TW201540138A - Printed wiring board - Google Patents

Abstract

The subject of the present invention is to provide a thin printed wiring board capable of inhibiting warpage in a component installation step. To solve the problem, the printed wiring board includes a first solder resist layer and a second solder resist layer, wherein the first solder resist layer has a thickness of t1 ([mu]m) and an elasticity rate of G1 (GPa) after being cured (23DEG C), and the second solder resist layer has a thickness of t2 ([mu]m) and an elasticity rate of G2 (GPa) after being cured (23DEG C). When the thickness of the printed wiring board is Z ([mu]m), the following equations (1)-(3) are satisfied: (1) Z ≤ 250, (2) (t1+t2)/Z ≤ 0.1, and (3) G1×(t1/(t1+t2))+G2×(t2/(t1+t2)) ≤ 6, where G1 is greater than 6.

Description

Printed wiring board

The present invention relates to a printed wiring board.

The outermost layer of the printed wiring board is usually provided with a solder resist layer in order to prevent the solder from adhering to the portion that does not need to adhere and prevent the circuit substrate from being corroded during the mounting step of the semiconductor wafer (hereinafter also referred to as "parts"). membrane. The solder resist layer is generally formed by providing a layer of a photocurable resin composition on a circuit board, and exposing/developing the layer (for example, Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-258613

In recent years, with the replacement of lead-containing solder by lead-free solder, the solder reflow temperature rises during the mounting step of the part. In recent years, in order to The miniaturization of electronic equipment has been achieved, and the thickness of printed wiring boards has been increasing.

As the thickness of the printed wiring board progresses, the inventors have found that in the mounting step of the component, the printed wiring board is warped, and there is a problem that the circuit is twisted or the contact of the component is poor.

The present invention has been made in an effort to provide a thin printed wiring board which can suppress warpage in the component mounting step.

As a result of reviewing the above-mentioned problems, the inventors of the present invention have found that the above problems can be solved by combining two solder resist layers having a specific thickness and an elastic modulus, and the present invention has been completed.

That is, the present invention encompasses the following.

[1] A printed wiring board comprising a printed wiring board having a first and a second solder resist layer, wherein a thickness of the first solder resist layer is t ₁ (μm), and an elastic modulus (23 ° C) after curing is G ₁ (GPa), the thickness of the second solder resist layer is t ₂ (μm), and the modulus of elasticity after hardening (23 ° C) is G ₂ (GPa), and when the thickness of the printed wiring board is Z (μm) , satisfying the following conditions (1) to (3): (1) Z ≦ 250; (2) (t ₁ + t ₂ ) / Z ≧ 0.1; and (3) G ₁ × [t ₁ / (t ₁ + t ₂ )]+G ₂ ×[t ₂ /(t ₁ +t ₂ )]≧6, and G ₁ is 6 or more.

[2] The printed wiring board according to [1], wherein the glass transition temperature (Tg) after curing of the first solder resist layer is 150 ° C or higher.

[3] The printed wiring board according to the above [1], wherein the first solder resist layer is formed by curing a resin composition having an inorganic filler content of 60% by mass or more.

[4] The printed wiring board according to any one of [1] to [3] wherein the condition (2) is 0.1 ≦(t ₁ + t ₂ ) / Z ≦ 0.5.

[5] The printed wiring board according to any one of [1] to [4] wherein G ₂ is 6 or more.

[6] The printed wiring board according to any one of [1], wherein the elastic modulus (200 ° C) after curing of the first solder resist layer is G ₁ ' (GPa), and the second resistance is obtained. When the elastic modulus (200 ° C) after hardening of the flux layer is G ₂ '(GPa), the following condition (4) is further satisfied: (4) G ₁ '×[t ₁ /(t ₁ +t ₂ )]+ G ₂ '×[t ₂ /(t ₁ +t ₂ )]≧0.2.

[7] A semiconductor device comprising the printed wiring board according to any one of [1] to [6].

[8] A resin sheet group which is a resin sheet group for a solder resist layer of a printed wiring board, comprising a first resin body and a first resin composition layer joined to the first support body. a resin sheet, a second resin sheet having a second support and a second resin composition layer joined to the second support, and having a thickness of the first resin composition layer of t _1p (μm) and after curing The elastic modulus (23 ° C) is G ₁ (GPa), the thickness of the second resin composition layer is t _2p (μm), and the elastic modulus after curing (23 ° C) is G ₂ (GPa), and the printed wiring is made. When the thickness of the plate is Z (μm), the following conditions (1') to (3') are satisfied: (1') Z ≦ 250; (2') (t _1p + t _2p ) / Z ≧ 0.1; 3') G ₁ ×[t _1p /(t _1p +t _2p )]+G ₂ ×[t _2p /(t _1p +t _2p )]≧6, and G ₁ is 6 or more.

According to the present invention, it is possible to provide a thin printed wiring board which can suppress warpage in the mounting step of a part.

[Formation of the Invention] [Printed wiring board]

The printed wiring board of the present invention includes the first and second solder resist layers, wherein the first solder resist layer has a thickness t ₁ (μm) and the cured elastic modulus (23 ° C) is G ₁ (GPa). When the thickness of the second solder resist layer is t ₂ (μm), and the elastic modulus after curing (23 ° C) is G ₂ (GPa), and the thickness of the printed wiring board is Z (μm), the following is satisfied. Conditions (1) to (3): (1) Z ≦ 250; (2) (t ₁ + t ₂ ) / Z ≧ 0.1; and (3) G ₁ × [t ₁ / (t ₁ + t ₂ )] +G ₂ ×[t ₂ /(t ₁ +t ₂ )]≧6, and G ₁ is 6 or more.

The printed wiring board of the present invention comprising a combination of the first and second solder resist layers having a specific thickness and an elastic modulus can suppress warpage and suppress the circuit in a mounting step of a component using a high solder reflow temperature. Problems such as twisting or poor contact of parts.

- Condition (1)-

The condition (1) is the thickness Z (μm) of the printed wiring board of the present invention. The thickness Z of the printed wiring board means the entire thickness of the printed wiring board including the circuit board and the first and second solder resist layers provided on both sides of the circuit board. The thickness (Z) of the printed wiring board of the present invention is 250 μm or less, preferably 240 μm or less, more preferably 230 μm or less, still more preferably 220 μm or less, still more preferably 210 μm or less, from the viewpoint of thinning. It is particularly preferably 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, or 150 μm or less. The printed wiring board of the present invention can suppress the warpage in the mounting step even when the thickness is as small as possible. The lower limit of the thickness (Z) is not particularly limited, and is usually 20 μm or more, or 30 μm or more.

- Condition (2)-

The condition (2) is the thicknesses t ₁ (μm) and t ₂ (μm) of the first and second solder resist layers contained in the printed wiring board of the present invention. Here, the thicknesses t ₁ (μm) and t ₂ (μm) of the first and second solder resist layers are the thicknesses of the base surface of the circuit board (the portion of the circuit board surface having no surface circuit). Suppressing warpage of the printed wiring board from the mounting step, the thickness of the first and second solder resist layer, and (t ₁ + t ₂₎ than the thickness of the printed wiring board of Z, i.e., (t ₁ + t ₂ ) The /Z ratio is 0.1 or more, and is preferably 0.15 or more, more preferably 0.2 or more, 0.22 or more, 0.24 or more, 0.26 or more, 0.28 or more, or 0.3 or more, depending on the value on the right side of the condition (3). The upper limit of the (t ₁ + t ₂ )/Z ratio is preferably 0.5 or less, more preferably 0.45 or less, still more preferably 0.4 or less, from the viewpoint of obtaining a printed wiring board having a desired wiring density. Hereinafter, it is 0.38 or less, 0.37 or less, 0.36 or less, 0.36 or less, or 0.34 or less.

The thickness t _{1 of the} first solder resist layer is not particularly limited as long as the specific (t ₁ + t ₂ )/Z ratio is satisfied, and is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more, 20 μm or more or 25 μm or more. The upper limit of the thickness t ₁ is not particularly limited, and is not particularly limited as long as the specific (t ₁ + t ₂ )/Z ratio is satisfied, and is preferably 120 μm or less, more preferably 100 μm or less, still more preferably 80 μm. Hereinafter, it is 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less.

The thickness t _{2 of} the second solder resist layer is not particularly limited when the specific (t ₁ + t ₂ )/Z ratio is satisfied, and the thickness t _{1 of the} first solder resist layer and the printed wiring board are considered. The thickness Z can be determined. The upper limit of the thickness t ₂ of the second solder resist layer may be usually 120 μm or less or 100 μm or less, and the lower limit of the thickness t ₂ is usually 5 μm or more or 10 μm or more.

- Condition (3) -

The condition (3) is the modulus of elasticity (23 ° C) after curing of the first and second solder resist layers contained in the printed wiring board of the present invention. The first and second solder resist layers can be formed by curing the resin composition as will be described later. The modulus of elasticity after hardening (23 ° C) is the modulus of elasticity of the solder resist layer at 23 ° C after the resin composition is cured. When the elastic modulus (23 ° C) after curing of the first and second solder resist layers is G ₁ (GPa) and G ₂ (GPa), respectively, the formula: G ₁ ×[t ₁ /(t ₁ +t ₂ ) The value of +G ₂ ×[t ₂ /(t ₁ +t ₂ )] (hereinafter also referred to as "the average thickness of the thicknesses of G ₁ and G ₂ "), from suppressing the warpage of the printed wiring board in the mounting step In view of the above, it is 6 or more, preferably 6.2 or more, more preferably 6.4 or more, still more preferably 6.6 or more, and still more preferably 6.8 or more. When the thickness average of G ₁ and G ₂ is 6.8 or more and the thickness Z of the printed wiring board is 200 μm or less, the warpage of the printed wiring board in the mounting step can be suppressed even when it is thin. The thickness of G ₁ and G ₂ is increased by the average value, and the printed wiring board in the mounting step is suppressed even if the thickness Z of the printed wiring board is made small and the (t ₁ + t ₂ )/Z ratio is made lower. From the viewpoint of warpage, it is particularly preferably 7 or more, 7.5 or more, 8 or more, 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, or 13 or more. . The upper limit of the thickness average of G ₁ and G ₂ is not particularly limited, and may be usually 40 or less, 30 or less, or the like. The elastic modulus (23 ° C) after curing of the first and second solder resist layers can be measured by a tensile tester at 23 ° C using a tensile tester. For the tensile tester, for example, "RTC-1250A" manufactured by ORIENTEC can be mentioned.

The elastic modulus (23 ° C) after hardening of the first solder resist layer, that is, G ₁ (GPa) is 6 or more. The value of G ₁ is 6 or more, and the average thickness of G ₁ and G ₂ is not particularly limited as long as it is within the above specific range, and it is preferable from the viewpoint of sufficiently suppressing warpage of the printed wiring board in the mounting step. It is 6.2 or more, more preferably 6.4 or more, still more preferably 6.6 or more, and even more preferably 6.8 or more, particularly preferably 7 or more, 7.5 or more, 8 or more, 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5. The above is 11 or more, 11.5 or more, 12 or more, 12.5 or more, or 13 or more. The upper limit of G ₁ is not particularly limited, but may be usually 40 or less, 30 or less, or the like.

The elastic modulus (23 ° C) after curing of the second solder resist layer, that is, G ₂ (GPa), is not particularly limited as long as the average thickness of G ₁ and G ₂ is within the above specific range. For example, as long as the value G ₂ is G ₁ and G ₂ the thickness of the average increase in the specific range may be determined to be in the range of 1 to 30. The value of G ₂ is easily suppressed from the viewpoint of suppressing the warpage of the printed wiring board in the mounting step even when the thickness Z of the printed wiring board is made small and the ratio of (t ₁ + t ₂ )/Z is made lower. It is especially good if it is 6 or more.

