TWI620474B - Hardened body, method of manufacturing cured body, laminated body, printed wiring board, and semiconductor device - Google Patents

Abstract

According to the present invention, in the production of a printed wiring board, even when a thin resin composition layer is used in order to reduce the thickness of the layer, a hardened body having a small surface relief which maintains sufficient dry film adhesion can be realized. A technique for suppressing uneven roughness.

The present invention provides a hardened body obtained by laminating a resin composition on a circuit board and thermally hardening the resin composition layer to obtain a hardened body provided on a circuit substrate, wherein a minimum melt viscosity of the resin composition layer is obtained. When the temperature is Tv (° C.), the lamination temperature of the resin composition layer is Tv-35° C. to Tv + 35° C., and the thickness of the resin composition layer is set to x (μm), and the circuit board is placed on the circuit wiring. When the thickness of the hardened body is y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15.

Description

Hardened body, method of manufacturing cured body, laminated body, printed wiring board, and semiconductor device

The present invention relates to a cured body, a method of producing a cured body, a laminate, a printed wiring board, and a semiconductor device.

A printed wiring board such as a multilayer printed wiring board or a flexible printed wiring board which is widely used in various electronic devices requires thinning of the layer or fine wiring of the circuit in order to reduce the size and function of the electronic device.

As a manufacturing technique of a printed wiring board, a manufacturing method using a build-up method in which an overlapping insulating layer and a conductor layer are alternately laminated is known. In the production method using the build-up method, the resin composition is generally thermally cured to form an insulating layer. For example, Patent Document 1 discloses that a resin composition is laminated on a circuit board using a bonding sheet containing a resin composition, and the resin composition layer is thermally cured to obtain a cured body, and then the cured body is subjected to a roughening treatment to form a cured body. The technology of the insulation layer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-37957

After the insulating layer is formed, a conductor layer (wiring layer) having a desired pattern can be formed by a technique such as a semi-additive method or a full additive method. Generally, after a dry film for pattern formation is placed on an insulating layer and a desired pattern is developed, a conductor layer having a desired pattern is formed by plating. At this time, from the viewpoint of the fine wiring formation property, the dry film forming the pattern is preferably sufficiently adhered to the insulating layer.

However, the present inventors have found that when a thin resin composition layer is used to form an insulating layer in order to reduce the thickness of the layer, the surface of the hardened body formed by the hardening of the resin composition layer may become a surface undulation of the circuit substrate with the underlayer. (There is a tendency due to the presence or absence of the circuit wiring), and the adhesion of the dry film for pattern formation is lowered by the undulation. The undulation of the surface of the hardened body can be slightly reduced by operating the laminated condition of the resin composition layer, etc., but the inventors have found the undulating convex portion (that is, the insulation on the circuit wiring of the circuit substrate) in this case. The surface of the layer and the recess (that is, the surface of the insulating layer on the portion of the circuit board where the circuit is not wired) may have a greatly different surface roughness after the roughening process (hereinafter, the phenomenon is also referred to as "roughness" Unevenness"). When the roughness is not uniform, the local fine wiring which is attributed to the surface of the insulating layer is poorly formed.

Therefore, in the manufacture of printed wiring boards, for both layers There is still room for improvement in thinning and fine wiring of circuits.

In the production of a printed wiring board, even when a thin resin composition layer is used in order to reduce the thickness of the layer, a hardened body having sufficient dry film adhesion and small surface undulation can be realized, and A technique that suppresses uneven roughness.

As a result of a review of the above-mentioned problems, the present inventors have found that the laminate temperature of the resin composition layer is Tv-35 ° C to Tv + 35 when the lowest melt viscosity temperature of the resin composition layer is Tv (° C.). In the range of °C, the thickness of the resin composition layer is set to x (μm), and when the thickness of the hardened body on the circuit board of the circuit board is y (μm), x and y satisfy 0.3 < y / x ≦ 1 Further, the relationship between y≦15 can solve the above problems, and thus the present invention has been completed.

That is, the present invention includes the following contents.

[1] A hardened body obtained by laminating a resin composition on a circuit board and thermally hardening the resin composition layer to obtain a hardened body provided on a circuit substrate, wherein a minimum melt viscosity of the resin composition layer is obtained. When the temperature is Tv (° C.), the lamination temperature of the resin composition layer is Tv-35 ° C to Tv + 35 ° C, and the thickness of the resin composition layer is set to x (μm), and the circuit board is placed on the circuit wiring. When the thickness of the hardened body is y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15.

[2] The hardened body according to [1], wherein x≦25.

[3] The hardened body according to [1] or [2], wherein a maximum cross-sectional height Rt of the surface of the hardened body is 3.5 μm or less.

[4] The hardened body according to any one of [1] to [3], wherein the resin composition layer is maintained at a temperature not exceeding Tv for 10 minutes or more, and then maintained at a temperature of Tv or higher for 10 minutes or longer. Heat hardened.

[5] A roughened body obtained by subjecting the hardened body according to any one of [1] to [4] to a roughening treatment.

[6] The roughened hardened body according to [5], wherein the arithmetic mean roughness of the surface of the roughened hardened body on the circuit wiring of the circuit substrate, and the roughened hardened body on the portion of the circuit board having no circuit wiring The difference in arithmetic mean roughness of the surface is 160 nm or less.

[7] A laminated body comprising the roughened hardened body according to [5] or [6] and a conductor layer formed on the surface of the roughened hardened body.

[8] A method for producing a hardened body, comprising the steps of: (A) laminating a resin composition on a circuit substrate, and (B) thermally curing the resin composition layer to provide a hardened body on the circuit substrate. In the step of setting the lowest melt viscosity temperature of the resin composition layer to Tv (° C.), the laminate temperature of the resin composition layer is Tv-35° C. to Tv + 35° C., and the thickness of the resin composition layer is set to x. (μm), when the thickness of the hardened body on the circuit wiring of the circuit board is y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15.

[9] The method for producing a hardened body according to [8], wherein x ≦ 25.

[10] The method for producing a hardened body according to [8] or [9], wherein The maximum cross-sectional height Rt of the surface of the chemical body is 3.5 μm or less.

[11] The method for producing a hardened body according to any one of [8], wherein in the step (B), the resin composition layer is maintained at a temperature less than Tv for 10 minutes or more, in Tv The above temperature is maintained for 10 minutes or more to perform thermal hardening.

[12] A printed wiring board in which an insulating layer is formed by the hardened body according to any one of [1] to [4].

[13] A semiconductor device comprising the printed wiring board according to [12].

According to the present invention, in the production of a printed wiring board, even when a thin resin composition layer is used in order to reduce the thickness of the layer, a hardened body which retains sufficient dry film adhesion and has a small surface undulation can be realized while suppressing Uneven roughness occurs.

1‧‧‧ resin composition layer

2‧‧‧hardened body

3‧‧‧ circuit board

4‧‧‧Circuit wiring

5‧‧‧Substrate

Fig. 1 is a view schematically showing a cross section of a resin composition layer.

Fig. 2 is a view schematically showing a cross section of a hardened body provided on a circuit board in an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the present invention. invention.

[hardened body]

The hardening system of the present invention is characterized in that a resin composition is laminated on a circuit board and the resin composition layer is thermally cured to obtain a hardened body provided on the circuit substrate, which is characterized in that the lowest melt viscosity temperature of the resin composition layer is set. In the case of Tv (°C), the laminate temperature of the resin composition layer is Tv-35° C. to Tv+35° C., and the thickness of the resin composition layer is set to x (μm), and the hardened body on the circuit wiring of the circuit board is used. When the thickness is y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15.

The "circuit board" on which the hardened body of the present invention is provided refers to a substrate having circuit patterns processed on one or both sides. The substrate used for the circuit board is exemplified by, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like. Further, when a printed wiring board is manufactured, an inner layer circuit board in which an intermediate layer of an insulating layer and/or a conductor layer is further formed is also included in the "circuit board" of the present invention.

The thickness of the circuit wiring to be patterned on one side or both sides of the substrate is not particularly limited, but from the viewpoint of thinning the layer, it is preferably 70 μm or less, more preferably 30 μm or less, and still more preferably 20 μm. the following. The lower limit of the thickness of the circuit wiring is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more.

The line/space ratio of the circuit wiring of the pattern processing on one side or both sides of the substrate is not particularly limited, but the surface of the hardened body is suppressed. The volt is preferably 200/200 μm or less, more preferably 100/100 μm or less, still more preferably 40/40 μm or less, still more preferably 20/20 μm or less, and most preferably 8/8 μm. The lower limit of the line/space ratio of the circuit wiring is not particularly limited, but is preferably 0.5/0.5 μm or more, more preferably 1/1 μm or more, in order to allow the resin to be well embedded in the space.

In the curing system of the present invention, a resin composition is laminated on the circuit board, and the resin composition layer is thermally cured.

