayaset Black G, manufactured by Nippon Kayaku Co., Ltd.) were mixed as colorants, and the mixture was stirred with a disperser stirrer at a peripheral speed of 4 m / sec for 60 minutes.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 11.2 parts by weight as a (C) novolak type epoxy resin in a dispersion in which (A) inorganic filler and (B) colorant are dispersed. 19.6 parts by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, biphenyldimethylene type phenolic resin (MEH-7851HHH, manufactured by Meiwa Kasei Co., Ltd.) as a curing agent 8.6 parts by weight and 0.2 part by weight of a coupling agent (manufactured by Nihon Unicar Co., A187) were added and stirred for 120 minutes using a disperser stirrer to produce a resin composition.

Example 4
Process (1)
(A) As an inorganic filler, 59.7 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 59.7 parts by weight of methyl ethyl ketone are mixed and vacuum-demulsified and kneaded. Dispersed with a stirrer. Next, (B) as a colorant, B1: perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.3 parts by weight are mixed and stirred with a disperser stirrer at a peripheral speed of 4 m / sec for 60 minutes. did.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 11.2 parts by weight as a (C) novolak type epoxy resin in a dispersion in which (A) inorganic filler and (B) colorant are dispersed. In addition, 19.8 parts by weight of novolak-type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, and biphenyldimethylene-type phenol resin (MEH-7851HHH, manufactured by Meiwa Kasei Co., Ltd.) as a curing agent 8.7 parts by weight and 0.3 part by weight of a coupling agent (manufactured by Nihon Unicar Company, A187) were added and stirred for 120 minutes using a disperser stirrer to prepare a resin composition.

(Example 5)
Process (1)
(A) As an inorganic filler, 59.7 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 59.7 parts by weight of methyl ethyl ketone are mixed, and vacuum demulsion kneading and stirring Dispersed by equipment. Next, (B) as a colorant, B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 1.2 parts by weight are mixed and stirred with a disperser stirrer at a peripheral speed of 4 m / sec for 60 minutes. did.

Step (2)
11.0 parts by weight of (C) biphenylaralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) as a novolak type epoxy resin in a dispersion in which (A) inorganic filler and (B) colorant are dispersed. In addition, 19.4 parts by weight of a novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, and biphenyldimethylene type phenolic resin (MEH-7851HHH, manufactured by Meiwa Kasei Co., Ltd.) as a curing agent 8.4 parts by weight and 0.3 part by weight of a coupling agent (manufactured by Nippon Unicar Co., Ltd., A187) were added and stirred for 120 minutes using a high-speed stirrer to produce a resin composition.

(Example 6)
Process (1)
(A) As an inorganic filler, 49.8 parts by weight of aluminum hydroxide (manufactured by Showa Denko KK, H-42M, average particle size 1.1 μm) and 49.8 parts by weight of methyl ethyl ketone are mixed, and a vacuum demulsifying and kneading stirrer Was dispersed. Next, (B) B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight are mixed as a colorant, and stirred for 60 minutes with a disperser stirrer at a peripheral speed of 4 m / sec. did.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 14.0 parts by weight as a (C) novolak type epoxy resin in the dispersion liquid in which (A) inorganic filler and (B) colorant are dispersed. In addition, 24.6 parts by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, and biphenyldimethylene type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851HHH) as a curing agent 10.8 parts by weight and 0.2 parts by weight of a coupling agent (manufactured by Nihon Unicar Co., A187) were added and stirred for 120 minutes using a disperser stirrer to produce a resin composition.

(Example 7)
Process (1)
(A) As an inorganic filler, 49.8 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 49.8 parts by weight of methyl ethyl ketone are mixed, and vacuum demulsification kneading is performed. Dispersed with a stirrer. Next, (B) B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight are mixed as a colorant, and stirred for 60 minutes with a disperser stirrer at a peripheral speed of 3 m / sec. did.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 14.0 parts by weight as a (C) novolak type epoxy resin in the dispersion liquid in which (A) inorganic filler and (B) colorant are dispersed. In addition, 24.6 parts by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, and biphenyldimethylene type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851HHH) as a curing agent 10.8 parts by weight and 0.2 parts by weight of a coupling agent (manufactured by Nihon Unicar Co., A187) were added and stirred for 120 minutes using a disperser stirrer to produce a resin composition.

(Example 8)
Process (1)
(A) As an inorganic filler, 49.8 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., “SO-25R”, average particle size 0.5 μm) and 49.8 parts by weight of methyl ethyl ketone are mixed, and vacuum demulsification kneading is performed. Dispersed with a stirrer. Next, (B) 0.6 part by weight of B3: organic dye (manufactured by Chuo Gosei Chemical Co., Ltd., Sudan Black 141) was mixed as a colorant, and the mixture was stirred with a disperser stirrer at a peripheral speed of 4 m / sec for 60 minutes.