From the viewpoint of further suppressing the warpage of the printed wiring board in the mounting step, the elastic modulus (200 ° C) after curing of the first and second solder resist layers is G ₁ '(GPa) and G _{2 .} In the case of '(GPa), the following condition (4) is satisfied: (4) G ₁ '×[t ₁ /(t ₁ +t ₂ )]+G ₂ '×[t ₂ /(t ₁ +t ₂ )] ≧0.2 is better.

The value of G ₁ '×[t ₁ /(t ₁ +t ₂ )]+G ₂ '×[t ₂ /(t ₁ +t ₂ )] (hereinafter also referred to as the thickness of "G ₁ ' and G ₂ ') It is more preferable that the average value is 0.22 or more, and more preferably 0.24 or more. When the average thickness of G ₁ ' and G ₂ ' is 0.24 or more, even when the thickness Z of the printed wiring board is made thinner than 200 μm, the warpage of the printed wiring board in the mounting step can be suppressed. The thickness average of G ₁ ' and G ₂ ' is increased, and the printed wiring in the mounting step is suppressed even if the thickness Z of the printed wiring board is made small and the ratio of (t ₁ + t ₂ )/Z is made lower. From the viewpoint of warpage of the sheet, it is particularly preferably 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, 1.2 or more, 1.3 or more, or 1.4 or more. The upper limit of the thickness average of G ₁ ' and G ₂ ' is not particularly limited, and may be usually 15 or less, 10 or less, or the like. In addition, the modulus of elasticity after hardening (200 ° C) is the modulus of elasticity of the solder resist layer at 200 ° C after curing the resin composition, and can be used in a tensile tester at 200 ° C by a tensile weighting method. Determination.

The elastic modulus (200 ° C) after curing of the first solder resist layer, that is, G ₁ '(GPa), is preferably 0.2 or more from the viewpoint of sufficiently suppressing the warpage of the printed wiring board in the mounting step. More preferably, it is 0.22 or more, more preferably 0.24 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, 1.2 or more, 1.3 or more, or 1.4 or more. Especially good. The upper limit of G ₁ ' is not particularly limited, but may be usually 15 or less, 10 or less, or the like.

The elastic modulus (200 ° C) after hardening of the second solder resist layer, that is, G ₂ '(GPa), in the relationship with G ₁ ', the thickness of G ₁ ' and G ₂ ' is increased by an average value as described above. The value of a particular range is preferred. For example, the 'value, as long as the G _1' G ₂ and a thickness G ₂ 'is the average increase in the specific range, preferably in the line to the range of 0.1 to 10. The value of G ₂ ' is easily suppressed from the viewpoint of suppressing the warpage of the printed wiring board in the mounting step even when the thickness Z of the printed wiring board is made small and the (t ₁ + t ₂ )/Z ratio is lower. It is particularly good if it is 0.2 or more.

In the printed wiring board of the present invention which satisfies the above conditions (1), (2) and (3), warpage can be suppressed even in a mounting step using a high solder reflow temperature. In one embodiment, the printed wiring board of the present invention can suppress the warpage of the printed wiring board to 50 μm or less in the mounting step of using a high solder reflow temperature of a peak temperature of 260 °C. In the present invention, the warpage of the printed wiring board is a difference between the maximum height and the minimum height of the displacement data when the warping behavior of the 25 mm corner portion of the center of the printed wiring board is observed by a Shadow Moire device. value. At the time of measurement, the reflow temperature profile described in IPC/JEDEC J-STD-020C ("Moisture/Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices", July 2004) was reproduced (the curve for lead-free components; peak temperature) After the reflow device was introduced into the printed wiring board once at 260 ° C for 5 minutes from 25 ° C to the peak temperature, the printed wiring was heat-treated by the reflow profile according to the above IPC/JEDEC J-STD-020C. One side of the board, and the grid line provided on the other side of the printed wiring board determines the displacement data. In addition, for the reflow device, for example, "HAS-6116" manufactured by ANTU Co., Ltd., and the "shadowing device" may be, for example, "TherMoire AXP" manufactured by Akrometrix. By setting the value of the right side in the condition (3) to the above preferred value, even if the thickness Z of the printed wiring board is made small and the (t ₁ + t ₂ )/Z ratio is lower, the mounting can be performed. In the step, the warpage of the printed wiring board is suppressed to 48 μm or less, 46 μm or less, 44 μm or less, 42 μm or less, or 40 μm or less.

[Resin sheet group for solder resist layer of printed wiring board]

The printed wiring board of the present invention can be manufactured by providing the first and second solder resist layers having a specific thickness and modulus of elasticity on both surfaces of the circuit board.

Hereinafter, a set of resin sheets ("resin sheet group") which are used in the production of the printed wiring board of the present invention will be described.

The resin sheet group for a solder resist layer of a printed wiring board according to the present invention is characterized in that it comprises a first resin sheet having a first support and a first resin composition layer joined to the first support, and a first resin sheet. (2) The second resin sheet formed of the second resin composition layer joined to the second support, and the thickness of the first resin composition layer is t _1p (μm) and the modulus of elasticity after curing (23) °C) is G ₁ (GPa), the thickness of the second resin composition layer is t _2p (μm), the elastic modulus after curing (23 ° C) is G ₂ (GPa), and the thickness of the printed wiring board is Z. (μm), the following conditions (1') to (3') are satisfied: (1') Z ≦ 250; (2') (t _1p + t _2p ) / Z ≧ 0.1; and (3') G ₁ ×[t _1p /(t _1p +t _2p )]+G ₂ ×[t _2p /(t _1p +t _2p )]≧6, and G ₁ is 6 or more.

By forming the first and second solder resist layers by using the resin sheet group, the printed wiring board of the present invention satisfying the conditions (1), (2), and (3) can be easily manufactured.

The condition (1') corresponds to the above condition (1). The preferred range of Z is as described in Condition (1).

The condition (2') corresponds to the above condition (2). When a resin composition layer is laminated on a circuit board and a solder resist layer is formed, the surface circuit of the circuit board is present as a cause. Generally, the thickness of the obtained solder resist layer is thicker than the thickness of the resin composition layer. Therefore, by satisfying the condition (2'), it is not affected by the thickness of the surface circuit of the circuit substrate or the density of the surface circuit, and the condition (2) is easily satisfied. In the condition (2'), when the preferred range of (t _1p + t _2p )/Z ratio is determined, "t ₁ " and "t ₂ " in condition (2) can be interpreted as "t _1p " and Applicable to "t _2p ". Similarly, in the preferred range of t _1p and t _2p , in the description of the preferred ranges of t ₁ and t ₂ described in the above condition (2), "t ₁ " and "t ₂ " can be respectively used. It is applicable to read "t _1p " and "t _2p ". Further, it is preferable to determine t _1p and t _2p so as to be thick or thicker than the surface circuit thickness of the circuit board.

The condition (3') corresponds to the above condition (3). When the modulus of elasticity after hardening of the solder resist layer (23 ° C) indicates the elastic modulus (23 ° C) after curing of the resin composition constituting the solder resist layer, as described above, the preferred ranges of G ₁ and G ₂ are As explained in condition (3). Further, the preferable range of the value on the right side of the condition (3') is as described in the condition (3).

From the viewpoint of further suppressing the warpage of the printed wiring board in the mounting step, the elastic modulus (200 ° C) after curing of the first and second resin composition layers is G ₁ '(GPa) and G ₂ ', respectively. In the case of (GPa), the following condition (4') is satisfied: (4') G ₁ '×[t _1p /(t _1p +t _2p )]+G ₂ '×[t _2p /(t _1p +t _2p )〕 ≧ 0.2 is good. The preferred range of the value on the right side of the condition (4') is as described in the condition (4), and the preferred range of G ₁ ' and G ₂ ' is as described in the condition (4).

<Resin composition>

The resin composition used in the first and second resin composition layers may have sufficient chemical resistance and insulation properties while exhibiting the specific elastic modulus after curing, and may be a thermosetting resin composition. The material may also be a photocurable resin composition. For example, a thermosetting resin composition is a resin composition containing a thermosetting resin and a curing agent. As the thermosetting resin, a conventionally known thermosetting resin used for forming a solder resist layer of a printed wiring board can be used, and among them, an epoxy resin is more preferable. Therefore, in one embodiment, the thermosetting resin composition used in the first and second resin composition layers contains (a) an epoxy resin and (b) a curing agent. Further, a preferred photocurable resin composition can be formed by further adding a photocurable resin to the thermosetting resin composition. In the case of the photocurable resin, a conventionally known photocurable resin used for forming a solder resist layer of a printed wiring board can be used from the viewpoint of easily forming an opening by exposure/development (photolithography). Photocuring alkali-soluble resin good. In the first embodiment, the photocurable resin composition used in the first and second resin composition layers includes (a) an epoxy resin, (b) a curing agent, and (c) a photocurable alkali-soluble resin. . The photocurable resin composition further contains one or more selected from the group consisting of (d) a photopolymerization initiator, (e) a photosensitizer, and (f) a diluent. Further, in the present invention, a resin composition containing a photocurable resin and having an opening formed by photolithography is used, and it is also called a "photocurable resin composition" even when it has thermosetting properties. The resin composition which can be used for the first and second resin composition layers may further contain (g) inorganic filler and (h) heat, depending on the classification of the thermosetting resin composition and the photocurable resin composition. Additives such as a plastic resin, (i) a hardening accelerator, (j) a flame retardant, and (k) an organic filler.

In the following, the epoxy resin, the curing agent, the photocurable alkali-soluble resin, the photopolymerization initiator, the photosensitizer, and the diluent which can be used as the resin composition in the first and second resin composition layers are used. And additives for description.

- (a) epoxy resin -

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, and dicyclopentadiene epoxy resin. Phenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-benzene diphenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin,蒽 type epoxy resin, epoxy propyl amine type epoxy resin, epoxy propyl ester type epoxy tree Grease, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, An epoxy resin containing a spiral ring, a cyclohexane dimethanol type epoxy resin, a naphthalene ether type epoxy resin, and a trimethylol type epoxy resin. Epoxy resins may be used alone or in combination of two or more.

The epoxy resin is preferably one containing an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, it is preferred that at least 50% by mass or more of the epoxy resin having two or more epoxy groups in one molecule is used. In addition, 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 groups in one molecule are contained. Further, a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C is preferred. In the case of an epoxy resin, a liquid epoxy resin and a solid epoxy resin are used together to obtain a resin composition having excellent flexibility. Further, the breaking strength of the solder resist layer formed by hardening the resin composition is also improved. In particular, when the resin composition is a thermosetting resin composition, it is preferred to use a liquid epoxy resin together with a solid epoxy resin. When the resin composition is a photocurable resin composition, it is preferred to use a solid epoxy resin as the epoxy resin.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, and a bisphenol A epoxy resin. Bisphenol F type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032" and "HP4032D" manufactured by DIC Co., Ltd. "HP4032SS" (naphthalene type epoxy resin), "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac) "Zeel-type epoxy resin", "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), and "EX" by Nagase ChemteX Co., Ltd. -721" (epoxypropyl ester type epoxy resin). These may be used alone or in combination of two or more.