From the viewpoint of thinning the layer of the printed wiring board, it is desirable to use a thin resin composition layer. However, when a thin resin composition layer is used, the surface of the formed hardened body tends to have a large undulation corresponding to the circuit wiring pattern of the underlying circuit substrate. The large undulation of the surface of the hardened body is attributed to the deterioration of the fine wiring formation property of the dry film of the pattern forming.

From the viewpoint of suppressing the surface undulation of the hardened body, when the lowest melt viscosity temperature of the resin composition layer is Tv (° C.), the temperature at which the resin composition is laminated on the circuit board (hereinafter also referred to as "layering" The temperature ") is in the range of Tv-35 ° C ~ Tv + 35 ° C, preferably in the range of Tv-30 ° C ~ Tv + 30 ° C, more preferably in the range of Tv - 25 ° C ~ Tv + 25 ° C, and better The range of Tv-20 ° C ~ Tv + 20 ° C, and more preferably Tv-15 ° C ~ Tv + 15 ° C range.

Here, the "lowest melt viscosity temperature" of the resin composition layer means the temperature at which the resin composition layer exhibits the lowest melt viscosity. Further, the term "minimum melt viscosity" of the resin composition layer means the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. detailed In other words, when the resin composition layer is heated at a certain heating rate to melt the resin, the melt viscosity in the initial stage decreases as the temperature rises, and then, when the temperature exceeds a certain temperature, the melt viscosity increases as the temperature rises, and the so-called "minimum melt viscosity" "" refers to the melt viscosity of this very small point. The lowest melt viscosity temperature of the resin composition layer can be determined by dynamic viscoelasticity. Specifically, the lowest melt viscosity temperature of the resin composition layer can be obtained by dynamic viscoelasticity measurement at a measurement start temperature of 60 ° C, a temperature increase rate of 5 ° C / min, a vibration number of 1 Hz, and a strain of 1 degree. The dynamic viscoelasticity measuring device is exemplified by "Rheosol-G3000" manufactured by UBM Co., Ltd.

The undulation of the surface of the hardened body can be evaluated by the maximum cross-sectional height Rt of the surface of the hardened body. When the maximum cross-sectional height Rt of the surface of the hardened body exceeds 4 μm, the adhesion of the dry film for pattern formation tends to be remarkably lowered. The surface maximum cross-sectional height Rt of the cured body of the present invention is preferably 3.5 μm or less, more preferably 3.3 μm or less, and still more preferably 3.1 μm or less from the viewpoint of achieving sufficient adhesion of the dry film for pattern formation. Further, it is more preferably 2.9 μm or less, 2.7 μm or less, 2.5 μm or less, 2.3 μm or less, 2.1 μm or less, or 1.9 μm or less.

The maximum cross-sectional height Rt of the surface of the hardened body can be measured using a non-contact type surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by Veeco Instruments.

The adhesion of the dry film for pattern formation is improved by suppressing the undulation of the surface of the hardened body. However, when a thin resin composition layer is used to form a hardened body, it is necessary to pay attention to the occurrence of roughness unevenness. In other words, when a thin resin composition layer is used to provide a hard surface having a small surface relief on the circuit substrate, there is a convex portion of the undulation (that is, a surface of the hard surface of the circuit substrate on the circuit wiring) and a concave portion (that is, The surface of the hardened body on the circuit-free wiring portion of the circuit board exhibits a greatly different surface roughness after the roughening treatment. This roughness can not by arithmetic average roughness (Ra ₁₎ of the convex portion of the rear surface roughening and hardening of the relief and the arithmetic mean roughness of the relief recess (Ra ₂₎ the difference (| Ra ₁ -Ra ₂ |) to be evaluated. When the value of |Ra ₁ -Ra ₂ | is higher than 160 nm, the formation of the conductor layer (circuit wiring) tends to be due to the formation of local fine wiring. In the case where a thin resin composition layer is used to form a hardened body having a small surface undulation on a circuit board, the inventors have found that roughness unevenness is particularly likely to occur in the following cases: i) When a resin composition layer having a high inorganic filler content is used, ii) when a cured product is formed using a subsequent sheet having a layer composed of a resin composition layer/support layer, the resin composition layer is thermally hardened in a state in which the support is attached. Wait.

Further, the arithmetic mean roughness Ra of the surface of the hardened body can be measured using a non-contact type surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by Veeco Instruments.

From the viewpoint of suppressing occurrence of roughness unevenness while achieving thinning of the layer, it is important to set the thickness of the resin composition layer to x (μm) and to set the thickness of the hardened body on the circuit wiring of the circuit board. In the case of y (μm), the resin composition layer is laminated and thermally cured so that x and y satisfy 0.3<y/x≦1 and y≦15. Further, the thickness x of the resin composition layer refers to the thickness of the resin composition layer laminated on the circuit substrate, and the thickness y of the hardened body on the circuit wiring of the circuit substrate means the circuit substrate. The thickness of the hardened body located directly above the circuit wiring.

When x and y satisfy the above relationship, even when a thin resin composition layer is used to form a hardened body, unevenness in roughness can be favorably suppressed. For example, the thickness x of the resin composition layer can be set to less than 50 μm. Further, when a resin composition layer having a thickness x of 40 μm or less, 35 μm or less, 30 μm or less, or 25 μm or less is used, occurrence of roughness unevenness can be favorably suppressed. The lower limit of the thickness x of the resin composition layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, and still more preferably 5 μm or more.

From the viewpoint of suppressing occurrence of roughness unevenness while achieving thinning of the layer, when y ≦ 15 , it is preferably 0.35 ≦ y / x ≦ 1, more preferably 0.4 ≦ y / x ≦ 1, and even more preferably 0.5 ≦ y / x ≦ 1, preferably 0.6 ≦ y / x ≦ 1.

From the viewpoint of thinning of the layer, it is preferably y≦14, more preferably y≦12, and more preferably y≦10, preferably y≦9, y≦8, y≦7 or y≦6. . When y is in the range, and the y/x ratio is in the above range, the occurrence of roughness unevenness can be favorably suppressed. The lower limit of y is not particularly limited as long as it can function as the insulating layer of the present invention, but is usually 0.5 ≦y, preferably 1 ≦y. Also, the upper limit of the y/x ratio may not be up to one.

The resin composition layer laminated on the circuit substrate is preferably maintained at a temperature not lower than the lowest melt viscosity temperature Tv of the resin composition layer from the viewpoint of reducing the undulation of the surface of the hardened body and suppressing occurrence of roughness unevenness. After a minute, the temperature was maintained at a temperature above Tv for 10 minutes for thermal hardening. The details of the thermal hardening of the resin composition layer are described later.

As described above, the hardened body of the present invention contributes to thinning of a layer having a thickness as thin as 15 μm or less on a circuit wiring, and having a surface having a small undulation can also suppress unevenness of roughness, thereby contributing to the circuit. Fine wiring. Therefore, in the production of the printed wiring board, the hardening system of the present invention contributes significantly to both the thinning of the layer and the fine wiring of the circuit.

Further, Fig. 1 schematically shows a cross section of a resin composition layer used for forming the cured body of the present invention. The above x is the thickness of the resin composition layer 1 before being laminated on the circuit board.

Further, Fig. 2 is a schematic cross-sectional view showing a cured body provided on a circuit board in an embodiment of the present invention. In FIG. 2, the circuit board 3 is provided with the wiring circuit 4 processed by the pattern on the board|substrate 5, and the hardening body 2 is provided in this circuit board 3. The above y refers to the thickness of the hardened body 2 on the circuit wiring 4 of the circuit board.

Hereinafter, the resin composition layer used to form the cured body of the present invention will be described.

<Resin composition layer>

The resin composition used in the resin composition layer is not particularly limited as long as the formed hardened body has sufficient hardness and insulation properties. The resin composition used in the resin composition layer is lowered from the viewpoint of lowering the thermal expansion coefficient of the obtained hardened body (insulating layer) and preventing cracking or circuit deformation due to a difference in thermal expansion between the insulating layer and the conductor layer. It contains inorganic fillers.

As described above, the present inventors have found that the use of an inorganic filler is included. When the resin composition layer having a high amount forms a hardened body, it is particularly likely to cause roughness unevenness. However, according to the present invention, occurrence of unevenness in roughness can be favorably suppressed even when a resin composition having a high content of the inorganic filler is used.

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more from the viewpoint of sufficiently lowering the thermal expansion coefficient of the obtained cured body. .

In the present invention, the content of each component in the resin composition is a value when the total amount of nonvolatile components in the resin composition is 100% by mass.

In the present invention, the content of the inorganic filler in the resin composition can be further improved while suppressing the occurrence of roughness unevenness. For example, the content of the inorganic filler in the resin composition may be as high as 66% by mass or more, 68% by mass or more, or 70% by mass or more.

The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of mechanical strength of the cured body obtained by thermal curing of the resin composition layer.

