JP2013041922A - Light receiving device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light receiving device including a via capable of blocking infrared rays.SOLUTION: The light receiving device includes: a first wiring circuit formed on an upper surface of a silicon substrate; a second wiring circuit formed on a lower surface of the silicon substrate; a via which is provided in the silicon substrate so as to connect the first wiring circuit and the second wiring circuit to each other; and a light receiving element provided on an upper surface of the first wiring circuit. The via is filled with a resin composition. A minimum transmittance T of the resin composition, which has a thickness of 20 μm and has been thermally cured, with respect to light of a wavelength of 800-2500 nm is 15% or less.

Description

  The present invention relates to a light receiving device. The present invention relates to a light receiving device in which a light receiving element is provided on a wiring board provided with a wiring board and vias connecting the wiring boards.

  As a light receiving device in which a light receiving element is provided on a wiring board, there is a light receiving device as described in Patent Document 1. In Patent Document 1, A) a step of bonding an image sensor wafer and a glass wafer and then forming a through hole in the image sensor wafer; B) conducting by filling the through hole formed in the image sensor wafer with a conductive material. A light receiving device manufactured by a wafer level chip size package manufacturing method for an image sensor module, the method comprising: forming a body; and C) forming a solder bump on the end of the conductor and connecting it to a PCB substrate on which a circuit is formed. An apparatus is disclosed. Patent Document 1 describes an attempt to prevent malfunction and malfunction that may occur when infrared rays are incident on an image sensor wafer from the outside by coating a glass wafer with an IR cut filter layer.

JP 2007-073958 A

  As a result of intensive studies on such a light receiving device, the present inventors have found that the light receiving element malfunctions due to infrared rays entering from a through hole connecting the wiring board. In addition, in the manufacturing process of the light receiving device, it has been found that in order to accurately arrange the light receiving elements on the wiring board, it is necessary to transmit visible light for visual inspection.

  The present invention has been made in view of the above-described problems, and provides a light receiving device including a via that transmits visible light and can block infrared light.

  According to the present invention for solving the above problems, the first wiring circuit formed on the upper surface of the silicon substrate, the second wiring circuit formed on the lower surface of the silicon substrate, and the second wiring circuit formed on the lower surface of the silicon substrate. A via provided to connect the one wiring circuit and the second wiring circuit, and a light receiving element provided on an upper surface of the first wiring circuit, the via comprising a resin composition There is provided a light receiving device in which the minimum transmittance T with respect to light having a wavelength of 800 nm to 2500 nm of the resin composition that is filled and thermally cured with a thickness of 20 μm is 15% or less.

  The light-receiving device of the present invention includes a via filled with a cured product of a resin composition, and the cured product of the resin composition has a minimum transmittance T of 15% or less for light with a wavelength of 800 nm to 2500 nm at a thickness of 20 μm. It is. For this reason, the infrared rays that cause the light receiving element to malfunction do not affect the operation of the light receiving element, whereby the light receiving device of the present invention can operate stably. Moreover, since the via | veer consisting of the hardened | cured material of this resin composition permeate | transmits visible light, the exact arrangement | positioning on the wiring board of the light receiving element in the manufacturing process of a light receiving device is possible.

  In the light-receiving device of the present invention, the minimum transmittance T ′ for light having a wavelength of 800 nm to 2500 nm after heating the resin composition having a thickness of 20 μm for 10 minutes at 260 ° C. may be 15% or less.

  In the light receiving device of the present invention, the resin composition may include an infrared absorber.

  In the light receiving device of the present invention, the infrared absorber includes metal boride, titanium oxide, zirconium oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), azo compound, aminium compound, cyanine compound, squarylium compound, It may contain at least one selected from an anthraquinone compound, a funatoquinone compound, a dithiol compound, and a polymethine compound.

  In the light receiving device of the present invention, the metal boride may be lanthanum hexaboride.

  ADVANTAGE OF THE INVENTION According to this invention, the light-receiving device provided with the via | veer which can permeate | transmit visible light and can shield infrared rays is provided.