The solid epoxy resin is a naphthalene type 4-functional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a phenol type epoxy resin, a naphthol novolac type epoxy. Resin, biphenyl type epoxy resin, or naphthalene ether type epoxy resin is preferred, naphthalene type 4-functional epoxy resin, biphenyl type epoxy resin, or naphthalene ether type epoxy resin is better, naphthalene type 4 functional epoxy Resin and biphenyl type epoxy resin are even better. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC Co., Ltd., "HP-4710" (naphthalene type 4-functional epoxy resin), and "N-690" (cresol novolac varnish). Type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", " "EXA7311-G4S", "EXA7311-G4S", "HP6000" (naphthalene ether type epoxy resin), "EPPN-502H" ("phenol epoxy resin", "NC7000L" (naphthol) manufactured by Nippon Kayaku Co., Ltd. "Novolak epoxy resin", "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (naphthol novolac type) Epoxy resin), "ESN485V" (naphthol novolak type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin) and "YX4000HK" (dixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., and "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

In the case of epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio (liquid epoxy resin: solid epoxy resin) is in a mass ratio of 1:0.1 to 1 The range of 4: is better. 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) having a moderate adhesiveness when used in the form of a resin sheet, and ii) a resin sheet When the form is used, sufficient flexibility can be obtained and the pick-up property can be improved, and iii) a solder resist layer having sufficient breaking strength 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 expressed by mass ratio: The range of 0.3~1:3.5 is better, the range of 1:0.6~1:3 is better, and the range of 1:0.8~1:2.5 is particularly good.

The content of the epoxy resin in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, or 9% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited, but is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less or 35% by mass or less.

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

The epoxy equivalent of the epoxy resin is preferably from 50 to 3,000, more preferably It is 80~2000, and even better it is 110~1000. In this range, the cured product has a sufficient crosslinking density and a solder resist layer excellent in heat resistance. Further, the epoxy equivalent system can be measured in accordance with JIS K7236, and is a mass of a resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, still more preferably from 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a colloidal permeation chromatography (GPC) method.

- (b) hardener -

The hardener is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. An ester curing agent. The curing agent may be used alone or in combination of two or more.

In the case of a phenol-based curing agent and a naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol having a novolak structure is used from the viewpoint of obtaining a solder resist layer excellent in heat resistance and water resistance. A hardener is preferred. Moreover, from the viewpoint of obtaining a solder resist layer excellent in adhesion to a circuit board, a nitrogen-containing phenol-based curing agent is preferred, and a benzene-based curing agent containing a triazine skeleton is more preferable. Among them, a phenol novolak resin containing a triazine skeleton is preferred from the viewpoint of obtaining a solder resist layer which satisfies high heat resistance, water resistance, and adhesion to a circuit board.

Specific examples of the phenolic curing agent and the naphthol-based curing agent include "MEH-7700" manufactured by Mingwa Kasei Co., Ltd., "MEN-7", "MEH-7851", "Ninon", "CBN", "GPH", and "Tosho" ("SN170", "SN190", "SN190") made by Nippon Kayaku Co., Ltd. "LA7052", "LA7054", "LA3018", etc., "SN475", "SN485", "SN495", "SN375", "SN395", DIC (share) system.

From the viewpoint of obtaining a solder resist layer excellent in heat resistance, an active ester-based hardener is also preferable. The active ester-based curing agent is not particularly limited, and two or more molecules having high reactivity such as phenol esters, thiophene esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds are generally used. The ester group compound is preferred. 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. In particular, from the viewpoint of heat resistance improvement, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is preferred. Better. Examples of the carboxylic acid compound include benzoic acid, citric acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol porphyrin, methylated bisphenol A, methylated bisphenol F, and methyl group. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, benzenediol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-benzenetriol, 1,2,4-benzenetriol , a dicyclopentadiene type diphenol compound, a phenol novolak, and the like. Here, the so-called "dicyclopentadiene type The diphenol compound is a diphenol compound obtained by condensing 2 molecules of phenol in one molecule of dicyclopentadiene.

Specifically, it is an active ester compound having a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound of an acetylated phenolic novolac-containing acetal, and a phenol containing novolac phenol varnish. The active ester compound of the mercapto compound is preferred, and an active ester compound having a naphthalene structure or an active ester compound having a dicyclopentadiene type diphenol structure is more preferable. The "dicyclopentadiene type diphenol structure" means a divalent structural unit composed of a phenyl-dicyclopentene-phenylene group.

As a commercial product of the active ester-based curing agent, "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" are mentioned as the active ester compound containing a dicyclopentadiene type diphenol structure. In the case of the active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Co., Ltd.) and an active ester compound of an acetylated phenolic phenolic aldehyde varnish may be mentioned. "DC808" (manufactured by Mitsubishi Chemical Corporation), and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), etc., may be mentioned as an active ester compound of a benzoquinone-based phenol phenol varnish.

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

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylphenyl cyanate), and 4,4. '-Methylene double (2,6-dimethylphenyl cyanate), 4,4'-Asia Ethyl diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane) ), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis ( Bifunctional cyanate resin such as 4-cyanate phenyl) sulfide and bis(4-cyanate phenyl) ether; polyfunctional cyanate derived from phenol novolac and cresol novolak A resin, a prepolymer of a part of such a cyanate resin which is triazineated, or the like. Specific examples of the cyanate ester-based curing agent, "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (all are phenol novolac type polyfunctional cyanate ester resins), and "BA230" (bisphenol A II) A part or all of the cyanate ester is triazineated and formed into a trimer prepolymer).

The ratio of the epoxy resin to the hardener is preferably from 1:0.2 to 1:2 in terms of the ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener]. Range, 1:0.3~1:1.5 is better, 1:0.4~1:1.2 is better. 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 the curing agent. In addition, the total number of epoxy groups of the epoxy resin is the total value of all the epoxy resins obtained by dividing the solid content of each epoxy resin by the epoxy equivalent, and the reaction group of the hardener. The total number of the hardeners is the total value of the hardeners obtained by dividing the solid content of each of the hardeners by the reaction group equivalent. By making the ratio of the epoxy resin to the hardener in this range, the heat resistance of the resulting solder resist layer is further enhanced.

- (c) Photocuring alkali-soluble resin -

In the photocurable alkali-soluble resin, the photocurable resin containing an alkali-soluble group (for example, a carboxyl group or a phenolic hydroxyl group) is not particularly limited, and may be used when a solder resist layer for forming a printed wiring board is used. A conventionally known photocurable alkali-soluble resin. Among them, the photocurable alkali-soluble resin is preferably a resin containing an alkali-soluble group and a radical polymerizable unsaturated group, a resin having a carboxyl group and a radical polymerizable unsaturated group, and a phenol-containing hydroxyl group. The radical polymerizable unsaturated group-based resin is more preferable. The photocurable alkali-soluble resin may be used alone or in combination of two or more.

The resin containing a carboxyl group and a radically polymerizable unsaturated group may, for example, be a tether-type unsaturated epoxy ester resin obtained by reacting an epoxy resin with an unsaturated carboxylic acid and then reacting an acid anhydride.

In terms of epoxy resin, it is only necessary to use the same component as (a). From the viewpoint of obtaining good developability and insulation reliability, it is a bisphenol F type epoxy resin or a bisphenol A type epoxy. A resin or a cresol novolac type epoxy resin is preferred, and a bisphenol F type epoxy resin or a cresol novolak type epoxy resin is more preferable. The epoxy resin may be used alone or in combination of two or more.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and acrylic acid and methacrylic acid are preferred from the viewpoint of obtaining good photocuring properties. The unsaturated carboxylic acid may be used alone or in combination of two or more.

The carboxylic acid anhydride may, for example, be anhydrous maleic acid, anhydrous succinic acid, anhydrous itaconic acid, anhydrous phthalic acid, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, anhydrous trimellitic acid, anhydrous benzene. Formic acid, The benzophenone tetracarboxylic acid di-anhydrous or the like is preferably anhydrous succinic acid or anhydrous tetrahydrophthalic acid from the viewpoint of obtaining good developability and insulating reliability. The acid anhydride may be used alone or in combination of two or more.

A tethered unsaturated epoxy ester resin, in the presence of a catalyst, forms an unsaturated epoxy ester resin by reacting an unsaturated carboxylic acid with an epoxy resin, and the unsaturated epoxy ester resin is Anhydride is obtained by reaction. The reaction is known, and the reaction conditions such as the reaction temperature, the reaction time, the type of the catalyst, and the amount used are appropriately determined by those skilled in the art.

Commercially available products can also be used as the acid-fork type unsaturated epoxy ester resin. For the commercially available product, for example, "ZFR-1533H" (a reaction product of bisphenol F type epoxy resin, acrylic acid, and anhydrous tetrahydrophthalic acid) and "ZAR-2000" (double) manufactured by Nippon Kayaku Co., Ltd. "Reactant of phenol A type epoxy resin, acrylic acid, and anhydrous succinic acid", "PR-3000" (reactive material of cresol novolac type epoxy resin, acrylic acid, and carboxylic anhydride) manufactured by Showa Denko.

The resin containing a phenolic hydroxyl group and a radical polymerizable unsaturated group can be synthesized, for example, by reacting a resin having a phenolic hydroxyl group with a compound containing a radical polymerizable unsaturated group and an isocyanate group.

Examples of the phenolic hydroxyl group-containing resin include a phenol novolak resin, a cresol novolak resin, a bisphenol A novolac resin, and a naphthol novolak resin, from the viewpoint of obtaining good developability and insulation reliability. It is preferable to use a phenol novolak resin or a cresol novolak resin. The phenolic hydroxyl group-containing resin may be used alone or in combination of two or more.

Examples of the compound containing a radical polymerizable unsaturated group and an isocyanate group include (meth)acryl decyl isocyanate and isocyanate ethyl (meth) acrylate; and a polyisocyanate compound having a reaction with an isocyanate group. The (meth) acrylate compound of a functional group (for example, a hydroxyl group) is partially added to the reaction product obtained by the reaction, and the like. Here, examples of the polyisocyanate compound include 3-isocyanate-3,5,5-trimethylcyclohexyl isocyanate, trichloroethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and methylene. Examples of the (meth) acrylate compound having a functional group reactive with an isocyanate group, such as a phenyl phenyl isocyanate or a polymethylene polyphenyl polyisocyanate, may, for example, be pentaerythritol tri(meth) acrylate or 2- Hydroxyethyl (meth) acrylate, N-methylol acrylamide, glycerol di(meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

The resin containing a phenolic hydroxyl group and a radical polymerizable unsaturated group can be obtained by reacting a phenolic hydroxyl group-containing resin with a compound containing a radical polymerizable unsaturated group and an isocyanate group in the presence of a catalyst. The reaction is known, and the reaction conditions such as the reaction temperature, the reaction time, the type of the catalyst, and the amount used are appropriately determined by those skilled in the art.

The polystyrene-equivalent number average molecular weight (Mn) of the photocurable alkali-soluble resin is preferably from 500 to 1,000,000, more preferably from 1,000 to 50,000, still more preferably from the viewpoint of obtaining good resolution. 1500~35000. The Mn of the photocurable alkali-soluble resin can be measured, for example, by a colloidal permeation chromatography (GPC) method. The (GPC) method (in terms of polystyrene) can be measured. For example, the Mn system is manufactured by Shimadzu Corporation. LC-9A/RID-6A was used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. was used for the column, and the mobile phase was chloroform, and the column temperature was measured at 40 ° C. Calculated using standard polystyrene calibration lines.

The solid acid value of the photocurable alkali-soluble resin is preferably 100 mgKOH/g or less, more preferably 90 mgKOH/g or less, from the viewpoint of obtaining a solder resist layer exhibiting good insulation reliability. It is 80 mgKOH/g or less or 70 mgKOH/g or less. As long as the sufficient developability is obtained, the solid acid value is preferably lower. From this point of view, the photocurable alkali-soluble resin is a phenol-containing hydroxyl group and a radical polymerizable property. Saturated base resins are particularly preferred.