The inorganic filler is exemplified by, for example, cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate. , barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, cerium oxide such as amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, and hollow cerium oxide is preferred. Further, the cerium oxide is preferably spherical cerium oxide. The inorganic filler may be used singly or in combination of two or more. Commercially available spherical molten cerium oxide Listed as "SOC2" and "SOC1" by Admatechs.

The average particle diameter of the inorganic filler is preferably in the range of 0.01 μm to 2 μm, more preferably in the range of 0.05 μm to 1.5 μm, still more preferably in the range of 0.07 μm to 1 μm, still more preferably in the range of 0.1 μm to 0.8 μm. The average particle size of the inorganic filler can be based on the Mie scattering theory, by laser diffraction. Determined by scattering method. Specifically, the particle size distribution of the inorganic filler can be determined on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. The measurement sample can be preferably used in which the inorganic filler is dispersed in water by ultrasonic waves. The laser diffraction scattering type particle size distribution measuring apparatus can use LA-500 manufactured by Horiba, Ltd., and the like.

In order to improve moisture resistance, the inorganic filler is preferably an amine decane coupling agent, an epoxy decane coupling agent, a decyl decane coupling agent, a decane coupling agent, an organic decazane compound, a titanate coupling agent, or the like. One or more kinds of surface treatment agents are treated. The commercially available product of the surface treatment agent is, for example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3- "Methyl propyl trimethoxy decane", "KBE903" (3-aminopropyl triethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl) manufactured by Shin-Etsu Chemical Co., Ltd. 3-Aminopropyltrimethoxydecane), "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

Further, the inorganic filler which has been surface-treated with a surface treatment agent can be measured by washing with a solvent (for example, methyl ethyl ketone (MEK)), and then the amount of carbon per unit surface area of the inorganic filler can be measured. Specifically, it will act as A sufficient amount of MEK of the solvent was added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After removing the supernatant liquid and drying the solid component, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As for the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg, from the viewpoint of improving the dispersibility of the inorganic filler. /m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin paint or the melt viscosity of the sheet form from increasing, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg. /m ² or less.

The resin composition used in the resin composition layer contains a thermosetting resin as a resin. As the thermosetting resin, a conventional thermosetting resin which is used in forming an insulating layer of a printed wiring board can be used, and an epoxy resin is preferable. The resin composition may also contain a hardener as needed. In one embodiment, a resin composition containing an inorganic filler, an epoxy resin, and a curing agent can be used. The resin composition used in the resin composition layer may further contain an additive such as a thermoplastic resin, a hardening accelerator, a flame retardant, and rubber particles.

Hereinafter, an epoxy resin, a curing agent, and an additive which can be used as a material of the resin composition will be described.

(epoxy resin)

As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F Type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolak type ring Oxygen resin, t-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, fluorene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin , cresol novolak type epoxy resin, biphenyl type epoxy resin, chain aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, Spiro epoxy resin, cyclohexane dimethanol epoxy resin, naphthalene ether epoxy resin and trimethylol epoxy resin. The epoxy resin may be used alone or in combination of two or more.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and having a liquid at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resin") and three or more epoxy resins in one molecule are preferable. An epoxy resin (hereinafter referred to as "solid epoxy resin") having a solid content at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin as an epoxy resin together, a resin composition having excellent flexibility is obtained. Further, the breaking strength of the hardened body formed by hardening the resin composition is also improved.

As for the liquid epoxy resin, it is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin, more preferably a bisphenol A type epoxy resin. Resin or naphthalene epoxy resin. Specific examples of the liquid epoxy resin are "HP4032" manufactured by DIC Co., Ltd. "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene epoxy resin), "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER807" (bisphenol F type epoxy resin) ), "jER152" (phenol novolak type epoxy resin). These may be used alone or in combination of two or more.

The solid epoxy resin is preferably a 4-functional naphthalene epoxy resin, a cresol novolak epoxy resin, a dicyclopentadiene epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy. The resin, the biphenyl type epoxy resin, or the naphthene ether type epoxy resin is more preferably a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthene ether type epoxy resin. Specific examples of the solid epoxy resin are "HP-4700", "HP-4710" (4-functional naphthalene type epoxy resin), and "N-690" ("phenol novolac type epoxy" manufactured by DIC Co., Ltd. Resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4" "EXA7311-G4S", "HP6000" (naphthyl ether type epoxy resin), "EPPN-502H" (trisphenol epoxy resin) made by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac ring) Oxygen resin, "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel Chemical Co., Ltd. (naphthol novolac type epoxy resin) "ESN485" (naphthol novolak type epoxy resin), "YX4000H", "YX4000HK", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

When a liquid epoxy resin and a solid epoxy resin are used as the epoxy resin, the ratio (liquid epoxy resin: solid epoxy resin) is preferably from 1:0.1 to 1:4 by mass ratio. range. When the ratio of the amount of the liquid epoxy resin to the solid epoxy resin is in this range, the following effects can be obtained: i) maintaining a proper adhesion when used in the form of a subsequent sheet, and ii) followed by sheeting. When the form is used, sufficient flexibility is obtained, workability is improved, and iii) a hardened body having sufficient fracture strength or the like can be obtained. From the viewpoint of the effects of the above i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1 in terms of mass ratio. The range of 0.3~1:3.5 is preferably in the range of 1:0.6~1:3, preferably in the range of 1:0.8~1:2.8.

The epoxy resin content in the resin composition is preferably from 3% by mass to 50% by mass, more preferably from 5% by mass to 45% by mass, even more preferably from 5% by mass to 40% by mass, most preferably 7% by mass. 35 mass%.

The epoxy equivalent of the epoxy resin is preferably from 50 to 3,000, more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By this range, an insulating layer having a low cross-linking density of a cured product and a low surface roughness is obtained. Further, the epoxy equivalent can be measured in accordance with JIS K7236 and is a resin containing 1 equivalent of an epoxy group.

(hardener)

The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanurate curing agent. . Hardener can be single One type may be used alone or two or more types may be used in combination.

The phenolic curing agent and the naphthol-based curing agent are preferably a phenolic curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure. Further, from the viewpoint of adhesion to the conductor layer (peeling strength), a nitrogen-containing phenol-based curing agent is preferred, and a benzene-based curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to a conductor layer (peeling strength), a phenol novolak resin containing a triazine skeleton is preferably used as a curing agent.

Specific examples of the phenolic curing agent and the naphthol-based curing agent are, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "Nippon Chemical Co., Ltd." manufactured by Mingwa Kasei Co., Ltd. "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", "NHN", "CBN", "GPH", and Dongdu Chemicals Co., Ltd. "LA7052", "LA7054", "LA3018", etc. of DIC (share) system.

From the viewpoint of adhesion to the conductor layer (peel strength), an active ester-based curing agent is also preferred. The active ester-based curing agent is not particularly limited, but preferably has two or more reactions in one molecule such as a general phenolic ester, a thiophenolic ester, an N-hydroxylamine ester, or an ester of a heterocyclic hydroxy compound. A compound having a high activity of an ester group. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, it is preferred that the active ester obtained from the carboxylic acid compound and the hydroxy compound is hard. The agent is more preferably an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound. The carboxylic acid compound is exemplified by, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Phenolic compounds or naphthol compounds are exemplified by, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene diphenol compound, phenol Novolac and the like. Here, the "dicyclopentadiene diphenol compound" means a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound of an acetal containing phenol novolac, and benzamidine containing a phenol novolac. The active ester compound of the compound, more preferably an active ester compound having a naphthalene structure or an active ester compound having a dicyclopentadiene diphenol structure.

As a commercial product of an active ester-based curing agent, as an active ester compound containing a dicyclopentadiene diphenol structure, it is exemplified as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (DIC) (manufactured by the company), the active ester compound containing a naphthalene structure is exemplified as "EXB9416-70BK" (manufactured by DIC Co., Ltd.), and the active ester compound of the acetal containing phenol novolac is exemplified as "DC808" (Mitsubishi Chemical Co., Ltd.) )), as an active ester compound of a benzamidine compound of a phenol novolak It is "YLH1026" (Mitsubishi Chemical Co., Ltd.).

Specific examples of the benzoxazine-based hardener are "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries Co., Ltd.

The cyanate-based curing agent is exemplified by, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4,4'- Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-double (4-cyanate group) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) sulfide, and bis(4-cyanate) a bifunctional cyanate resin such as phenyl)ether, a polyfunctional cyanate resin derived from a phenol novolac and a cresol novolak, or a prepolymer obtained by triazine-forming a part of the cyanate resin. Specific examples of the cyanate-based curing agent are "PT30" and "PT60" manufactured by Japan LONZA Co., Ltd. (all are phenol novolac type polyfunctional cyanate resins), and "BA230" (bisphenol A II). A part or all of a cyanate ester is triazine-formed into a prepolymer of a trimer) and the like.