It is typical sectional drawing of the light-receiving device in one Embodiment of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention. It is typical sectional drawing which shows the manufacturing process of the light-receiving device of this invention.

  Hereinafter, preferred embodiments of the light receiving device of the present invention will be described.

  The light receiving device of the present invention includes a first wiring circuit formed on the upper surface of a silicon substrate, a second wiring circuit formed on the lower surface of the silicon substrate, and the first wiring circuit in the silicon substrate. And a via provided to connect the second wiring circuit and a light receiving element provided on the upper surface of the first wiring circuit, and the via is filled with a resin composition and has a thickness. The minimum transmittance T with respect to light having a wavelength of 800 nm to 2500 nm of the resin composition cured by 20 μm is 15% or less.

The light receiving device of the present invention will be described below with reference to FIG. FIG. 1 is a schematic cross-sectional view of a light receiving device of the present invention. As shown in FIG. 1, the light receiving device 1 of the present invention includes a first wiring circuit 11 formed on the upper surface of the silicon substrate 14, a second wiring circuit 12 formed on the lower surface of the silicon substrate 14, Vias 20 provided through the silicon substrate 14 so as to connect the one wiring circuit 11 and the second wiring circuit 12, and a light receiving element 19 provided on the upper surface of the first wiring circuit 11 Is provided. A resin layer 13 is formed inside the via 20.
The light receiving device 1 may further include a spacer 15 formed on the upper surface of the silicon substrate 14 and a transparent substrate 16 disposed on the upper surface of the spacer 15. The transparent substrate 16 is arranged on the upper surface of the spacer 15 so that a gap 21 is formed between the transparent substrate 16 and the light receiving element 19. Moreover, the solder 18 for connecting with another circuit board (not shown) may be provided.
The silicon substrate 14 of the light receiving device 1 is provided with a via 20 that is a through hole. The via 20 is provided so as to connect the first wiring circuit 11 and the second wiring circuit 12. A wiring circuit 22 that connects the first wiring circuit 11 and the second wiring circuit 12 is formed on the inner surface of the via 20. Solder 18 may be provided in the second wiring circuit 14.

  As the first wiring circuit 11 and the second wiring circuit 12, a wiring circuit in which nickel, gold, or the like is plated on a circuit pattern obtained by etching a copper foil or the like can be used.

  Examples of the light receiving element 19 used in the present invention include a CMOS image sensor.

  Examples of the transparent substrate 16 include a glass substrate or an organic substrate such as acrylic, polycarbonate, and polyethersulfone. The transparent substrate 16 is disposed above the light receiving element 19 via the spacer 15 so as to face the light receiving element 19 with a gap 21 between the transparent substrate 16 and the light receiving element 19.

  The spacer 15 is disposed to form a gap 21 between the transparent substrate 16 and the light receiving element 19.

  A light receiving element 19 is provided on the upper surface of the silicon substrate 14 via the first wiring circuit 11. A second wiring circuit 12 is formed on the lower surface of the silicon substrate 14. The silicon substrate 14 is provided with a via 20, and a wiring circuit 22 is formed on the inner surface of the via 20. The first wiring circuit 11 and the second wiring circuit 12 are connected via the wiring circuit 22.

  The wiring circuit 22 formed on the inner surface of the via 20 and the second wiring circuit 12 are covered with a resin layer 13 made of a resin composition except for the solder connection portion. Solder 18 is disposed on the solder connection portion on the second wiring circuit 12.

  By forming the resin layer 13 in the via 20, infrared rays entering from the lower surface of the via 20 can be shielded. Further, since the resin layer 13 functions as an insulating layer, only the solder connection portion on the second wiring circuit 12 is connected to the solder 18, and the portion covered with the resin layer 13 is not connected to the solder 18. it can.

  Next, with reference to FIGS. 2 to 11, a method for manufacturing the light receiving device of the present invention will be described. 2 to 11 are schematic cross-sectional views illustrating the manufacturing process of the light receiving device 1. 7 to 11 are enlarged views of the vicinity of the vias provided in the light receiving device. Therefore, the entire light receiving device is not shown.