Step (2)
(C) Biphenyl aralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) 14.0 parts by weight as a (C) novolak type epoxy resin in the dispersion liquid in which (A) inorganic filler and (B) colorant are dispersed. In addition, 24.6 parts by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) as other thermosetting resin, and biphenyldimethylene type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851HHH) as a curing agent 10.8 parts by weight and 0.2 parts by weight of a coupling agent (manufactured by Nihon Unicar Co., A187) were added and stirred for 120 minutes using a disperser stirrer to produce a resin composition.

(Comparative Example 1)
(Process 1)
(C) 14.0 parts by weight of a biphenyl aralkyl type novolak epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) as a novolak type epoxy resin, and a novolak type cyanate resin (Lonza Japan Co., Ltd., Primaset PT) as a thermosetting resin -30) 24.6 parts by weight, biphenyldimethylene type phenolic resin (Maywa Kasei Co., Ltd., MEH-7851HHH) 10.8 parts by weight as curing agent, (A) spherical fused silica (manufactured by Admatechs Co., Ltd.) “SO-25R”, average particle diameter 0.5 μm) 49.8 parts by weight, coupling agent (Nihon Unicar Co., Ltd., A187) 0.2 parts by weight, spherical fused silica and methyl ethyl ketone having the same weight were mixed at once. The mixture was stirred for 120 minutes using a disperser stirrer.

(Process 2)
B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 0.6 parts by weight as (B) colorant are added to the dissolved dispersion and stirred for 60 minutes using a disperser stirrer. Thus, a resin composition was obtained.

(Comparative Example 2)
(Process 1)
(B) As a coloring agent, B1: Perinone and anthraquinone organic dye (Nippon Kayaku Co., Ltd., Kayase Black A-N) 1.2 parts by weight and methyl ethyl ketone (MEK) 49.8 parts by weight are mixed, and a high-speed stirring device is used. And stirred for 60 minutes at a peripheral speed of 4 m / sec.

(Process 2)
(C) 28.0 parts by weight of biphenylaralkyl type novolac epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) as the novolak type epoxy resin in the dispersion obtained in the above step 1, and novolak type as the other thermosetting resin 49.2 parts by weight of cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30) and 21.6 parts by weight of biphenyldimethylene type phenol resin (Maywa Kasei Co., Ltd., MEH-7851HHH) as a curing agent are added at high speed. The resin composition was manufactured by stirring for 120 minutes using a stirrer.

The following evaluations were performed on the resin compositions, laminates, and insulating resin sheets of Examples 1 to 8, Comparative Example 1, and Comparative Example 2. The evaluation contents are shown together with the items. The results obtained from Examples 1 to 8 and Comparative Examples 1 and 2 are shown in Table 1.

The evaluation method is as follows.

1. Filtration residue The resin compositions of Examples 1 to 8, Comparative Example 1 and Comparative Example 2 were filtered through 400 mesh, and the presence or absence of residues of inorganic filler, colorant, and other resin components was visually observed. Confirmed.

2. Particle size distribution measurement Using a particle size distribution meter (SALD-7000-WJA1 manufactured by Shimadzu Corporation), particle size distribution measurement of the resin compositions of Examples 1 to 8 and Comparative Example 1 and Comparative Example 2 produced. Went. The measurement was performed under conditions of a refractive index of 1.60 to 0.10i, and an average particle diameter, a 90% particle diameter, and a standard deviation of distribution were calculated in terms of volume.

3. Appearance inspection of prepreg A glass woven fabric (thickness 94 μm, manufactured by Nitto Boseki Co., Ltd., WEA-2116) was impregnated using the resin compositions of Examples 1 to 8 and Comparative Example 1 and Comparative Example 2. And dried in a heating furnace at 150 ° C. for 2 minutes to obtain a prepreg having a varnish solid content of about 50 wt% in the prepreg. About each obtained prepreg, the presence or absence of the external appearance nonuniformity by aggregation of an inorganic filler or an organic compound was confirmed visually.

4). Appearance inspection of insulating resin sheet A comma coater device on one side of a PET (polyethylene terephthalate) film having a thickness of 25 μm using the resin compositions of Examples 1 to 8 and Comparative Example 1 and Comparative Example 2 A resin layer was formed using and dried for 10 minutes with a drying apparatus at 160 ° C. to produce an insulating resin sheet. The resin layer after drying was coated so as to have a thickness of 60 μm. In each of the produced insulating resin sheets, the presence or absence of appearance unevenness due to aggregation of the inorganic filler or the organic compound was visually confirmed.