The ratio of the epoxy resin to the hardener is preferably in the range of 1:0.2 to 1:2, preferably in the ratio of [epoxy group of epoxy resin]: [counting ratio of reactive groups of hardener]. It is 1:0.3~1:1.5, and more preferably 1:0.4~1:1. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, which varies depending on the type of each curing agent. Further, the epoxy group count of the epoxy resin is a value obtained by dividing the solid content of each epoxy resin by the value of the epoxy equivalent for all the epoxy resins, so-called hardener. The total number of reaction groups is a value obtained by dividing the solid component mass of each of the hardeners by the value of the reaction group equivalent for all the hardeners. When the ratio of the amount of the epoxy resin to the curing agent is in this range, the heat resistance of the cured product of the resin composition is further improved.

In one embodiment, the resin composition used to form the cured body of the present invention comprises the inorganic filler, the epoxy resin, and the curing agent. The resin composition preferably contains cerium oxide as an inorganic filler, and contains a mixture of a liquid epoxy resin and a solid epoxy resin (liquid epoxy resin: the quality of the solid epoxy resin is preferably 1:0.1~ The range of 1:4, preferably in the range of 1:0.3 to 1:3.5, more preferably in the range of 1:0.6 to 1:3, preferably in the range of 1:0.8 to 1:2.8) as epoxy resin One or more selected from the group consisting of a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate curing agent are used as a curing agent. The resin composition layer containing the specific component is preferably a content of the inorganic filler, the epoxy resin, and the hardener as described above, but among them, the content of the inorganic filler is preferably 50% by mass to 95% by mass. The content of the oxygen resin is 3% by mass to 50% by mass, the content of the inorganic filler is preferably 50% by mass to 90% by mass, and the content of the epoxy resin is 5% by mass to 45% by mass. The content of the hardener is preferably a ratio of the total number of epoxy groups of the epoxy resin to the total of the reactive groups of the hardener, preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3. The range of ~1:1.5 is better included in the range of 1:0.4 to 1:1.

The resin composition may further contain an additive such as a thermoplastic resin, a hardening accelerator, a flame retardant, and rubber particles as needed.

(thermoplastic resin)

The thermoplastic resin is exemplified by, for example, a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, a polyphenylene ether resin. And polyanthrene resin and the like. The thermoplastic resin may be used singly or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is LC-9A/RID-6A manufactured by Shimadzu Corporation, and the Shodex K-800P/K manufactured by Showa Denko Co., Ltd. is used. -804L/K-804L was used as a column, and chloroform was used as a mobile phase, and the column temperature was measured at 40 ° C, and was calculated using a calibration line of standard polystyrene.

The phenoxy resin is exemplified by, for example, having a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, a dicyclopentadiene skeleton, and a descending A phenoxy resin having one or more kinds of skeletons selected from the group consisting of a borneol skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any one of a phenolic hydroxyl group, an epoxy group and the like. The phenoxy resin may be used singly or in combination of two or more. Specific examples of the phenoxy resin are listed as "1256" by Mitsubishi Chemical Corporation. "4250" (all phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton), and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), In addition, "FX280" and "FX293" manufactured by Dongdu Chemicals Co., Ltd., "YL7553", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation are listed.

Specific examples of the polyethylene acetal resin are electro-chemical butyraldehyde 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Electrochemical Industry Co., Ltd., S-LEC BH manufactured by Sekisui Chemical Industry Co., Ltd. Series, BX series, KS series, BL series, BM series, etc.

Specific examples of the polyimine resin are "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Publication No. 2006-37083) The modified polyimine, such as those which are described in JP-A-2002-12667 and JP-A-2000-319386, and the like.

Specific examples of the polyamidoximine resin are "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin are modified polyamines such as polyacrylamide skeletons "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. amine.

Specific examples of the polyether oxime resin are "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polyanthracene resin are those of the "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

The content of the thermoplastic resin in the resin composition is preferably from 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin to such a range, the viscosity of the resin composition can be made moderate, and a uniform resin composition having a thickness or a bulk property can be formed. The content of the thermoplastic resin in the resin composition is more preferably from 0.5% by mass to 10% by mass.

Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and an lanthanum-based curing accelerator. Among them, a phosphorus-based curing accelerator, an amine-based curing accelerator, and an imidazole-based system are preferable. The hardening accelerator is more preferably an amine hardening accelerator or an imidazole hardening accelerator.

Phosphorus-based hardening accelerators are exemplified by, for example, triphenylphosphine, bismuth borate, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonate, (4-methylbenzene) The group is triphenylsulfonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate or the like, preferably triphenylphosphine or tetrabutylphosphonate.

The amine-based hardening accelerator is exemplified by a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine or 2,4,6-gin(dimethylaminomethyl). Phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0) - undecene.

The imidazole-based hardening accelerator is exemplified by, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl -2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2 -Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamine -6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'- Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline Imidazole compound such as 2-phenylimidazoline and imidazole compound and epoxy resin Into the composition, preferably 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole.

The lanthanide hardening accelerator is exemplified by, for example, dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-tolyl) fluorene, and dimethyl Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1, 1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., preferably two Cyanamide, 1,5,7-triazabicyclo[4.4.0]non-5-ene.

The curing accelerator may be used singly or in combination of two or more. In a preferred embodiment, the curing accelerator contained in the resin composition is one or more selected from the group consisting of a phosphorus-based curing accelerator, an amine-based curing accelerator, and an imidazole-based curing accelerator. The content of the hardening accelerator in the resin composition is preferably from 0.05% by mass to 3% by mass based on the total amount of the non-volatile components of the epoxy resin and the curing agent as 100% by mass.

The flame retardant is exemplified by, for example, an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxygenated flame retardant, a metal hydroxide, or the like. The flame retardant may be used singly or in combination of two or more. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably from 0.5% by mass to 10% by mass, more preferably from 1% by mass to 9% by mass, even more preferably from 1.5% by mass to 8% by mass. .

For example, the rubber particles are not dissolved in an organic solvent to be described later, and are incompatible with the above-mentioned epoxy resin, curing agent, thermoplastic resin, or the like. The rubber particles are generally prepared in a granular form such that the molecular weight of the rubber component is so large that it is not dissolved in the organic solvent or the resin.

Examples of the 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, and are exemplified by a two-layer structure in which a shell layer of an outer layer is a glassy polymer, a core layer of an inner layer is a rubbery polymer, or a shell of an outer layer. The layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. Glassy poly The layer is composed of, for example, a methyl methacrylate polymer, and the rubber-like polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. The rubber particles may be used singly or in combination of two or more.

The average particle diameter of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured by dynamic light scattering. For example, the rubber particles may be uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and a particle size distribution of the rubber particles may be prepared on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). The value diameter is determined as the average particle diameter. The content of the rubber particles in the resin composition is preferably from 1% by mass to 10% by mass, more preferably from 2% by mass to 5% by mass.

The resin composition used to form the hardened body of the present invention may optionally contain other additives, such as organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and organic fillers and tackifiers. A resin additive such as an antifoaming agent, a leveling agent, an adhesion imparting agent, a coloring agent, and a curable resin.

As the hardened body of the present invention, a hardened body (hardened body for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board can be used. Among them, a cured body (hardened body for a build-up insulating layer of a printed wiring board) for forming an insulating layer in the production of a printed wiring board using a build-up method can be preferably used as a use pattern. A hardened body (a hardened body for a build-up insulating layer of a printed wiring board in which a pattern-processed conductor layer is formed by using a dry film for pattern formation) is formed by using a dry film to form a patterned conductor layer.

The resin composition layer can be used in the form of a subsequent sheet in order to easily and efficiently form a resin composition layer for forming a cured body of the present invention.

In one embodiment, the succeeding sheet comprises a support and a resin composition layer (adjacent layer) joined to the support.

The support can preferably use a film made of a plastic material. The plastic material is exemplified by polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") or polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonate ( Hereinafter, it may be simply referred to as "PC"), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triethyl fluorenyl cellulose (TAC), polyether thioether (PES), polyether ketone, Polyimine and the like. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred, and polyethylene terephthalate is preferably inexpensive. In a preferred embodiment, the support is a polyethylene terephthalate film.

The support may also be subjected to a matte treatment or a corona treatment on the surface on the side joined to the resin composition layer. Further, as the support, a support having a release layer with a release layer on the surface on the side joined to the resin composition layer may be used.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Further, when the support is a support having a release layer, the thickness of the entire support having the release layer is preferably in the above range.

Then, the sheet can be prepared by dissolving the resin composition in an organic solvent to prepare a resin paint, and coating the resin paint using a die coater or the like. The organic solvent is dried on the support by heating or by blowing with hot air to form a resin composition layer.