The content of the photocurable alkali-soluble resin in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more from the viewpoint of obtaining good developability. . The upper limit of the content of the photocurable alkali-soluble resin is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less from the viewpoint of obtaining a solder resist layer having excellent heat resistance.

-(d) Photopolymerization initiator -

The photopolymerization initiator is not particularly limited, and examples thereof include 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone and 2-(dimethylidene). Amino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-[4-(methyl Thio)phenyl]-morpholinyl-1-propanone, benzophenone, methylbenzophenone, o-benzylidene benzoin Acid, benzhydryl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, bis(2,4,6-trimethylbenzene) Mercapto)-phenylphosphine oxide, ethyl-(2,4,6-trimethylbenzylidene)phenylphosphonate, 4,4'-bis(diethylamino)benzol Ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)- Alkyl benzene-based photopolymerization initiators such as phenyl]-2-hydroxy-2-methyl-1-propan-1-one; bis(2,4,6-trimethylbenzylidene)- a mercaptophosphine oxide photopolymerization initiator such as phenylphosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzamide)肟)) and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) The oxime-based photopolymerization initiator, and the sulfonium-based photopolymerization initiator are preferably a mercaptophosphine oxide photopolymerization initiator or an oxime ester photopolymerization initiator. The photopolymerization initiator may be used singly or in combination of two or more.

For the commercially available product of the photopolymerization initiator, for example, "IRGACURE 819" (bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide) manufactured by BASF JAPAN Co., Ltd., " IRGACURE 907" (2-methyl-[4-(methylthio)phenyl]-morpholinyl-1-propanone), "OXE-01" (1,2-octanedione, 1-[ 4-(phenylthio)-, 2-(O-benzylidene hydrazide)]), "OXE-02" (ethanone, 1-[9-ethyl-6-(2-methylbenzene) Mercapto)-9H-carbazol-3-yl]-, 1-(O-ethylindenyl)) and the like.

The content of the photopolymerization initiator in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3, from the viewpoint of obtaining good photocuring properties and insulation reliability. quality More than %. The upper limit of the content of the photopolymerization initiator is preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1% by mass or less from the viewpoint of preventing a decrease in dimensional stability due to excessive sensitivity. .

- (e) Photosensitizer -

Examples of the photosensitizer include tertiary amines, pyrarizones, anthraquinones, coumarins, xanthones, and thioxanthones, and thioxanthones are preferred. More preferably, 2,4-diethylthioxanthone. The photosensitizer may be used alone or in combination of two or more. For the commercial product of the photosensitizer, for example, "DETX-S" (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd. can be mentioned.

The content of the photosensitizer in the resin composition is preferably from 0.01% by mass to 1% by mass, and more preferably from 0.05% by mass to 0.5% by mass, from the viewpoint of obtaining good photocuring properties.

- (f) thinner -

The diluent is used to promote the photohardening reaction of the resin composition. The diluent may, for example, be a photosensitive (meth) acrylate compound which has a liquid, a solid or a semi-solid at room temperature, and has one or more (meth) acryloyl fluorenyl groups in the molecule.

Examples of the photosensitive (meth) acrylate compound include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol and methoxytetraethylene a single or a diol compound of an alcohol, polyethylene glycol, propylene glycol, tricyclodecane dimethanol or the like Diacrylates; acrylamides such as N,N-dimethyl decylamine, N-methylol acrylamide; aminoalkyl groups such as N,N-dimethylaminoethyl acrylate a polyvalent acrylate such as an acrylate; a polyhydric alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol; or an adduct of such ethylene oxide, propylene oxide or ε-caprolactone; phenoxy acrylate; a phenol such as phenoxyethyl acrylate or an acrylate such as an ethylene oxide or propylene oxide addition; a ring derived from a glycopropyl ether such as trimethylolpropane triepoxypropyl ether Oxy acrylates; melamine acrylates; and/or methacrylates corresponding to the above acrylates. Among them, mono or di(meth)acrylates and polyvalent (meth)acrylates of the diol compound are more preferred.

The diluent may be used singly or in combination of two or more. For the commercial product of the diluent, for example, Nippon Chemical Co., Ltd. "DPHA" (dipentaerythritol hexaacrylate) and Kyoritsu Chemical Industry Co., Ltd. "DCPA" (tricyclodecane dimethanol diacrylate) )Wait.

The content of the diluent in the resin composition is preferably from 0.5% by mass to 10% by mass, more preferably from 2% by mass to 8% by mass, from the viewpoint of promoting the photocuring reaction and preventing adhesion of the cured product.

- (g) inorganic filler -

Examples of the inorganic filler include cerium oxide, aluminum oxide, glass, cordierite, ceric acid, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and the like. Boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, titanic acid Magnesium, barium titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Among these, cerium oxide such as amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide or the like is particularly preferable. In addition to cerium oxide, spherical cerium oxide is preferred. The inorganic filler may be used singly or in combination of two or more. For example, "UC1", "SOC2", "SOC3" and "SOC4" manufactured by Admatechs, "UFP-30" manufactured by Electrochemical Industry Co., Ltd., and "UFP-" are commercially available. 80".

The average particle diameter of the inorganic filler is not particularly limited, and may be appropriately determined depending on desired characteristics. The average particle diameter of the inorganic filler is preferably 0.01 μm or more, and more preferably 0.05 μm or more, from the viewpoint of improving the dispersibility of the inorganic filler. The average particle diameter of the inorganic filler is preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less from the viewpoint of obtaining sufficient insulation reliability. In addition, when the resin composition is a photocurable resin composition, the upper limit of the average particle diameter of the inorganic filler is preferably 1 μm or less, and more preferably 0.8 μm or less from the viewpoint of obtaining good photocuring properties. More preferably, it is 0.6 μm or less or 0.4 μm or less. The average particle size of the inorganic filler is by laser diffraction based on the Mie scattering theory. Determine by scattering method. Specifically, the laser diffraction scattering type particle size distribution measuring apparatus can measure the particle size distribution of the inorganic filler by volume and measure the median diameter as the average particle diameter. The sample is preferably measured by dispersing the inorganic filler in water by ultrasonic waves. For the laser diffraction scattering type particle size distribution measuring device, it can be used by the market. "LA-500" and so on.

The inorganic filler is an amine decane-based coupling agent, an epoxy decane-based coupling agent, a mercapto decane-based coupling agent, a decane-based coupling agent, and an organic decazane compound from the viewpoint of improving moisture resistance and dispersibility. It is preferred to treat one or more kinds of surface treatment agents such as a titanate-based coupling agent. For the commercially available product of the surface treatment agent, for example, KBM403 (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3) - "Ketidylpropyltrimethoxydecane", "KBE903" (3-aminopropyltriethoxydecane) 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.

The degree of surface treatment achieved by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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 0.2 mg/m ² or more from the viewpoint of improving the dispersibility of the inorganic filler. Better again. On the other hand, from the viewpoint of preventing the melt viscosity of the resin paint or the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ^{2 .} The following is even better.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, in terms of solvent, a sufficient amount of MEK can be added to the surface treatment of the surface treatment agent. In the inorganic filler, the ultrasonic wave was washed at 25 ° C for 5 minutes. After the supernatant was removed and the solid fraction was dried, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The content of the inorganic filler in the resin composition is not particularly limited as long as a solder resist layer exhibiting a desired elastic modulus can be obtained. Although depending on the type of the epoxy resin or the curing agent, when the content of the inorganic filler in the resin composition is increased, the elastic modulus of the resin composition after curing tends to be high. For example, a resin composition layer having a high modulus of elasticity (23 ° C) of 6 GPa or more after curing is formed, and when the solder resist layer is formed, the content of the inorganic filler in the resin composition is preferably 60% by mass or more. The resin composition layer having a higher modulus of elasticity (23 ° C) after hardening, and further, when the solder resist layer is formed, the content of the inorganic filler in the resin composition is preferably 65 mass% or more, and 70 mass% or more. Or 75 mass% or more is even better.

In one embodiment, the content of the inorganic filler in the resin composition used in the first resin composition layer and the first solder resist layer is preferably 60% by mass or more, more preferably 65% by mass or more, and still more. Preferably, it is 70% by mass or more or 75% by mass or more. The upper limit of the content of the inorganic filler in the resin composition used in the first resin composition layer is not particularly limited, and is usually 95% by mass or less from the viewpoint of mechanical strength of the obtained solder resist layer. 90% by mass or less.

The content of the inorganic filler in the resin composition used in the second resin composition layer and the second solder resist layer can be obtained. In the case of the second solder resist layer having a desired modulus of elasticity, it may be appropriately determined depending on the desired characteristics, and is preferably in the range of preferably 0% by mass to 95% by mass, more preferably 20%. It is preferable to suitably determine the range of the mass % to 85% by mass.

In a preferred embodiment, the resin composition used in the first resin composition layer is a thermosetting resin composition comprising the above (a) epoxy resin, (b) a curing agent, and (g) inorganic Filling material. In the embodiment, the thermosetting resin composition used in the first resin composition layer preferably contains the following components: a liquid epoxy resin as the (a) epoxy resin and a solid epoxy resin. A mixture of resins (liquid epoxy resin: solid epoxy resin is preferably in the range of 1:0.1 to 1:4, more preferably in the range of 1:0.3 to 1:3.5, 1:0.6~) The range of 1:3 is better, the range of 1:0.8~1:2.5 is even better), as the (b) hardener, phenolic hardener, naphthol hardener, active ester hardener and cyanic acid One or more selected from the group consisting of ester-based curing agents (preferably one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent), as (g) Antimony oxide of inorganic filler. The preferred content of the (a) epoxy resin, (b) curing agent, and (g) inorganic filler in the thermosetting resin composition containing the specific components is as described above.

In a preferred embodiment, the resin composition used in the first resin composition layer is a photocurable resin composition, the above (a) epoxy resin, (b) curing agent, and (c) photocuring type. The base contains a soluble resin and (g) an inorganic filler. In this embodiment, the first resin The photocurable resin composition used in the composition layer preferably contains the following components: a mixture of the liquid epoxy resin as the (a) epoxy resin and the solid epoxy resin (liquid ring) Oxygen resin: The mass ratio of the solid epoxy resin is preferably in the range of 1:0.1 to 1:4, the range of 1:0.3 to 1:3.5 is better, and the range of 1:0.6 to 1:3 is more preferable. 1:0.8~1:2.5 is even better) or only solid epoxy resin, phenolic hardener as a hardener (b), naphthol hardener, active ester hardener and cyanate One or more selected from the group consisting of ester-based curing agents (preferably one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent), and (c) photohardening a resin containing an alkali-soluble group and a radically polymerizable unsaturated group (preferably a resin having a carboxyl group and a radical polymerizable unsaturated group, a phenol-containing hydroxyl group, and a radical polymerizable unsaturated group) The resin is more preferably a resin containing a phenolic hydroxyl group and a radical polymerizable unsaturated group, and (g) an inorganic filler. A preferred content of the thermosetting resin composition comprising the specific component, (a) epoxy resin, (b) hardener, (c) photocurable alkali-soluble resin, and (g) inorganic filler In the above, the (a) ring is obtained when the non-volatile content of the (c) photocurable alkali-soluble resin is 100% by mass from the viewpoint of obtaining good heat resistance, insulation reliability, and development. The oxygen resin is preferably from 5% by mass to 100% by mass, more preferably from 10% by mass to 85% by mass. Further, when the resin composition used in the first resin composition layer is a photocurable resin composition, the photocurable resin composition further contains (d) a photopolymerization initiator, and (e) a light gain. One or more selected from the group of the sensitizer and (f) diluent good.