  First, as shown in FIG. 2, the first wiring circuit 11 is formed on the upper surface of the silicon substrate 14, and the light receiving element 19 is formed on the upper surface of the first wiring circuit 11.

  Next, as shown in FIG. 3, a photosensitive resin composition layer for spacer 15 a is formed so as to cover the entire top surface of the light receiving element 19. The photosensitive resin composition layer 15a for spacers is comprised from the photosensitive resin composition for spacers. After forming the photosensitive resin composition for spacers in a layer form on the light receiving element 19, exposure and development are performed, and patterning into a desired shape is performed to form the spacers 15. Such a photosensitive resin composition for spacer is not particularly limited as long as it can be patterned by exposure and development. The photosensitive resin composition for spacers may be a negative type or a positive type. Moreover, the photosensitive resin composition for spacers may be liquid or film-like at 25 ° C. When the spacer photosensitive resin composition is liquid at 25 ° C., the spacer photosensitive resin composition layer 15a can be formed by a technique such as spin coating or printing. When the photosensitive resin composition for spacers is a film form at 25 degreeC, formation of the photosensitive resin composition layer 15a for spacers can be performed by methods, such as a lamination.

  Next, as shown in FIG. 4, a mask 33 having a predetermined pattern is disposed above the photosensitive resin composition layer 15a for spacers. Subsequently, the exposure light 34 is irradiated and the part which is not masked with the mask 33 among the photosensitive resin compositions 15a for spacers is exposed. Here, when the photosensitive resin composition for spacers is a negative type, the part in which the gap 21 is formed is masked, and the part in which the spacer 15 is formed is irradiated with exposure light. On the other hand, when the spacer photosensitive resin composition is a positive type, the portion where the spacer 4 is formed is masked, and the portion where the gap 21 is formed is irradiated with the exposure light 34. The exposure light 34 is ultraviolet light, and examples of the light source of the exposure light include g-line, i-line, and excimer laser.

  Next, as shown in FIG. 5, the exposed photosensitive resin composition layer for spacer 15 a is developed with a developer to form a spacer 15. Here, when the photosensitive resin composition for spacers is a negative type, an unexposed part (part in which the gap 21 is formed) is removed. On the other hand, when the photosensitive resin composition for spacers is a positive type, an exposed part (part in which the gap 21 is formed) is removed. The formed spacer 15 functions to form a gap 21 between the light receiving element 19 and the transparent substrate 16 and to bond the silicon substrate 14 and the transparent substrate 16 in a later step. Examples of the developer include, but are not limited to, a solvent and an alkali developer. Among these, an alkaline developer having a low environmental load is preferable.

  Next, as illustrated in FIG. 6, the transparent substrate 16 is disposed on the light receiving element 19 via the spacer 15. The light receiving element 19 and the transparent substrate 16 can be bonded by, for example, aligning the silicon substrate 14 and the transparent substrate 16 and heating and pressurizing from the silicon substrate 14 side or the transparent substrate 16 side.

Next, as shown in FIG. 7, a via hole 20 is formed in the silicon substrate 14. 7 to 11 described below are enlarged views of the vicinity of the via 20 in the light receiving device 1, and do not show the entire light receiving device 1.
Specifically, as shown in FIG. 7, via holes 20 that are through holes are formed in the silicon substrate 13 by dry etching or the like. At this time, the lower surface of the first wiring circuit 11 is exposed. Next, an insulating film 17 made of SiO ₂ or the like is formed on the entire inner surface of the via hole 20 and the lower surface of the silicon substrate 14 by chemical vapor deposition (CVD) or the like. Next, the insulating film 17 formed on the lower surface of the first wiring circuit 11 is removed by dry etching or the like to expose the first wiring circuit 11.