The organic solvent may, for example, be a ketone such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, fibrin acetate, propylene glycol monomethyl ether acetate, and carbitol acetic acid. Acetates such as esters, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide and N-methylpyrrole A guanamine-based solvent such as ketone or the like. The organic solvent may be used singly or in combination of two or more.

The drying conditions are not particularly limited, but the organic solvent content (residual solvent amount) in the resin composition layer is preferably 10% by mass or less, preferably 5% by mass or less. The lower limit of the amount of the residual solvent is not particularly limited, but is preferably 0.5% by mass or more, and more preferably 1% by mass or more from the viewpoint of workability of the resin composition layer or prevention of increase in melt viscosity in the form of a sheet. Although it varies depending on the boiling point of the organic solvent in the resin paint, when a resin composition containing, for example, 30% by mass to 60% by mass of an organic solvent is used, it can be dried at 50 ° C to 150 ° C for 3 to 10 minutes. And a resin composition is formed.

Next, in the sheet, the surface of the resin composition layer which is not bonded to the support (that is, the surface opposite to the support) may be further laminated with a protective film according to the support. The thickness of the protective film is not particularly limited, but may be, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dirt or the like from adhering to the surface of the resin composition layer or to prevent scratches. Then, the sheet can be wound up in a roll shape, and can be protected by peeling when manufacturing the hardened body of the present invention. Use as a film.

[Method of Manufacturing Hardened Body]

A method for producing a cured body of the present invention, comprising the steps of: (A) laminating a resin composition on a circuit board, and (B) thermally curing the resin composition layer to form a hardened body on the circuit board; When the lowest melt viscosity temperature of the resin composition layer is Tv (° C.), the laminate temperature of the resin composition layer is Tv-35° C. to Tv + 35° C., and the thickness of the resin composition layer is set to x (μm). When the thickness of the hardened body on the circuit wiring of the circuit board is y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15.

In the step (A), the resin composition is laminated on the circuit board. The circuit board and the resin composition layer used in the step (A) are as described above.

In the method for producing a cured body of the present invention, the resin composition is laminated on the circuit substrate in a temperature range of Tv-35 ° C to Tv + 35 ° C from the viewpoint of suppressing the surface roughness of the hardened body formed on the circuit board. . The layer temperature of the resin composition layer in the step (A) is preferably in the range of Tv-30 ° C to Tv + 30 ° C, more preferably Tv - 25 , from the viewpoint of suppressing the surface undulation of the hardened body formed on the circuit substrate. The range of °C~Tv+25°C is preferably in the range of Tv-20°C~Tv+25°C, preferably in the range of Tv-15°C~Tv+15°C.

The resin composition layer is preferably laminated on the circuit substrate in the above The laminate treatment is carried out by laminating or pressing under pressure at a laminate temperature to bond the resin composition layer to the circuit board. Among them, it is more preferable to carry out lamination or vacuum lamination under reduced pressure.

In a preferred embodiment, the laminate of the resin composition layer on the circuit board can be carried out using the above-mentioned succeeding sheet. In detail, a lamination process may be performed to bond the resin composition layer of the subsequent sheet to the circuit substrate. When the sheet has a protective film, it can be supplied to the step (A) after the protective film is removed. Further, the peeling of the support may be carried out between the step (A) and the step (B), or may be carried out after the step (B), but it is preferably in the step (A) from the viewpoint of suppressing unevenness in roughness. Implemented with step (B).

Laminating process is preferably the one side to consider the relationship of x and y is, one side of the pressing pressure was set in the range of ^{1kgf / cm 2 ~ 11kgf / cm} 2 (0.098MPa ~ 1.078MPa) , the pressing time is set to 5 seconds to In the range of 180 seconds, the air pressure was set to 20 mmHg (26.7 hPa) or less under reduced pressure.

After the lamination treatment, the smoothing treatment of the subsequent sheet by the lamination treatment may be performed by hot pressing of a metal plate. This smoothing treatment can be carried out under normal pressure (at atmospheric pressure) with a metal plate such as a heated SUS mirror plate by heating or pressurizing the sheet. The heating and pressurizing conditions may be the same conditions as the above lamination treatment.

The lamination treatment (and smoothing treatment) can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machines are, for example, vacuum press laminators manufactured by Nippon Seisakusho Co., Ltd., vacuum coaters manufactured by Nichigo Morton Co., Ltd., and the like.

In the step (B), the resin composition layer is thermally hardened in the circuit A hardened body is formed on the substrate.

In the step (B), it is preferred that the resin composition layer is kept at a temperature T ₁ for a certain period of time and is higher than the temperature T _{1 from} the viewpoint of reducing the surface roughness of the formed hardened body and suppressing occurrence of roughness unevenness. The temperature is maintained at a temperature T ₂ for a certain period of time.

The temperature T _{1 is} preferably a temperature (° C.) which is less than Tv, more preferably Tv - 10 ° C or less, more preferably Tv - 20 ° C or less, and most preferably Tv - 25 ° C or less. The lower limit of the temperature T ₁ is preferably Tv-60 ° C or higher, more preferably Tv - 50 ° C or higher, and even more preferably Tv - 40 ° C or higher.

The time during which the temperature T _{1 is} maintained depends on the value of the temperature T ₁ , but is preferably 10 minutes or longer, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

The temperature T _{2 is} preferably a temperature above Tv (° C.), more preferably Tv+10° C. or more, more preferably Tv+20° C., and even more preferably Tv+30° C., preferably Tv+40° C. or higher. . The upper limit of the temperature T ₂ is preferably less Tv + 100 ℃, more preferably less Tv + 90 ℃, and more preferably less Tv + 80 ℃, further more preferably less Tv + 70 ℃, preferably Tv + 60 ℃ the following.

Holding at the temperature T ₂ of the system over time of the value of temperature T ₂ may be, but is preferably 10 minutes or more, more preferably 10 minutes to 100 minutes, and more preferably from 10 minutes to 80 minutes.

The thermal hardening of the resin composition layer in the step (B) is preferably carried out at a temperature less than Tv for more than 10 minutes from the viewpoint of reducing the surface roughness of the formed hardened body and suppressing occurrence of roughness unevenness. The temperature above Tv is maintained for more than 10 minutes, preferably above Tv-60 °C. And after the temperature of Tv is not maintained for 10 minutes or more, it is carried out at a temperature of Tv or more and Tv+100 ° C or lower for 10 minutes, and more preferably after Tv-60 ° C or more and the temperature of Tv is not maintained for 10 minutes or more. It is carried out at a temperature of Tv + 10 ° C or higher and Tv + 100 ° C or lower for 10 minutes, and more preferably at a temperature of Tv - 50 ° C or higher and at a temperature of Tv - 10 ° C or lower for 10 minutes or more, and then at Tv + 10 ° C or higher. And the temperature below Tv+90 ° C is maintained for 10 minutes, and it is better to maintain the temperature above Tv-40 ° C and above Tv -20 ° C for more than 10 minutes, after Tv + 20 ° C and above and at Tv + 80 The temperature below °C was maintained for 10 minutes.

Step (B) may be carried out under pressure, may be carried out under normal pressure or may be carried out under reduced pressure, but in terms of reducing the surface roughness of the formed hardened body and suppressing occurrence of roughness unevenness, It is preferably carried out in the range of 0.075 mmHg to 3751 mmHg (0.1 hPa to 5000 hPa), more preferably in the range of 1 mmHg to 1875 mmHg (1.3 hPa to 2500 hPa). Among them, the step (B) is preferably carried out under normal pressure.

The temperature increase rate from the temperature T ₁ to the temperature T ₂ is not particularly limited, but is preferably from 1.5 ° C / min to 30 ° C / min, more preferably from 2 ° C / min to 30 ° C / min, and even more preferably 4 ° C / Minutes ~ 20 ° C / min, and more preferably 4 ° C / min ~ 10 ° C / min.

As described above, from the viewpoint of suppressing occurrence of roughness unevenness while achieving thinning of the layer, it is important to set the thickness of the resin composition layer to x (μm) to circuit the circuit board. When the thickness of the hardened body is y (μm), the resin composition layer is laminated and thermally cured so that x and y satisfy 0.3<y/x≦1 and y≦15. x, y, and y/x The preferred range is as described above.

[roughened hardened body]

The roughened and hardened body of the present invention can be formed by subjecting the hardening of the present invention to a roughening treatment.