From the viewpoint of the warpage of the printed wiring board, the resin composition used in the first resin composition layer and the first solder resist layer is not limited to the thermosetting resin composition or the photocurable resin. The type of the composition is preferably such that the glass transition temperature (Tg) after hardening is 150° C. or higher and 155° C. or higher. The upper limit of the Tg is not particularly limited, but is usually 300 ° C or lower, and may be 250 ° C or lower. The Tg system of the cured resin composition can be measured by thermomechanical analysis by a tensile weighting method. In the measurement of the resin composition Tg after the hardening, the thermomechanical analysis device which can be used is, for example, "Thermo Plus TMA8310" manufactured by Seiko Instruments Co., Ltd. and "TMA-SS6100" manufactured by Seiko Instruments Co., Ltd.

In a preferred embodiment, the resin composition used in the second resin composition layer is a thermosetting resin composition containing the above (a) epoxy resin and (b) a curing agent. In the embodiment, the thermosetting resin composition used in the second resin composition layer preferably contains the following components: a liquid epoxy resin as the (a) epoxy resin and a solid epoxy resin. The resulting mixture (liquid epoxy resin: the mass ratio of the solid epoxy resin is preferably in the range of 1:0.1 to 1:4, and the range of 1:0.3 to 1:3.5 is better, 1:0.6 to 1) The range of :3 is better, the range of 1:0.8~1:2.5 is even better), as the (b) hardener, the phenolic hardener, the naphthol hardener, the active ester hardener and the cyanic acid One or more selected from the group consisting of ester-based curing agents (preferably one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent). Have The thermosetting resin composition containing the specific component is preferably contained, and the preferred contents of (a) epoxy resin and (b) hardener are also as described above. As described above, the thermosetting resin composition used in the second resin composition layer contains (g) an inorganic filler (preferably yttrium oxide) in order to achieve a second solder resist layer exhibiting a desired elastic modulus. The content in the resin composition is in the range of 0% by mass to 95% by mass. In the case where the constituent component of the resin composition is contained in the range of 0% by mass to n% by mass, both the case where the component is not contained and the case where it is contained in the range of n% by mass or less are included.

In a preferred embodiment, the resin composition-based photocurable resin composition used in the second resin composition layer includes the above (a) epoxy resin, (b) curing agent, and (c) light. Hardening type alkali soluble resin. In the embodiment, the photocurable resin composition used in the second resin composition layer preferably contains the following components: a liquid epoxy resin as the (a) epoxy resin and a solid epoxy resin. The resulting mixture (liquid epoxy resin: the mass ratio of the solid epoxy resin is preferably in the range of 1:0.1 to 1:4, and the range of 1:0.3 to 1:3.5 is better, 1:0.6 to 1) The range of :3 is better, the range of 1:0.8~1:2.5 is even better) or only the solid epoxy resin, the phenolic hardener as the (b) hardener, the naphthol hardener, One or more selected from the group consisting of an active ester-based curing agent and a cyanate ester-based curing agent (preferably one selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent) (c) a resin containing an alkali soluble group and a radical polymerizable unsaturated group as (c) a photocurable alkali-soluble resin (preferably having a carboxyl group and being free) The resin of the radically polymerizable unsaturated group, the resin containing a phenolic hydroxyl group and a radical polymerizable unsaturated group, more preferably a resin containing a phenolic hydroxyl group and a radical polymerizable unsaturated group). The preferred content of the thermosetting resin composition containing the specific component, (a) epoxy resin, (b) curing agent, and (c) photocuring alkali-soluble resin is as described above, but is good from the above. (a) The epoxy resin, when the non-volatile content of the (c) photocurable alkali-soluble resin is 100% by mass, preferably 5% by mass, from the viewpoint of heat resistance, insulation reliability, and development. It is preferably from 100% by mass, more preferably from 10% by mass to 85% by mass. When the resin composition used in the second resin composition layer is a photocurable resin composition, the photocurable resin composition further contains (d) a photopolymerization initiator, (e) photosensitization One or more selected from the group consisting of the agent and the (f) diluent are preferred. In the photocurable resin composition used in the second resin composition layer, as described above, in order to achieve the second solder resist layer exhibiting a desired elastic modulus, the content in the resin composition is 0% by mass to 95% by mass. The range may be (g) an inorganic filler (preferably ruthenium oxide).

The resin composition used in the second resin composition layer and the second solder resist layer, regardless of the type of the thermosetting resin composition or the photocurable resin composition, can be obtained as long as the desired elastic modulus is obtained. The glass transition temperature (Tg) is not particularly limited. From the viewpoint of further suppressing warpage of the printed wiring board in the mounting step, the resin composition used in the second resin composition layer and the second solder resist layer is cured at a temperature of 150 ° C or higher. Better, better than 155 °C. The upper limit of the Tg is not particularly limited, and is usually 300 ° C or lower, and may be 250 ° C or lower. Wait.

In a preferred embodiment, the resin compositions used in the first and second resin composition layers are all thermosetting resin compositions. In other preferred embodiments, the resin compositions used in the first and second resin composition layers are all photocurable resin compositions. In another preferred embodiment, the resin composition used in the first resin composition layer is a thermosetting resin composition, and the resin composition used in the second resin composition layer is a photocurable resin composition. Things. In another preferred embodiment, the resin composition used in the first resin composition layer is a photocurable resin composition, and the resin composition used in the second resin composition layer is a thermosetting resin composition.

- (h) thermoplastic resin -

The resin composition used in the first and second resin composition layers may further contain a thermoplastic resin. In the case of the thermoplastic resin, any thermoplastic resin generally available can be used in forming the solder resist layer of the printed wiring board, and examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, and a polybutadiene. Resin, polyimine resin, polyamidoximine resin, polyether oxime resin, polyphenylene ether resin and polyfluorene resin. 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, and even more preferably in the range of 20,000 to 60,000. Polystyrene-equivalent weight average molecular weight of thermoplastic resin (GPC) method to determine. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is used as a measuring device using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P manufactured by Showa Denko Co., Ltd. The K-804L/K-804L and the mobile phase were measured by using a chloroform or the like at a column temperature of 40 ° C and using a calibration curve of standard polystyrene.

The content of the thermoplastic resin in the resin composition is not particularly limited as long as a solder resist layer exhibiting a desired elastic modulus is obtained, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 3 or more. 5% by mass or more, 5% by mass or more, or 7% by mass or more. The upper limit of the content of the thermoplastic resin is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. Depending on the type of the epoxy resin or the curing agent and the content of the inorganic filler, if the content of the thermoplastic resin is increased in the resin composition, the elastic modulus of the resin composition after curing tends to be low.

- (i) hardening accelerator -

The resin composition used in the first and second resin composition layers may further contain a curing accelerator. In the case of forming a solder resist layer of a printed wiring board, any hardening accelerator which is generally used may be used, and examples thereof include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, and an imidazole-based hardening accelerator. In addition, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, and an imidazole-based hardening accelerator are preferable, and an amine-based hardening accelerator and an imidazole-based hardening accelerator are more preferable. Hardening accelerators can be made separately One type may be used, or two or more types may be used in combination.

The content of the hardening accelerator in the resin composition is not particularly limited as long as a solder resist layer exhibiting a desired elastic modulus is obtained, and when the total amount of the non-volatile components of the epoxy resin and the curing agent is 100% by mass, It is preferably used in the range of 0.03 mass% to 3% by mass.

-(j) flame retardant -

The resin composition used in the first and second resin composition layers may further contain a flame retardant. In the case of forming a solder resist layer of a printed wiring board, any flame retardant which is generally used may be used, and examples thereof include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, and a polyoxygen system. Flame retardant, metal hydroxide, etc. The flame retardant may be used alone or in combination of two or more. The content of the flame retardant in the resin composition is not particularly limited as long as a solder resist layer exhibiting a desired elastic modulus is obtained, and is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass. .

-(k)Organic filler -

The resin composition used in the first and second resin composition layers may further contain an organic filler. In the case of forming the solder resist layer of the printed wiring board, any organic filler generally used may be used, for example, rubber particles, polyamide fine particles, polyoxyn oxide particles, and the like, and rubber particles are preferred.

In the case of rubber particles, if it is a resin which is chemically cross-linked to a resin exhibiting rubber elasticity and which is insoluble and insoluble in an organic solvent The fine particle body is not particularly limited, and examples thereof include acrylonitrile butadiene rubber particles, butadiene rubber particles, and acrylic rubber particles. In terms of rubber particles, specifically, XER-91 (made by Nippon Synthetic Rubber Co., Ltd.), Staphiroid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, GANTSU KASEI (share)) Pararoid EXL2655, EXL2602 ( Above, Wu Yu Chemical Industry Co., Ltd.).

The average particle diameter of the organic filler 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 size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler can be uniformly dispersed by ultrasonic waves or the like in a suitable organic solvent, and a thick filler particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) can be used to form an organic filler on a mass basis. The particle size distribution was measured by taking the median diameter as the average particle diameter.

The content of the organic filler in the resin composition is not particularly limited as long as a solder resist layer exhibiting a desired elastic modulus is obtained, and is preferably 0.1% by mass to 6% by mass, more preferably 0.5% by mass to 4% by mass. .

-Other ingredients -

The resin composition used in the first and second resin composition layers may contain other additives as needed, and examples of the other additives include organometallic compounds such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, and A resin additive such as a tackifier, an antifoaming agent, a leveling agent, a tackifier, and a coloring agent.

<Support>

In terms of the support, the difference between the first support and the second support may be, for example, a film made of a plastic material, a metal foil, or a release paper, and a film made of a plastic material or a metal foil is preferred.

In the case of a support material, when a film made of a plastic material is used, examples of the plastic material include polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate (hereinafter referred to as " Polyesters such as PEN"), polycarbonate (hereinafter referred to as "PC"), polymethyl methacrylate (PMMA), acrylate, cyclic polyolefin, triethyl fluorene cellulose (TAC), poly Ether sulfide (PES), polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is particularly preferred.

In the case of using a metal foil, the metal foil may, for example, be a copper foil or an aluminum foil, and a copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, etc.) may be used.

The support can be subjected to a matting treatment or a corona treatment on a surface joined to the resin composition layer. Further, as the support, a support having an release layer of a release layer on a surface joined to the resin composition layer may be used. The release agent to be used on the release layer of the support of the release layer may, for example, be an alkyd resin, a polyolefin resin, a urethane resin, or a polyoxymethylene resin. One or more kinds of release agents selected from the group formed.

For the commercial products of the support, for example, "SK-1", "AL-5", "AL-7" manufactured by LINTEC Co., Ltd., "NS80A" manufactured by Toray Co., Ltd., and Mitsubishi Resin Co., Ltd. "R310-16B" and so on.

The thickness of the support is not particularly limited, and is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm, and even more preferably in the range of 10 μm to 45 μm. Further, when the support of the release layer is used, the thickness of the entire support of the release layer is preferably in the above range.

The resin sheet can be prepared by dissolving the resin composition in an organic solvent, for example, by dissolving the resin composition in an organic solvent, and applying the resin coating to a support using a die coater or the like. It is made by drying the resin and drying it.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl phthalate, butyl phthalate, 赛 succinate, propylene glycol monomethyl ether acetate, and carbitol. a phthalic acid ester such as acetate, a carbitol such as sucrose or butyl carbitol, an aromatic hydrocarbon such as toluene or xylene, dimethylformamide or dimethylacetamide. A guanamine-based solvent such as N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

The drying of the resin coating can be carried out by a known drying method such as heating, hot air blowing or the like. Although depending on the boiling point of the organic solvent in the resin coating, for example, when painting with a resin containing 30% by mass to 60% by mass of an organic solvent, it can be dried at 50 ° C to 150 ° C for 3 minutes. ~10 minutes, a resin composition layer was formed on the support.