  Next, as shown in FIG. 8, the second wiring circuit 12 covering the insulating film 17 is formed. The second wiring circuit 12 is formed by forming a seed layer (not shown) on the insulating film 17, forming a copper plating layer on the seed layer by an electroless plating method, an electrolytic plating method, and the like. The seed layer and the copper plating layer can be formed by etching into a predetermined pattern. Examples of seed layers include, but are not limited to, Ti, Ti / Cu, Cu, Ni, Cr / Ni. Through the above process, the second wiring circuit 12 formed on the lower surface of the silicon substrate 14, the first wiring circuit 11 formed on the inner surface of the via hole 20, and the wiring circuit 22 that connects the second wiring circuit 12. And are formed.

  Next, as shown in FIG. 9, the inside of the via hole 20 is filled with the resin composition of the present invention, and the entire insulating layer 17 and the second wiring circuit 12 are covered with the resin composition of the present invention. A resin layer 13 is formed. For the resin layer 13, the resin composition of the present invention dissolved or dispersed in a solvent is applied to the lower surface of the silicon substrate 14 with the lower surface of the silicon substrate 14 facing upward, and then the solvent is volatilized. It can be formed by removing. Alternatively, the resin layer 13 is prepared by preparing a paste-like resin composition of the present invention and then applying the paste-like resin composition to the lower surface of the silicon substrate 13 with the lower surface of the silicon substrate 14 facing upward. Can be formed. Alternatively, the resin layer 13 can be formed by forming a film-like resin composition of the present invention on a resin sheet to form an adhesive film, and pressing the adhesive film on the lower surface of the silicon substrate 14.

Next, as shown in FIG. 10, a portion of the resin layer 13 corresponding to the solder mounting portion is removed. The resin layer 13 can be removed by exposure and development using a mask. The resin layer 13 present in the solder mounting portion on the second wiring circuit 12 is removed by exposure and development, and the solder mounting portion of the second wiring circuit 12 is exposed.
Note that in order to form the resin layer 13 at a desired position on the lower surface side of the silicon substrate 13, it is necessary to align the mask before the resin layer 13 is exposed. This alignment is performed by matching the alignment mark previously arranged on the lower surface of the silicon substrate 13 with the alignment mark provided on the mask. Although the resin layer 13 is formed on the entire lower surface of the silicon substrate 14, the resin layer 13 obtained from the resin composition of the present invention has a property of transmitting visible light. It can be visually recognized. Next, the patterned resin layer 13 is heated and cured.

  Next, as shown in FIG. 11, the solder 18 is mounted on the solder mounting portion. Thereby, the light receiving device 1 of the present invention is obtained.

  2 to 11 show a mode in which the light receiving element 19 is mounted on the first wiring circuit 11 before the formation of the spacer 15, the light receiving element 19 is attached to the first wiring circuit after the formation of the spacer 15. 11 may be employed.

  Next, the resin composition of the present invention constituting the resin layer 13 will be described. The resin composition of the present invention has a minimum transmittance T of 15% or less with respect to light having a wavelength of 800 nm to 2500 nm at a thickness of 20 μm. As a result, the wiring board provided with the via filled with the resin composition of the present invention is prevented from receiving infrared rays from the side of the wiring board. Moreover, the resin composition of this invention has the property in which the hardened | cured material permeate | transmits visible light. Such a resin composition contains a resin and an infrared absorber.

  The resin composition of the present invention contains a resin and an infrared absorber. The resin used in the present invention is preferably a photopolymerizable resin that is polymerized by irradiation with exposure light 34. Such a resin is preferably an alkali-soluble resin that can be patterned by irradiation with exposure light 34 and an alkali developer. Furthermore, the resin used in the present invention is preferably a resin that can be thermoset by heating to become a thermoset.

  Such an alkali-soluble resin has an alkali-soluble group and can contribute to heat curing by heating, such as a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, a cyanate group, and the like. It is preferable to have.