The order and conditions of the roughening treatment are not particularly limited, and conventional sequences and conditions which are generally used when forming an insulating layer of a printed wiring board can be employed. For example, the surface of the hardened body may be subjected to a roughening treatment by a swelling treatment of the swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid. The swelling liquid is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferred. The alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swelling liquids are exemplified by, for example, Sweering Dip Securiganth P, Sweering Dip Securiganth SBU, etc., manufactured by ATOTECH Co., Ltd., Japan. The swelling treatment of the swelling liquid is not particularly limited, and it can be carried out, for example, by immersing the hardened body in a swelling liquid at 30 to 90 ° C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the hardened body to an appropriate degree, the cured body is preferably immersed in a swelling liquid at 40 to 80 ° C for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the hardened body in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably from 5% by mass to 10% by mass. Commercially available oxidizing agents are listed, for example, as Concentrate manufactured by ATOTECH Co., Ltd. of Japan. Alkaline permanganic acid solution such as Compact CP, Doesing Solution Securiganth P, etc. Further, the neutralizing liquid is preferably an acidic aqueous solution, and a commercially available product is, for example, a Reduction Solution Securigant P manufactured by ATOTECH Co., Ltd., Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface subjected to the roughening treatment with the oxidizing agent solution in 30 to 80 ° C and in the liquid for 5 minutes to 30 minutes. From the viewpoint of workability, the object to be subjected to the roughening treatment with the oxidizing agent solution is preferably immersed in 40 to 70 ° C and in the liquid for 5 minutes to 20 minutes.

In the past, when a thin resin composition layer was used and a hard surface having a small surface relief was placed on a circuit substrate, the convex portion of the undulation (that is, the surface of the hardened body on the circuit wiring of the circuit substrate) and the concave portion (that is, the circuit) The surface of the hardened body on the portion of the substrate having no circuit wiring may have a problem of unevenness in roughness due to a surface roughness which is greatly different after the roughening treatment. On the other hand, the roughness unevenness of the roughened hardened body of the present invention obtained by the roughening treatment of the cured body of the present invention is suppressed. That is, the roughened hardened body of the present invention is characterized by the arithmetic mean roughness (Ra ₁ ) of the surface of the roughened hardened body on the circuit wiring of the circuit substrate and the roughened hardened surface on the circuit-free wiring portion of the circuit substrate. The difference in arithmetic mean roughness (Ra ₂ ) (|Ra ₁ -Ra ₂ |) is small. In the roughened and hardened body of the present invention, the value of |Ra ₁ -Ra ₂ | is preferably 160 nm or less, more preferably 140 nm or less, still more preferably 120 nm or less, from the viewpoint of fine wiring formation properties. It is 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, or 50 nm or less. The lower the value of |Ra ₁ -Ra ₂ |, the lower the lower limit can be 0 nm.

When a thin resin composition layer is used to mount a hard surface having a small surface relief on a circuit board, the arithmetic mean roughness (Ra ₁ ) of the surface of the roughened hard surface on the circuit wiring of the circuit substrate may be lower than that of the circuit substrate. The arithmetic mean roughness (Ra ₂ ) of the surface of the roughened hardened body on the circuit wiring portion tends to be high. In the roughened and cured body of the present invention, Ra _{1 is} preferably 300 nm or less, more preferably 270 nm or less, still more preferably 240 nm or less, and most preferably 210 nm or less, 200 nm or less, and 190 nm. Hereinafter, it is 180 nm or less, 170 nm or less, or 160 nm or less. In the roughened and hardened body of the present invention, in the relationship between Ra ₂ and Ra ₁ , the value of |Ra ₁ -Ra ₂ | is preferably a value within the above range. Further, roughening of the cured body of the present invention, Ra Ra ₁ and _2, as the lower limit is not particularly limited, but in order to make the peeling of the conductor layer on the roughened hardened strength and stability of formed thereon, and is set to 10nm or more, 30nm or more.

The roughening and hardening system of the present invention is obtained by subjecting the hardened body of the present invention to a roughening treatment, and the physical property values such as the maximum cross-sectional height Rt or the thickness of the surface are in accordance with the hardened body of the present invention. For example, the roughened hardened body of the present invention is characterized in that the surface maximum cross-sectional height Rt is 3.5 μm or less and the surface undulation is small. The surface maximum cross-sectional height Rt of the roughened and hardened body of the present invention is preferably 3.3 μm or less, more preferably 3.1 μm or less, still more preferably 2.9 μm or less, 2.7 μm or less, 2.5 μm or less, 2.3 μm or less, or 2.1 μm or less. , or 1.9μm or less. Further, in the roughened and cured body of the present invention, the thickness of the roughened and hardened body on the circuit wiring of the circuit board is 15 μm or less, preferably 14 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, and even better. 9 μm or less, 8 μm or less, 7 μm or less, or 6 Below μm. The lower limit of the thickness of the roughened and hardened body on the circuit wiring of the circuit board is usually 0.5 μm or more, preferably 1 μm or more.

[layered body]

The laminate of the present invention comprises the roughened and hardened body of the present invention and a conductor layer formed on the surface of the roughened and hardened body.

The conductor layer is made of a metal layer, and the metal used in the conductor layer is not particularly limited. However, in a preferred embodiment, the conductor layer comprises gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, One or more metals selected from the group consisting of titanium, tantalum, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer is exemplified by an alloy of two or more metals selected from the above group (for example, nickel, chromium alloy, copper, nickel alloy, copper, titanium alloy). The layer formed. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or nickel is preferable from the viewpoints of generality of metal layer formation, cost, ease of etching removal, and the like. . Chrome alloy, copper. Nickel alloy, copper. The alloy layer of titanium alloy is preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or nickel. The alloy layer of chrome alloy is better as a single metal layer of copper.

The conductor layer may have a single layer structure, or may be a multilayer structure in which two or more layers of a single metal layer or an alloy layer made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer adjacent to the roughened hardened body is preferably a single metal layer of chromium, zinc or titanium, or nickel. Alloy layer of chrome alloy.

The thickness of the conductor layer is finely wired to the printed wiring board From the viewpoint of the above, it is preferably 40 μm or less, more preferably 1 to 35 μm, still more preferably 3 to 20 μm. When the metal layer has a multilayer structure, the thickness of the entire metal layer is also preferably in the above range.

The conductor layer can be formed by a desired wiring pattern by a conventional technique such as a semi-additive method or a full additive method. Generally, a dry film for pattern formation is disposed on a roughened hardened body (insulating layer) and a desired pattern is developed, and then a conductor layer having a desired pattern is formed by plating.

In the prior art, when a thin resin composition layer is used to form a hardened body on a circuit board, the surface of the obtained hardened body tends to have a large undulation corresponding to the circuit wiring pattern of the underlying circuit substrate, resulting in a pattern. The problem of the adhesion of the dry film for forming a type is lowered. In the prior art, when a thin resin composition layer is used to provide a hard surface having a small surface roughness on a circuit board, unevenness in roughness may occur. On the other hand, in the technique of the present invention, as described above, since the problem that the adhesion of the dry film for pattern formation is not lowered and the roughness unevenness does not occur, the surface of the hardened body can be roughened. It is advantageous to form a conductor layer having a fine wiring pattern.

In the laminate of the present invention, the line/interval of the conductor layer formed on the surface of the roughened and hardened body is preferably 20/20 μm or less, more preferably 15/15 μm or less, still more preferably 10/10 μm or less, and most preferably 8/8 μm or less.

[Printed wiring board]

The printed wiring board of the present invention is characterized by using the hardened body shape of the present invention. Into the insulation layer.

In one embodiment, the printed wiring board of the present invention can be produced by using the above-described succeeding sheet. In this embodiment, the above-mentioned "Step (A)" and "Step (B)" for bonding the resin composition layer of the sheet to the circuit board can be performed to form the cured body of the present invention on the circuit board. Further, when the sheet has a protective film, the protective film can be removed and then produced.

Next, the hardened body formed on the circuit board is subjected to the above-described "roughening treatment" to form a roughened and hardened body, and then a conductor layer is formed on the surface of the roughened and hardened body. Further, in the production of the printed wiring board, a step of forming a via on the insulating layer, a step of removing the resin residue (slag) inside the via hole, and the like may be further included. These steps are well known in the art and can be carried out in accordance with various methods used in the manufacture of printed wiring boards.

The printed wiring board of the present invention has a high degree of thickness reduction and a fine wiring of a circuit.

[semiconductor device]

A semiconductor device can be manufactured using the above printed wiring board.

The semiconductor device is exemplified by various semiconductor devices such as electric products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, locomotives, automobiles, electric cars, ships, airplanes, etc.).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention It is not limited to the embodiments. In the following description, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.

First of all, for various measurement methods. The evaluation method will be explained.

[Measurement. Preparation of sample for evaluation] (1) Underlying processing of circuit board

On the two sides of the glass cloth substrate epoxy resin laminated copper plate (copper foil thickness 18μm, substrate thickness 0.3mm, "R5715ES" made by Matsushita Electric Works), according to IPC MULTI-PURPOSE TEST BOARD NO.IPC B- The pattern of 25 (line/space ratio = 175/175 μm comb pattern (50% residual copper ratio) forms a circuit. Both sides of the obtained circuit board are immersed in "CZ8100" manufactured by Merck Co., Ltd. for copper surface The roughening process.