The resin sheet may further include a protective film on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support), regardless of the difference between the first resin sheet and the second resin sheet. The protective film acts to prevent adhesion or damage such as dirt on the surface of the resin composition layer. The material of the protective film can be the same as that described for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The resin sheet is used by peeling off the protective film when manufacturing a printed wiring board.

[Manufacturing method of printed wiring board]

When a printed wiring board that satisfies the above conditions (1), (2), and (3) is obtained, the method of manufacturing the printed wiring board of the present invention is not particularly limited. Hereinafter, a method of producing a printed wiring board using a resin sheet for a solder resist layer of the above-described printed wiring board will be described as a preferred example of a method of manufacturing the printed wiring board of the present invention.

In a preferred embodiment, the printed wiring board of the present invention is produced by a method comprising the following steps (I) to (III) using the resin sheet group for a solder resist layer of the printed wiring board.

(I) a first resin sheet including a first support and a first resin composition layer joined to the first support on the first main surface of the circuit board having the first and second main faces Step of laminating the first resin composition layer and the first main surface of the circuit board

(II) Thin second resin including the second support and the second resin composition layer joined to the second support on the second main surface of the circuit board Step of laminating the second resin composition layer so as to be bonded to the second main surface of the circuit board

(III) Step of curing the first and second resin composition layers to form the first and second solder resist layers

-Step (I)-

In the step (I), the first resin including the first support and the first resin composition layer joined to the first support is formed on the first main surface of the circuit board having the first and second main faces. The sheet is laminated such that the first resin composition layer is bonded to the first main surface of the circuit board.

In the step (I), the first resin sheet to be used is contained in the above-mentioned [resin sheet group for a solder resist layer of a printed wiring board).

In the present invention, the term "circuit board" means a substrate on which a solder resist layer is formed on both sides when manufacturing a printed wiring board, and for example, the first and second main surfaces are opposed to each other, and the first and second main surfaces are 2 Both sides of the main surface have a substrate for circuit wiring processed by the pattern. The layer configuration including the number of layers of the circuit wiring is not particularly limited, and may be appropriately determined depending on the characteristics of the desired printed wiring board.

The thickness of the circuit board is not particularly limited as long as the printed wiring board satisfying the above conditions (1) and (2) is obtained, and is preferably 240 μm or less, more preferably 220 μm or less, still more preferably 200 μm or less. According to the present invention, even when a thinner circuit substrate is used, warpage of the printed wiring board in the mounting step can be suppressed. Even when a circuit board having a thickness of, for example, 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 120 μm or less, 110 μm or less, or 100 μm or less is used, the mounting step can be suppressed. Warping. The lower limit of the thickness of the circuit board is not particularly limited, and is preferably 10 μm or more, and more preferably 20 μm or more from the viewpoint of improving the pick-up property at the time of production of the printed wiring board. Further, the thickness of the circuit board is the thickness of the entire circuit board including the thickness of the surface circuit. Here, when the value obtained by removing the thickness of the surface circuit from the thickness of the circuit substrate is t ₃ (μm), the above Z, t ₁ , t ₂ and the t ₃ satisfy t ₁ + t ₂ + t ₃ = Z. relationship.

The thickness of the surface circuit of the circuit board is not particularly limited, and is preferably 40 μm or less, more preferably 30 μm or less, still more preferably 25 μm or less, and still more preferably 20 μm from the viewpoint of reducing the thickness of the printed wiring board. Hereinafter, it is 18 μm or less, 16 μm or less, 14 μm or less, 12 μm or less, or 10 μm or less. The lower limit of the thickness of the surface circuit is not particularly limited, and may be usually 1 μm or more, 3 μm or more, or 5 μm or more.

The thermal expansion coefficient of the circuit board is preferably 16 ppm/° C. or less, more preferably 14 ppm/° C. or less, and still more preferably 12 ppm/° C. or less from the viewpoint of suppressing the occurrence of cracks or cracks in the circuit. The lower limit of the thermal expansion coefficient of the circuit board varies depending on the composition of the resin composition used for forming the solder resist layer, but is preferably -2 ppm/° C or more, more preferably 0 ppm/° C. or more, still more preferably 4 ppm/° C. the above. In the present invention, the coefficient of thermal expansion of the circuit substrate is a linear thermal expansion coefficient of 25 to 150 ° C in the plane direction obtained by thermomechanical analysis (TMA) by a tensile weighting method. The thermomechanical analysis device that can be used in the measurement of the linear thermal expansion coefficient of the circuit substrate can be exemplified For example, "Thermo Plus TMA8310" is a scientific research system and "TMA-SS6100" manufactured by Seiko Instruments.

The bending elastic modulus of the circuit board is not particularly limited. In the present invention, regardless of the bending elastic modulus of the circuit board, warpage in the mounting step can be suppressed.

The laminate of the circuit board and the first resin sheet can be performed, for example, by heating and pressing the first resin sheet on the circuit board from the first support side. The member for heating and pressing the first resin sheet on the circuit board (hereinafter also referred to as "heating and pressing member") may, for example, be a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). In addition, the first resin sheet is not sufficiently adhered to the first resin sheet due to the surface unevenness of the circuit board, and the first resin sheet is sufficiently followed by the elastic material such as heat-resistant rubber. The person who pressurizes is better.

The heating and pressing temperature is preferably in the range of 80 ° C to 160 ° C, more preferably in the range of 100 ° C to 140 ° C, and the heating pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The heating pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7 hPa or less.

The laminate can be carried out through a commercially available vacuum laminator. For example, a vacuum press laminator manufactured by Nippon Machine Co., Ltd., a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., or the like can be used.

After lamination, under normal pressure (at atmospheric pressure), for example, borrow The smoothing treatment of the laminated first succeeding sheet is performed by pressurizing the heating and pressing member from the first support side. The pressurization conditions of the smoothing treatment may be the same conditions as the above-described laminated heating press conditions. The smoothing process can be carried out by a commercially available laminator. Further, the lamination and smoothing treatment can also be carried out continuously using the commercially available vacuum laminator described above.

-Step (II)-

In the step (II), the second resin sheet including the second support and the second resin composition layer joined to the second support is a second resin composition layer on the second main surface of the circuit board. Lamination is performed so as to be bonded to the second main surface of the circuit board.

In the step (II), the second resin sheet to be used is contained in the above-mentioned [resin sheet group for a solder resist layer of a printed wiring board).

The lamination of the circuit board and the second resin sheet can be carried out in the same manner as in the step (I). After the circuit board and the second resin sheet are laminated, the smoothing treatment described in the step (I) can be carried out in the second resin sheet.

Step (I) and step (II) can be carried out simultaneously using a commercially available vacuum laminator.

The first and second supports can be removed prior to step (III). Alternatively, the first and second supports may be removed after the step (III) (when the thermosetting resin composition layer is used) or may be removed between the steps (III) (using the photocurable resin composition layer) Case).

-Step (III)-

In the step (III), the first and second resin composition layers are cured to form first and second solder resist layers.

The curing conditions of the resin composition layer are not particularly limited, and the conditions generally employed in forming the solder resist layer of the printed wiring board may be used.

When at least one of the first and second resin composition layers is a thermosetting resin composition layer, the step (III) includes thermally curing the thermosetting resin composition layer to form a solder resist layer.

The heat curing conditions vary depending on the composition of the resin composition used in the thermosetting resin composition layer, and the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, more preferably The range of 170 ° C to 190 ° C) and the hardening time are in the range of 5 minutes to 150 minutes (preferably 10 minutes to 120 minutes, more preferably 15 minutes to 90 minutes). Thermal curing is preferred at atmospheric pressure (under normal pressure). In addition, thermal hardening can be performed multiple times. For example, the step (III) may be carried out plural times before the step (IV) described later, and the step (III) may be carried out once or more before the step (IV) described later, and after the steps (IV) and (V), the method 1 may be carried out. More than one time of thermal hardening. When the thermosetting is performed n times, the above-mentioned "elasticity after hardening" means the elastic modulus after n times of thermal curing.

When at least one of the first and second resin composition layers is a photocurable resin composition layer, the step (III) includes exposing, developing, and baking the photocurable resin composition layer to form a solder resist layer.

The exposure of the photocurable resin composition layer can be carried out, for example, by irradiating a predetermined portion of the photocurable resin composition layer with active light rays using a mask pattern. Thereby, the photocurable resin composition of the irradiation portion can be photocured. Examples of the active light include ultraviolet rays, visible rays, electron beams, and X-rays, and particularly ultraviolet rays. The amount of the ultraviolet ray to be irradiated is not particularly limited, and may be a range generally used when a solder resist layer is formed using a photocurable resin composition, but is preferably 10 mJ/cm ² to 1000 mJ/cm ² . When a support is present on the photocurable resin composition layer, it can be exposed from the support.

The development system uses a developing solution, and can also be carried out after removing the portion (unexposed portion) which has not been photohardened. Thereby, the desired pattern can be formed. Further, when a support is present on the photocurable resin composition layer, the support may be removed and developed. In the case of the developing solution, an alkaline developing solution is preferred, and examples thereof include an aqueous solution of sodium carbonate and an aqueous solution of sodium hydroxide. Examples of the development method include spraying, shaking, scouring, scraping, and the like.

The baking condition varies depending on the composition of the resin composition used in the photocurable resin composition layer, and the baking temperature may be in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, More preferably, it is in the range of 170 ° C to 190 ° C. The baking time may be in the range of 5 minutes to 150 minutes (preferably 10 minutes to 120 minutes, more preferably 15 minutes to 90 minutes). Baking is preferably carried out under atmospheric pressure (under normal pressure). In addition, baking can be carried out multiple times. When the baking is performed n times, the above-mentioned "elasticity after hardening" means the elastic modulus after n times of baking.

When one side of the first and second resin composition layers is a thermosetting resin composition layer and the other side is a photocurable resin composition layer, the light is applied Baking of the curable resin composition layer can be carried out simultaneously with thermal hardening of the thermosetting resin composition layer.

By carrying out the steps (I) to (III) by using the resin sheet group of the present invention, it is possible to easily manufacture a printed wiring board which satisfies the above conditions (1), (2) and (3).

-Other steps -

The method for producing a printed wiring board may further include (IV) a step of forming an opening and (V) a step of electroless copper plating. These steps (IV) and (V) are used in the manufacture of printed wiring boards and can be carried out in accordance with various methods well known to those skilled in the art. Further, when the first and second supports are peeled off after the step (III) (when the thermosetting resin composition layer is used), the peeling of the first and second supports may be in the step (III) and the step. Between (IV), between step (IV) and step (V), or after step (V).

Step (IV) is a step of forming an opening. Thereby, an opening portion can be formed on the solder resist layer formed using the thermosetting resin composition. Further, if necessary, in order to form an opening on the solder resist layer formed using the photocurable resin composition, the step (IV) may be carried out. The step (IV) is carried out in accordance with, for example, drilling, laser, plasma, or the like in accordance with the composition of the resin composition constituting the solder resist layer. The size or shape of the opening portion can be appropriately determined depending on the design of the component mounting substrate (also referred to as "semiconductor device").

When a laser is used to form an opening, the laser source can be Examples are carbon dioxide gas lasers, YAG lasers, excimer lasers, and the like. Among them, from the viewpoint of processing speed and cost, it is preferable to use a carbon dioxide gas laser.