5). Laminate Appearance Inspection Etching the copper clad laminate obtained using the resin compositions of Examples 1 to 8, Comparative Example 1 and Comparative Example 2, and measuring the L value using a color difference meter. went. The smaller the L value is, the more colored it is.

6). Heat Resistance of Laminate Plate The copper foil of the laminate plate obtained using the resin compositions of Examples 1 to 8 and Comparative Example 1 and Comparative Example 2 was etched, cut to an appropriate size, and a sample Was determined by weight loss during heating.
In Table 1, the heat resistance value of the laminate is determined by TG-DTA (simultaneous differential thermogravimetric measurement) by heating the sample from room temperature to 450 ° C. under the condition of 10 ° C./min. The sample was traced to a value obtained by ((100 ° C. sample weight) − (300 ° C. sample weight)) / (100 ° C. sample weight) × 100.

7). Solder heat resistance A 50 mm square sample was cut out from a laminate obtained by using the resin compositions of Examples 1 to 8, Comparative Examples 1 and 2, and D-2. After the / 100 treatment, the substrate was immersed in 260 ° C. solder for 30 seconds, and the presence or absence of swelling was observed.

8). Thermal expansion coefficient of laminated board The laminated board obtained by using the resin composition of Examples 1 to 8 and Comparative Example 1 and Comparative Example 2 was etched, and the coefficient of thermal expansion was measured using a TMA apparatus (TA instrument). Measured at 10 ° C./min. Measurements were made in the MD direction.

9. Elastic modulus of laminated plate The laminated plate was etched using the resin compositions of Examples 1 to 8, Comparative Example 1 and Comparative Example 2, and the elastic modulus was DMA (DMA 983 manufactured by TA Instruments). The resonance frequency shift mode was used, and the measurement was performed at a temperature rising rate of 5 ° C./min.

Examples 1 to 8 are resin compositions obtained by the production method of the present invention, and prepregs and insulating resin sheets produced using the resin compositions. The obtained prepreg and insulating resin sheet have a good appearance without agglomeration, and in the particle size distribution, the average particle size is small and the σ value of the particle size distribution is also small, indicating that there are no aggregates.

  On the other hand, Comparative Example 1 is an example in which a colorant is added after adding other components and stirred, and the appearance unevenness due to aggregation of inorganic filler and colorant on the resin surface of the obtained prepreg or insulating resin sheet. There has occurred. Moreover, also about a particle size distribution, it turns out that the average particle diameter is large compared with Example 1, and since the (sigma) value of a particle size distribution is also large, the aggregate has generate | occur | produced. Comparative Example 2 is an example that does not contain an inorganic filler, and there is no unevenness in appearance, but since it does not contain an inorganic filler, the thermal expansion coefficient of the laminate is large and the elastic modulus is also reduced. . Therefore, when a multilayer printed wiring board is manufactured using the laminated board obtained in Comparative Example 2, it is considered that the reliability is lowered.

  According to the method for producing a resin composition of the present invention, it becomes uniform even when a colorant having low solvent solubility is used, so that the appearance of a prepreg or an insulating resin sheet produced using the resin composition Is free from unevenness and aggregates. Therefore, it is effective for the production of a resin composition used when producing a thin multilayer printed wiring board in which unevenness in appearance is easily noticeable.

Claims (7)

(A) Step (1) of dissolving and / or dispersing a colorant in a dispersion in which an inorganic filler is dispersed in a solvent, and then (C) Step (2) of dissolving a novolac type epoxy resin. The manufacturing method of the resin composition characterized by including. The method for producing a resin composition according to claim 1, wherein the step (1) is a step of dispersing by stirring at a peripheral speed of 3 m / sec or more. The method for producing a resin composition according to claim 1 or 2, wherein the content of the colorant (B) is 0.5 to 6.5 parts by weight with respect to 100 parts by weight of the inorganic filler (A). The method for producing a resin composition according to any one of claims 1 to 3, wherein the colorant (B) has a weight loss due to sublimation or decomposition at 260 ° C of 10% or less. The method for producing a resin composition according to claim 1, wherein the colorant (B) is a compound having an anthraquinone structure. 6. The inorganic filler (A) is at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, silica, talc, calcined talc, and alumina. A method for producing a resin composition. The method for producing a resin composition according to any one of claims 1 to 6, wherein a content of the solvent used in the step (1) is 25 to 300 parts by weight with respect to 100 parts by weight of the inorganic filler.