(2) Lamination of the resin composition layer

A batch vacuum laminate laminator ("MVLP-500" manufactured by Nihon Seisakusho Co., Ltd.) was used to laminate the resin composition layer and the circuit substrate, and the laminate sheets produced in the examples and the comparative examples were laminated. On both sides of the circuit board. The laminates of the resin composition layers were subjected to a lamination treatment at 120 ° C and a pressure of 0.74 MPa for 30 seconds by subjecting the gas pressure to 13 hPa or less under reduced pressure for 30 seconds in Examples 1 to 3 and Comparative Example 2. Subsequently, the mixture was heat-pressed at 120 ° C and a pressure of 0.5 MPa for 60 seconds to carry out a smoothing treatment.

Regarding Comparative Example 1, the temperature of the laminating treatment and the smoothing treatment was changed. The lamination treatment and the smoothing treatment were carried out under the same conditions as in Examples 1 to 3 and Comparative Example 2 except for 90 °C.

(3) Thermal hardening of the resin composition layer

After the resin composition was laminated, the PET film of the support was peeled off. Subsequently, the resin composition layer was held at 100 ° C for 30 minutes, and then heat-hardened at 180 ° C for 30 minutes to form a hardened body on the circuit board.

The obtained cured body was evaluated for the maximum cross-sectional height Rt of the surface of the cured body, the thickness of the hardened body on the circuit wiring, and the resin embedding property.

(4) Formation of through holes

Hitachi VIA MECHANICS (shares) manufactured by CO ₂ laser processing machine of the "LC-2E21B / 1C ', of the cured body is punched to form the through hole. The diameter (diameter) of the tip end of the through hole on the surface of the hardened body was 50 μm. Moreover, the conditions of the perforation processing are a mask diameter of 1.60 mm, a focus offset value of 0.050, a pulse width of 25 μs, an energy of 0.33 mJ/emission (output of 0.66 W, frequency of 2000 Hz), aperture 13 and number of shots 2, Burst mode.

(5) roughening treatment

After the via holes are formed, the circuit board on which the hardened body is formed is subjected to a roughening treatment in the following order to obtain a roughened and hardened body. In other words, the circuit board on which the hardened body is formed is immersed in a swelling liquid at 60 ° C (Sweeling Dip Securiganth P, manufactured by ATOTECH Co., Ltd., diethylene glycol monobutyl ether, and hydrogen). 5 minutes in an aqueous solution of sodium oxide, followed by immersion in an oxidizing agent solution (Concentrate. Compact CP) manufactured by ATOTECH Co., Ltd., an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%. The mixture was immersed in a solution (Reduction Solution Securigant P, manufactured by ATOTECH Co., Ltd., Aqueous Sulfate, Japan) for 5 minutes, and after immersion, it was dried at 130 ° C for 15 minutes.

The roughness unevenness was evaluated about the obtained roughened hardened body.

(6) Formation of conductor layer

A conductor layer is formed on the surface of the roughened hardened body according to a semi-additive method.

That is, the circuit board on which the roughened and hardened body was formed was immersed in an electroless copper plating solution containing PdCl ₂ , and then annealed at 150 ° C for 30 minutes. Thereby, a plating seed layer is formed on the surface of the roughened hardened body.

The surface of the obtained plating seed layer was treated with a 5% sulfuric acid aqueous solution for 30 seconds, and then a dry film for pattern formation ("ALPHO 20A263" manufactured by Nichigo Morton Co., Ltd., thickness: 20 μm) was laminated on the plating seed layer. For the lamination of the dry film for pattern formation, a batch vacuum lamination machine ("MVLP-500" manufactured by Nihon Seisakusho Co., Ltd.) was used, and the pressure was reduced to 13 hPa or less after 30 seconds of decompression, and the pressure was changed to 70 ° C and 0.1 at 70 ° C. MPa lamination treatment was carried out for 20 seconds. Next, a glass mask configuration of a comb pattern (wire length 15 mm, 16 lines) of 16 μm pitch of L (dry film line) / S (interval) = 8 / 8 μm was formed. On the PET film of the protective layer of the dry film, UV irradiation was performed by a UV lamp at an irradiation intensity of 150 mJ/cm ^{2 ,} and after UV irradiation, a 1% sodium carbonate aqueous solution at 30 ° C was used, and a spray treatment was performed at a spray pressure of 0.15 MPa for 30 seconds. Subsequently, washing with water was carried out to develop a dry film (formation pattern). After dry film development, the adhesion of the dry film was evaluated.

Electrolytic copper plating was performed on the substrate having good dry film adhesion to form a conductor layer having a thickness of 15 μm. Next, a spray treatment was carried out using a 3% sodium hydroxide solution at 50 ° C at a spray pressure of 0.2 MPa, and the dry film was peeled off. Subsequently, the excess plating plating layer was removed by a SAC process manufactured by Ebara Electric Co., Ltd. to form a printed wiring board.

The fine wiring formation property was evaluated about the obtained printed wiring board.

<Measurement of the lowest melt viscosity temperature Tv of the resin composition layer>

The lowest melt viscosity temperature Tv of the resin composition layer of the succeeding sheet produced in the examples and the comparative examples was measured by a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM Co., Ltd.), and the amount of the resin composition sample was 1 g. Using a parallel plate having a diameter of 18 mm, the temperature was raised from the start temperature of 60 ° C to 200 ° C at a temperature increase rate of 5 ° C / min, and the lowest melt viscosity was measured at a temperature interval of 2.5 ° C, a vibration number of 1 Hz, and a strain of 1 degree. The temperature.

<Measurement of the maximum profile height Rt of the surface of the hardened body>

The maximum cross-sectional height Rt of the surface of the hardened body on the circuit board is a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Veeco Instruments Co., Ltd.), and the measurement range is set by using a VSI contact mode and a 10x lens. The value obtained by 0.82 mm × 1.1 mm was obtained. In addition, the measurement system is for a comb pattern with a wire/space ratio ratio of 175/175 μm. The area of the circuit wiring (the residual copper ratio is 50%) is obtained by calculating the average value of the three parts so as to cross the part having the circuit wiring and the portion having no circuit wiring.

In addition, in Table 1, the case where the maximum profile height Rt is 3.5 μm or less is referred to as "○", and the case where the maximum profile height Rt exceeds 3.5 μm is referred to as "x".

<Measurement of Thickness of Hardened Body on Circuit Board of Circuit Board>

The thickness (y) of the hardened body on the circuit board of the circuit board is a square of a circuit pattern of a comb-tooth pattern having a wire/space ratio ratio of 175/175 μm, and is cut into a square having a side length of 1 cm to form a transparent sealing resin (Marumoto). The unsaturated polyester resin manufactured by Struers Co., Ltd. was sealed, and after the cross section was polished, it was measured by a scanning electron microscope ("S4800" manufactured by Hitachi High-Tech Co., Ltd.). The measurement was performed by calculating the average value of 5 points.

<Evaluation of the embedding property of resin>

The embedding property of the resin was evaluated by observing the surface of the hardened body with a scanning electron microscope ("S4800" manufactured by Hitachi High-Tech Co., Ltd.).

In addition, in Table 1, the case where the hole was not formed or the resin was oozing out was marked as "○", and the case where the hole occurred or the resin bleed out was recorded as "x".

<Evaluation of roughness unevenness>

The unevenness of the surface roughness of the roughened hardened body is the arithmetic mean roughness (Ra ₁ ) of the surface of the roughened hardened body on the circuit wiring of the circuit board, and the surface of the roughened hardened body on the circuit-free wiring portion of the circuit board The arithmetic mean roughness (Ra ₂ ) is calculated by finding the value of |Ra ₁ -Ra ₂ |. The arithmetic mean roughness (Ra ₁ and Ra ₂ ) of the surface of the roughened hardened body is measured by using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Veeco Instruments Co., Ltd., by VSI contact mode, 50-fold lens). The value obtained by the range of 92 × 123 μm was obtained, and the average of three points was obtained for Ra ₁ and Ra ₂ , respectively.

In addition, in Table 1, when the value of |Ra ₁ -Ra ₂ | is 160 nm or less, it is indicated as "○", and when it exceeds 160 nm, it is indicated as "X".

<Evaluation of adhesion of dry film for pattern formation>

The adhesion of the dry film for pattern formation is directed to a region of a circuit wiring having a comb-tooth pattern of a line/space ratio ratio of 175/175 μm, and a scanning electron microscope ("S4800" manufactured by Hitachi High-Tech Co., Ltd.). The state in which the roughened hardened body (plated seed layer) and the dry film were adhered was observed.

In addition, in Table 1, the film on the dry film is not peeled off. The situation of the uplift is recorded as "○" and there is stripping. The situation of the uplift is recorded as "X".

<Evaluation of the formation of fine wiring>

The fine wiring formation property was confirmed by an optical microscope to confirm the presence or absence of peeling of the conductor layer, and the insulation resistance of the comb pattern was measured to confirm the presence or absence of unnecessary plating seed layer.