Step (V) is a step of electroless copper plating. In the step (IV), resin residues (stains) are generally adhered to the inside of the formed opening. This stain causes a cause of poor electrical connection. Therefore, in the step (V), the stain removing treatment (electroless copper plating treatment) is performed.

The electroless copper plating treatment can be carried out by combining a dry electroless copper plating treatment, a wet electroless copper plating treatment, or a combination thereof.

Examples of the dry electroless copper plating treatment include, for example, electroless copper plating treatment using plasma. The electroless copper plating process using plasma can be carried out using a commercially available plasma electroless copper plating apparatus. Among the commercially available plasma electroless copper plating apparatuses, a microwave electric plasma apparatus manufactured by Nissin and a Sekisui Chemical Industry Co., Ltd. are used as a preferred example of the production of the printed wiring board. Normal piezoelectric plasma etching device, etc.

The wet electroless copper plating treatment may, for example, be an electroless copper treatment using an oxidizing agent solution. When the electroless copper plating treatment is performed using the oxidizing agent solution, it is preferred to carry out the swelling treatment of the swelling liquid, the oxidation treatment with the oxidizing agent solution, and the neutralizing treatment with the neutralizing liquid. Examples of the swelling liquid include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN Co., Ltd., and the like. The swelling treatment is preferably performed by heating the substrate on which the opening is formed to 60° C. to 80° C. and immersing it in the swelling liquid for 5 minutes to 10 minutes. Oxidant The solution is preferably an alkaline permanganic acid aqueous solution, and for example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using the oxidizing agent solution is preferably carried out by immersing the swelled substrate in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. For the commercial product of the alkaline permanganic acid aqueous solution, for example, "Concentrate Compact CP" manufactured by ATOTECH JAPAN Co., Ltd., "Dosing Solution Securiganth P", or the like can be mentioned. The neutralization treatment using the neutralizing liquid is preferably carried out by immersing the substrate after the oxidation treatment in a neutralization liquid at 30 ° C to 50 ° C for 3 minutes to 10 minutes. In the case of the neutralization liquid, an acidic aqueous solution is preferred, and a commercially available product may be, for example, "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN Co., Ltd.

When the dry electroless copper plating treatment and the wet electroless copper plating treatment are combined, the dry electroless copper plating treatment may be performed first, or the wet electroless copper plating treatment may be performed first.

As described above, the method of manufacturing a printed wiring board using the resin sheet group of the present invention has been described, but the printing of the present invention can be produced as long as a printed wiring board satisfying the above conditions (1), (2), and (3) can be obtained. The method of the wiring board is not particularly limited. For example, a coating of a resin composition can be applied to both surfaces of a circuit board, and dried and hardened to produce a printed wiring board.

[semiconductor device]

A semiconductor device can be manufactured using the printed wiring board of the present invention. this invention Even if the printed wiring board is thin, it is possible to suppress warpage in the mounting step of the component using the high solder reflow temperature, and it is advantageous in that the circuit is twisted or the contact failure of the component is reduced.

Examples of the semiconductor device include various semiconductor devices such as power supply products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, electric cars, ships, and airplanes).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. In addition, the terms "parts" and "%" in the following terms mean "parts by mass" and "% by mass" unless otherwise stated.

First, various measurement methods and evaluation methods will be described.

[Modulation of Evaluation Substrate] (1) Preparation of circuit board

A two-layer laminate of a glass cloth substrate epoxy resin having a circuit formed on both sides thereof was etched by a microetching agent ("CZ8100" manufactured by MEC Co., Ltd.) to a thickness of 1 μm, and a surface circuit was roughened to prepare a circuit board. For the two-layer laminates of the glass cloth substrate epoxy resin on both sides of the circuit, the first, second and fourth and the comparative examples 1 and 2 are made of Mitsubishi Gas Chemical Co., Ltd. "HL832NSF-LCA" (size 100mm × 150mm) , thickness 100μm, The thermal expansion coefficient was 4 ppm/° C., the bending elastic modulus was 34 GPa, and the thickness of the surface copper circuit was 16 μm. Example 3 and Comparative Examples 3 and 4 were “E679FGR” (100 mm × 150 mm, thickness 200 μm, thermal expansion) manufactured by Hitachi Chemical Co., Ltd. The ratio was 14 ppm/K, the bending elastic modulus was 26 GPa, the thickness of the surface copper circuit was 16 μm (Example 3 and Comparative Example 3), and 8 μm (Comparative Example 4).

(2) Lamination of resin sheets

The circuit board obtained in the above (1) is a two-stage build-up laminator manufactured by Nichigo-Morton Co., Ltd. in the following production example. The CVP 700") is laminated on both surfaces of the circuit board so that the resin composition layer and the circuit board are next. After the laminate was decompressed for 30 seconds and the gas pressure was 13 hPa or less, the laminate was pressed at 100 ° C and a pressure of 0.74 MPa for 30 seconds. Next, it was subjected to a smoothing treatment under normal pressure at 100 ° C and a pressure of 0.5 MPa for 60 seconds.

Further, the combination of the first and second resin sheets on the two-area layers of the circuit board is shown in Table 1.

Next, as described below, the resin composition layer is cured to form a solder resist layer.

- In the case of using the resin sheets 1 and 2 containing a thermosetting resin composition layer - (3) Thermal hardening of the resin composition layer

The substrate was peeled off from the substrate obtained in the above (2). Then, at 180 The resin composition layer was thermally hardened under a hardening condition of ° C for 30 minutes to form a solder resist layer.

(4) Formation of the opening

Using a CO ₂ laser processing machine ("ML605GTWIII-5200U" manufactured by Mitsubishi Electric Corporation), a circular hole having an opening diameter of 60 μm was formed under the following condition 1, and a circular hole having an opening diameter of 500 μm was formed under the following condition 2.

Condition 1: Mask diameter 0.9mm, pulse width 19μs, energy 0.24mJ, number of shots 2, pulse pause mode

Condition 2: mask diameter 10mm, pulse width 15μs, energy 18mJ, number of shots 4, pulse pause mode

(5) Electroless copper plating

After the formation of the opening, the circuit board was immersed in a swelling liquid ("Swelling Dip Securiganth P" manufactured by Atotech JAPAN Co., Ltd., an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes, and impregnated. In the oxidizing agent solution (Concentrate Compact CP, manufactured by ATOTECH JAPAN Co., Ltd., KMnO ₄ : 60 g/L, NaOH: 40 g/L), at 80 ° C for 10 minutes, and finally neutralized solution (ATOTECH JAPAN Co., Ltd.) Reduction Solution Securiganth P", aqueous solution of hydroxylamine sulfate) at 40 ° C for 5 minutes. Thereafter, it was dried at 100 ° C for 30 minutes, and then further thermally cured at 180 ° C to prepare an evaluation substrate.

- In the case of using the resin sheets 3, 4 and 5 containing the photocurable resin composition layer - (3') Exposure, development and baking of the resin composition layer

The substrate obtained in the above (2) was allowed to stand at room temperature for 1 hour. Thereafter, using a mask pattern, ultraviolet rays of 100 mJ/cm ² were exposed from the support so as to form circular holes having an opening diameter of 60 μm and 500 μm. The exposure system was implemented using a pattern forming device ("US-2O Motor Co., Ltd.""UX-2240"). Then, it was allowed to stand at room temperature for 30 minutes to peel off the support.

With respect to the obtained substrate, a developing solution (2% by mass aqueous sodium hydroxide solution at 30 ° C) was sprayed at a spray pressure of 0.2 MPa for 40 seconds on the entire surface of the resin composition layer. Further, in Comparative Example 2 using the resin sheet 4, a 30 ° C, 1% by mass aqueous sodium carbonate solution was used for the developing liquid.

After the development, the film was dried at 80 ° C for 30 minutes, and then baked at 180 ° C for 90 minutes to obtain an evaluation substrate.

[Modulation of cured product for evaluation]

The hardened material for evaluation was prepared by the following procedure.

- When using the thermosetting resin composition layer resin sheets 1 and 2 -

The resin composition layers of the resin sheets 1 and 2 are placed in contact with the release surface of the PET film ("PET501010" manufactured by LINTEC Co., Ltd.; hereinafter referred to as "evaluation support"). The configuration was carried out using a vacuum laminator ("VP160" manufactured by Nichigo-Morton Co., Ltd.). Laminated. The lamination conditions were evacuation for 20 seconds, pressing temperature of 80 ° C, pressing pressure of 0.2 MPa, and pressurization time of 20 seconds.

After the obtained laminate was peeled off from the support of the resin sheet, the resin composition layer was thermally cured at 180 ° C for 90 minutes. Next, the support for evaluation was peeled off, and the hardened material for evaluation was obtained.

- In the case of using the resin sheets 3, 4 and 5 containing the photocurable resin composition layer -

The resin composition layers of the resin sheets 3, 4, and 5 were carried out in the same manner as in the above [Preparation 1 of the cured product for evaluation], and a PET film ("PET501010" manufactured by LINTEC Co., Ltd.) was also laminated on the release layer. The release surface of the "evaluation support").

After the obtained laminate was allowed to stand at room temperature for 1 hour, the resin composition layer was exposed to ultraviolet rays of 100 mJ/cm ² from the support. After the support from the resin sheet was peeled off, the resin composition layer was treated at 80 ° C for 30 minutes, followed by 180 ° C for 90 minutes. Next, the support for evaluation was peeled off, and the hardened material for evaluation was obtained.

<evaluation of warpage>

First, the evaluation substrate was passed through a reflow device ("HAS-6116" manufactured by ANTM Co., Ltd.) which reproduces the solder reflow temperature at a peak temperature of 260 ° C (the reflow temperature curve is based on IPC/JEDEC J-STD-020C). Next, use a shadow overlay device ("TherMoire AXP" by Akrometrix) to IPC/JEDEC J-STD-020C The reflow temperature profile (the peak temperature of 260 ° C) was used to heat the evaluation substrate, and the displacement of the 25 mm corner portion in the center of the evaluation substrate was measured based on the lattice line disposed on the upper surface of the evaluation substrate.

The difference between the maximum height and the minimum height of the obtained displacement data is "x" for 50 μm or more in the full temperature range, and "○" if it is less than 50 μm.

<Measurement of elastic modulus>

The cured product for evaluation was cut out into a dumbbell shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by ORIENTEC Co., Ltd., and the elastic modulus at 23 ° C and 200 ° C was determined. The measurement was carried out in accordance with JIS K7127.

<Measurement of glass transition point temperature (Tg)>

The cured product for evaluation was cut into test pieces having a width of 5 mm and a length of 15 mm. A thermomechanical analysis apparatus ("TMA-SS6100" manufactured by Seiko Instruments Co., Ltd.) was used for the test piece, and thermomechanical analysis by a tensile weighting method was performed. Specifically, after the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. In the second measurement, the glass transition point temperature Tg (° C.) was calculated from the point where the slope of the dimensional change signal was changed.

The resin sheets 1, 2, 3, 4, and 5 used in the examples and the comparative examples were produced in the following flow steps.