In Table 1, those in which the conductor layer is not peeled off and the plating seed layer is not left are referred to as "○", and those in which the conductor layer is peeled off and/or the residual plating layer is left are referred to as "x".

[Production Example 1] (1) Modification of resin paint

10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "jER828EL" by Mitsubishi Chemical Co., Ltd.) and biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Kayaku Co., Ltd.) "NC3000L") 20 parts, 4 parts of a naphthalene type epoxy resin (epoxy equivalent 163, "HP4700" manufactured by DIC), and phenoxy resin ("LM7553BH30" manufactured by Mitsubishi Chemical Corporation), solid 10 parts by mass of a 1:1 solution of MEK and cyclohexanone) 10 parts of a mixed solvent of 5 parts of MEK, 5 parts of cyclohexanone and 15 parts of solvent naphtha were heated and dissolved while stirring. After cooling to room temperature, 15 parts of a triazine-containing phenol novolak-based curing agent (hydroxyl equivalent of 125, "LA7054" by DIC (manufactured by DIC), and 60% by mass of MEK solution of solid content) was mixed therein, and naphthol-based hardening was carried out. 15 parts of a reagent (hydroxyl equivalent 215, "SN-485" manufactured by Tohto Kasei Co., Ltd., 60% solid solution of MEK), an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid component 5) 1 part by mass of MEK solution), an imidazole-based hardening accelerator (1-benzyl-2-phenylimidazole, "1B2PZ" manufactured by Shikoku Chemicals Co., Ltd., and a solid content of 5% by mass of MEK solution) 0.3 parts , a flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, manufactured by Sanguang Co., Ltd., Spherical cerium oxide (average particle diameter: 0.5 μm, "SOC2" manufactured by ADMATECHS), which is surface-treated with an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), having an average particle diameter of 2 μm. The amount of carbon per unit area is 0.39 mg/m ² ) 140 parts, polyvinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd.), solid content 15% by weight of ethanol and toluene 1: 1 solution) 15 parts, rotating at high speed Uniformly dispersed to prepare a resin varnish.

(2) followed by modulation of sheet 1

A PET film (manufactured by LINTEC Co., Ltd., a polyethylene terephthalate film with an alkyd type release agent (AL-5)) having a release layer was prepared as a support. The resin paint obtained in the above (1) is uniformly applied to the release surface of the support by a die coater so as to have a thickness of the resin composition layer after drying to 15 μm, at 80 to 110 ° C ( Drying for an average of 100 to 4 minutes for 2 to 4 minutes to form a subsequent sheet 1. Next, the lowest melt viscosity temperature Tv of the resin composition layer of the sheet 1 was 130 °C.

[Production Example 2]

The subsequent sheet 2 was produced in the same manner as in Production Example 1, except that the resin coating material was uniformly applied to the die coater so that the thickness of the resin composition layer after drying was 20 μm. Next, the lowest melt viscosity temperature Tv of the resin composition layer of the sheet 2 was 127 °C.

[Production Example 3]

The subsequent sheet 3 was produced in the same manner as in Production Example 1, except that the resin coating material was uniformly applied to the die coater so that the thickness of the resin composition layer after drying was 25 μm. Next, the lowest melt viscosity temperature Tv of the resin composition layer of the sheet 3 was 127 °C.

[Production Example 4]

The subsequent sheet 4 was produced in the same manner as in Production Example 1, except that the resin coating material was uniformly applied to the die coater so that the thickness of the resin composition layer after drying was 15 μm. Next, the lowest melt viscosity temperature Tv of the resin composition layer of the sheet 4 was 130 °C.

[Production Example 5]

The subsequent sheet 5 was produced in the same manner as in Production Example 1, except that the resin coating material was uniformly applied to the die coater so that the thickness of the resin composition layer after drying was 10 μm. Next, the lowest melt viscosity temperature Tv of the resin composition layer of the sheet 5 was 140 °C.

<Example 1>

Use the following sheet 1, according to the above [Measurement. A printed wiring board was produced in the order of the preparation of the sample for evaluation. The results of each evaluation are shown in Table 1.

<Example 2>

Use the following sheet 2, according to the above [Measurement. A printed wiring board was produced in the order of the preparation of the sample for evaluation. The results of each evaluation are shown in Table 1.

<Example 3>

Use the following sheet 3, according to the above [Measurement. A printed wiring board was produced in the order of the preparation of the sample for evaluation.

The results of each evaluation are shown in Table 1.

<Comparative Example 1>

Use the following sheet 4, according to the above [Measurement. A printed wiring board was produced in the order of the preparation of the sample for evaluation. Further, as shown in the above [Preparation of Sample for Evaluation A Evaluation], the laminate temperature of the resin composition layer of Comparative Example 1 was 90 °C. The results of each evaluation are shown in Table 1.

<Comparative Example 2>

Use the following sheet 5, according to the above [Measurement. A printed wiring board was produced in the order of the preparation of the sample for evaluation. The results of each evaluation are shown in Table 1.

A thin resin composition layer is used to make the layer thinner When confirming that the laminate temperature of the resin composition layer is Tv-35 ° C~ When the range of Tv + 35 ° C is carried out, it is attributed to a hardened body having a large surface undulation and poor adhesion of the dry film (Comparative Example 1). It is also confirmed that the surface temperature of the resin composition layer is in the range of Tv - 35 ° C to Tv + 35 ° C, although the surface of the hardened body can be suppressed from fluctuating, but if x and y do not satisfy 0.3 < y / x ≦ 1 and y ≦ In the relationship of 15, significant roughness unevenness occurred (Comparative Example 2).

On the other hand, the laminate temperature of the resin composition layer is in the range of Tv - 35 ° C - Tv + 35 ° C, and x and y satisfy the relationship of 0.3 < y / x ≦ 1 and y ≦ 15 in Examples 1 to 3, even if When a thin resin composition layer is used for the thinning of the layer, a hardened body which retains sufficient dry film adhesion and has a small surface undulation can be realized, and occurrence of roughness unevenness can be suppressed.

Claims (15)

A hardened body obtained by laminating a resin composition on a circuit board and thermally curing the resin composition layer to obtain a hardened body provided on a circuit board, wherein a minimum melt viscosity temperature of the resin composition layer is set to In Tv (°C), the lamination temperature of the resin composition layer is Tv-35° C. to Tv+35° C., the thickness of the resin composition layer is set to x (μm), and the thickness of the hardened body on the circuit board of the circuit board is set. When it is set to y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15. The hardened body of claim 1, wherein x ≦ 25. The hardened body of claim 1, wherein the surface of the hardened body has a maximum cross-sectional height Rt of 3.5 μm or less. The hardened body of claim 1, wherein the resin composition layer contains an inorganic filler, and the content of the inorganic filler in the resin composition layer is 50% by mass or more. The hardened body according to claim 1, wherein the resin composition layer is maintained at a temperature less than Tv for 10 minutes or more, and then thermally cured at a temperature of Tv or higher for 10 minutes or longer. A roughened hardened body obtained by subjecting a hardened body of claim 1 to a roughening treatment. The roughened hardened body of claim 6, wherein the arithmetic mean roughness of the surface of the roughened hardened body on the circuit wiring of the circuit substrate and the arithmetic mean roughness of the roughened hardened surface on the portion of the circuit board without the circuit wiring The difference between the degrees is 160 nm or less. A laminated body comprising the roughened hardened body according to claim 6 or 7, and a conductor layer formed on the surface of the roughened hardened body. A method for producing a hardened body, comprising the steps of: (A) laminating a resin composition on a circuit substrate, and (B) thermally curing the resin composition layer to form a hardened body on the circuit substrate, When the lowest melt viscosity temperature of the resin composition layer is Tv (° C.), the laminate temperature of the resin composition layer is Tv-35 ° C to Tv + 35 ° C, and the thickness of the resin composition layer is set to x (μm). When the thickness of the hardened body on the circuit wiring of the circuit board is y (μm), it is 0.3 < y / x ≦ 1 and y ≦ 15. A method of producing a hardened body according to claim 9, wherein x ≦ 25. The method for producing a hardened body according to claim 9, wherein the maximum cross-sectional height Rt of the surface of the hardened body is 3.5 μm or less. The method for producing a cured body according to claim 9, wherein the resin composition layer contains an inorganic filler, and the content of the inorganic filler in the resin composition layer is 50% by mass or more. The method for producing a cured body according to any one of claims 9 to 12, wherein in the step (B), the resin composition layer is maintained at a temperature not higher than Tv for 10 minutes or more, and then maintained at a temperature of Tv or higher for 10 minutes or longer. And it is thermally hardened. A printed wiring board in which an insulating layer is formed by the hardened body according to any one of claims 1 to 5. A semiconductor device comprising a printing package as claimed in claim 14 Wire board.