<Production Example 1> Production of Resin Sheet 1

Bisphenol A type epoxy resin ("JER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) 12 parts, naphthalene type epoxy resin ("HD4032SS" manufactured by DIC Co., Ltd., epoxy equivalent of about 144) 3 Separate, bi-xylenol type epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy resin equivalent: 185), 6 parts, biphenyl type epoxy resin ("30003000" made by Nippon Kayaku Co., Ltd., epoxy Equivalent to 288) 25 parts, 10 parts of phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone in 30% by mass), and dissolved in solvent petroleum brain 15 while stirring The mixture was heated to dissolve it. After cooling to room temperature, 20 parts of a phenol novolac-based curing agent ("LA-7054" manufactured by DIC Co., Ltd., a hydroxyl group equivalent of 125, and a 60% solid MEK solution) containing a triazine skeleton was mixed therein, and naphthalene was added. Phenolic curing agent ("SN485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 215, 60% MEK solution), hardening accelerator (4-dimethylaminopyridine (DMAP), solid form 5% by mass of MEK solution) 0.4 parts, flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-, manufactured by Sanguang Co., Ltd. A spherical cerium oxide surface-treated with an average particle diameter of 1 μm, (phosphonophene-10-oxide, average particle diameter: 2 μm), and an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) In the company, "SOC4" manufactured by Admatechs, with a carbon content of 0.47 mg/m ² per unit surface area, 240 parts, was uniformly dispersed by a high-speed rotary mixer to prepare a resin paint 1 .

For the support, a PET film with a thickness of 38 μm is prepared. (Toray (share) system "NS80A"). The resin paint 1 was uniformly applied to the smooth surface of the support, and the thickness of the resin composition layer after drying was 16 μm, and dried at 80 ° C to 120 ° C (average 100 ° C) for 3 minutes to prepare a resin sheet 1 .

<Production Example 2> Production of Resin Sheet 2

In place of phenoxy resin (Mitsubishi Chemical Co., Ltd.), 30 parts of phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd., 30% by mass of MEK/cyclohexanone = 1/1 solution) The surface treated with an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used for 10 parts of YX6954BH30", a solid content of 30% by mass of MEK/cyclohexanone = 1/1 solution). 75 parts of cerium oxide (average particle diameter: 0.5 μm, "SOC2" manufactured by Admatechs, 0.39 mg/m ² of carbon per unit surface area) was substituted for the amine decane-based coupling agent (Shin-Etsu Chemical Co., Ltd.) "KBM573") The spherical cerium oxide (average particle size: 1 μm, "SOC4" manufactured by Admatechs, 0.47 mg/m ² per unit surface area) treated with 240 parts of the surface, and the solvent petroleum brain The resin paint 2 was prepared in the same manner as in Production Example 1 except that the amount of use was changed from 15 parts to 10 parts, and the resin sheet 2 was produced.

<Production Example 3> Production of Resin Sheet 3

Mixed bi-xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 185, 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) 100 parts, the following synthesis example 1 Synthetic photocuring alkali-soluble resin A 73 parts, photopolymerization initiator ("OXE-02" manufactured by BASF JAPAN Co., Ltd., ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene) Mercapto)-9H-carbazol-3-yl]-, 1-(0-ethenylhydrazine), 10% by mass of MEK solution with nonvolatile content) 18 parts, with amine decane-based coupling agent (Shin-Etsu Chemical) In the industrial (stock) system "KBM573"), spherical cerium oxide (average particle diameter: 0.5 μm, "SOC2" manufactured by Admatechs, carbon content per unit surface area: 0.39 mg/m ² ) 120 parts, amine 20 parts of spherical cerium oxide (average particle diameter: 0.1 μm, "UFP-30" manufactured by Electrochemical Industry Co., Ltd.) and thinner treated by a sulfonium-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("DPHA", dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., 10 parts, hardening accelerator (2P4MZ, 4-phenyl-4-methylimidazole, non-volatile content, manufactured by Shikoku Kasei Co., Ltd.) 2.5% by mass of MEK solution) 8.8 parts, rubber particles (GA NTSU KASEI ("AC3816N") (2.4 parts), photo-sensitizer ("TX-S" made by Nippon Kayaku Co., Ltd., 2, 4-ethylthioxyxanthone, non-volatile component 10 4.4 parts by mass of MEK solution) and 10 parts of diethylene glycol monoethyl ether acetal were uniformly dispersed by a high-speed rotary mixer to prepare a resin paint 3.

For the support, a PET film ("R310-16B" manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 16 μm was prepared. The resin paint 3 was uniformly applied to the support so that the thickness of the dried resin composition layer was 23 μm, and it was dried at 75 ° C to 120 ° C (average 100 ° C) for 5 minutes to prepare a resin sheet 3.

(Synthesis Example 1) Synthesis of photocurable alkali-soluble resin A

In a separate flask of 300 mL, 25 g of carbitol acetate and 50 g of 3-isocyanato-3,5,5-trimethylcyclohexyl isocyanate (manufactured by EVONIK Co., Ltd.) were weighed and heated at 40 ° C. Stir. Further, 92.23 g of a pentaerythritol triacrylate-containing material ("M306" manufactured by Toagosei Co., Ltd.), 25 g of carbitol acetate, and 0.45 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) and hydrogen were weighed. 0.4 g of 醌 (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed for 8 minutes with a stirrer ("Hot-Taro" manufactured by THINKY Co., Ltd.) to obtain a mixed solution 1. The obtained mixed solution 1 was dropped into the above-mentioned 300 mL separation flask using a dropping funnel over 1 hour. Thereafter, the mixture was heated and stirred at 40 ° C for 30 minutes to obtain 193.08 g of a reaction product of 3-isocyanato-3,5,5-trimethylcyclohexyl isocyanate and pentaerythritol triacrylate.

On the other hand, 132.26 g of carbitol acetate and 132.26 g of phenol novolak resin ("TD-2090" manufactured by DIC) were weighed in a 500 mL separation flask, and stirred at 75 ° C until completely dissolved. . Next, 193.08 g of the above reactant was added, and the mixture was stirred with IR at 85 ° C until the isocyanate group disappeared. After cooling to 40 ° C, 3.11 g of ethanol (manufactured by Pure Chemical Co., Ltd.) was added, and the mixture was further stirred for 2 hours or more to obtain a photocurable alkali-soluble resin A (acrylate-modified phenol resin) containing an acrylate group and a phenolic hydroxyl group. g. The properties of the obtained photocurable alkali-soluble resin A are as follows.

. 60% by mass solid solvent dissolved product

. Acrylate group ratio of 18%

. Polystyrene-converted average molecular weight (Mn): 4000

. Hydroxyl equivalent: 246

<Production Example 4> Production of Resin Sheet 4

Mixed dimethyl phenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185, 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) 80 parts, containing acrylate group Photocurable alkali-soluble resin with carboxyl group (ZFR-1533H, manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type epoxy acrylate, and 68% diethylene glycol monoethyl ether acetate solution. 147 parts of acid value 70 mgKOH/g), photopolymerization initiator (IRGACURE 907, manufactured by BASF JAPAN Co., Ltd., 2-methyl-[4-(methylthio)phenyl]morpholinyl-1- Alumina spheroidal cerium oxide (average particle diameter: 0.5 μm, (stock) Admatechs "SOC2", per unit) of an amine-based decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The amount of carbon on the surface area is 0.39 mg/m ² ) 80 parts, and the spherical cerium oxide surface-treated with an amino decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter: 0.1 μm, electrical chemical industry ( 20 parts of "UFP-30"), 10 parts of thinner ("DCPA" manufactured by Kyoeisha Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate), and hardening accelerator (Four countries) )"2" 8.8 parts of P4MZ", 2-phenyl-4-methylimidazole, 2.5% by mass of MEK solution of nonvolatile matter), 2.4 parts of rubber particles ("AC3816N" manufactured by GANTSU KASEI), and photosensitizer (Japan) "DETX-S", 2, 4-diethylthioxanthone, 10% by mass of MEK solution of non-volatile content) 2 parts, diethylene glycol monoethyl ether acetal 3 parts of organic solvent) was uniformly dispersed by a high-speed rotary mixer to prepare a resin paint 4.

For the support, a PET film ("R310-16B" manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 16 μm was prepared. The resin paint 4 was uniformly applied to the support, and the thickness of the resin composition layer after drying was 23 μm, and dried at 75 ° C to 120 ° C (average 100 ° C) for 5 minutes to prepare a resin sheet 4.

<Production Example 5> Production of Resin Sheet 5

The resin coating layer 3 was uniformly applied so that the thickness of the dried resin composition layer was 8 μm, and it was dried at 75 to 120 ° C (average 100 ° C) for 2 minutes, and the same procedure as in Production Example 3 was carried out. A resin sheet 5 was produced.

The obtained resin sheets 1 to 5 were combined as shown in the following Table 1, and resin sheet groups 1 to 6 were prepared. In the resin sheets 1 to 5 used in the resin sheet group, the cured product for evaluation was prepared in accordance with the above [Preparation of cured product for evaluation], and the modulus of elasticity and the glass transition temperature (Tg) were measured. The results are shown together in Table 1.

<Example 1>

Using the resin sheet group 1, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Example 2>

Using the resin sheet group 2, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Example 3>

Using the resin sheet group 1, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Example 4>

Using the resin sheet group 3, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Comparative Example 1>

Using the resin sheet group 4, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Comparative Example 2>

Using the resin sheet group 5, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Comparative Example 3>

Using the resin sheet group 4, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

<Comparative Example 4>

Using the resin sheet group 6, the evaluation substrate was obtained in accordance with the above [modulation of the evaluation substrate]. The evaluation results are shown in Table 2.

Claims (8)

A printed wiring board comprising a printed wiring board of a first and a second solder resist layer, wherein a thickness of the first solder resist layer is t ₁ (μm), and an elastic modulus after hardening (23 ° C) is G ₁ ( GPa), the thickness of the second solder resist layer is t ₂ (μm), and the elastic modulus after curing (23 ° C) is G ₂ (GPa), and when the thickness of the printed wiring board is Z (μm), the following is satisfied. Conditions (1) to (3): (1) Z ≦ 250; (2) (t ₁ + t ₂ ) / Z ≧ 0.1; and (3) G ₁ × [t ₁ / (t ₁ + t ₂ ) ]+G ₂ ×[t ₂ /(t ₁ +t ₂ )]≧6, and G ₁ is 6 or more. The printed wiring board according to claim 1, wherein the glass transition temperature (Tg) after curing of the first solder resist layer is 150 ° C or higher. The printed wiring board according to claim 1, wherein the first solder resist layer is formed by curing a resin composition having an inorganic filler content of 60% by mass or more. The printed wiring board according to claim 1, wherein the condition (2) is 0.1 ≦(t ₁ + t ₂ ) / Z ≦ 0.5. The printed wiring board according to claim 1, wherein G ₂ is 6 or more. The printed wiring board according to claim 1, wherein the elastic modulus (200 ° C) after curing of the first solder resist layer is G ₁ ' (GPa), and the elastic modulus after curing of the second solder resist layer ( When 200 ° C) is G ₂ '(GPa), the following condition (4) is further satisfied: (4) G ₁ '×[t ₁ /(t ₁ +t ₂ )]+G ₂ '×[t ₂ /( t ₁ + t ₂ )] ≧ 0.2. A semiconductor device comprising the printed wiring board according to any one of claims 1 to 6. A resin sheet group which is a resin sheet group for a solder resist layer of a printed wiring board, comprising a first resin sheet having a first support and a first resin composition layer joined to the first support, The second resin sheet formed of the second resin composition layer having the second support and the second support is made to have a thickness of the first resin composition layer of t _1p (μm) and an elastic modulus after curing. (23 ° C) is G ₁ (GPa), the thickness of the second resin composition layer is t _2P (μm), and the elastic modulus after curing (23 ° C) is G ₂ (GPa), and the thickness of the printed wiring board is made. When Z (μm), the following conditions (1') to (3') are satisfied: (1') Z ≦ 250; (2') (t _1p + t _2p ) / Z ≧ 0.1; and (3') G ₁ ×[t _1p /(t _1p +t _2p )]+G ₂ ×[t _2p /(t _1p +t _2p )]≧6, and G ₁ is 6 or more.