  Examples of the alkali-soluble resin that can be used in the present invention include an alkali-soluble resin (A-1) having no photopolymerizable double bond and having an alkali-soluble group, and a photopolymerizable double bond and an alkali. And an alkali-soluble resin (A-2) having a soluble group. A photopolymerizable double bond is a group that undergoes a polymerization reaction with a photopolymerizable double bond of another molecule when irradiated with exposure light. Examples thereof include a vinyl group, a (meth) acryl group, and an allyl group. The double bond in substituents, such as, and the double bond in a molecular chain are mentioned.

  Examples of the alkali-soluble resin (A-1) having no photopolymerizable double bond and having an alkali-soluble group include cresol type, phenol type, bisphenol A type, bisphenol F type, catechol type, resorcinol type, Pyrogallol type novolak resin, phenol aralkyl resin, trisphenylmethane type phenol resin, biphenyl aralkyl type phenol resin, α-naphthol aralkyl type phenol resin, β-naphthol aralkyl type phenol resin, hydroxystyrene resin, methacrylic acid resin, acrylic acid Resin, cyclic olefin resin containing hydroxyl group, carboxyl group, etc., polyamide resin (specifically, having at least one of polybenzoxazole structure and polyimide structure and having hydroxyl group, carboxy group in the main chain or side chain Resin having a poly group, an ether group or an ester group, a resin having a polybenzoxazole precursor structure, a resin having a polyimide precursor structure, a resin having a polyamic acid ester structure, and the like. It has a phenolic hydroxyl group or carboxyl group which is an alkali-soluble group. The alkali-soluble resin (A-1) includes cresol type, phenol type, bisphenol A, and low molecular weight compounds having one repeating unit such as cresol, bisphenol A, bisphenol F, catechol, resorcinol, and pyrogallol. High molecular weight compounds in which the number of repeating units is 2 or more, such as novolak resins such as type, bisphenol F type, catechol type, resorcinol type, pyrogallol type and the like are also included.

  The resin composition of the present invention may contain an alkali-soluble thermoplastic resin such as a carboxyl group-containing acrylic resin.

  Examples of the alkali-soluble resin (A-2) having a photopolymerizable double bond and having an alkali-soluble group include, for example, a resin having an alkali-soluble group such as the alkali-soluble resin (A-1). Resin in which a group having a bond is introduced; a resin in which an alkali-soluble group is introduced into a resin having a photopolymerizable double bond, and the like. In the present invention, (meth) acryl refers to acryl or methacryl, and (meth) acryloyl refers to acryloyl or methacryloyl.

As a resin in which a group having a double bond is introduced into a resin having an alkali-soluble group such as an alkali-soluble resin (A-1), for example, glycidyl (meth) is partially added to the phenolic hydroxyl group of the phenol resin. Examples include (meth) acryl-modified phenolic resin obtained by reacting acrylate, (meth) acryl-modified bisphenol obtained by reacting one hydroxyl group of bisphenol compound such as bisphenol A and glycidyl (meth) acrylate. In addition, as a resin in which an alkali-soluble group is introduced into a resin having a photopolymerizable double bond, for example, a compound having a (meth) acryl group and an epoxy group at both hydroxyl groups of a bisphenol compound, for example, glycidyl ( Resin in which an acid anhydride is reacted with a hydroxyl group of a resin obtained by reacting an epoxy group of (meth) acrylate to introduce a carboxyl group, a compound having a (meth) acryl group and an epoxy group on both hydroxyl groups of a bisphenol compound For example, the resin etc. which introduce | transduced the carboxyl group by making dicarboxylic acid react with the hydroxyl group of resin obtained by making the epoxy group of glycidyl (meth) acrylate react are mentioned.
Among these, alkali-soluble resin (A-2) is preferable, and (meth) acryl-modified phenol resin is particularly preferable. The alkali-soluble resin (A-2) can reliably crosslink the exposed portion during exposure and prevent the exposed portion from dissolving in the developer during subsequent development. Moreover, the mechanical strength of the exposed part after exposure can be improved. Therefore, the shape retention characteristic of the obtained via can be improved.

  Here, of the alkali-soluble resin (A-2), a resin in which a group having a double bond is introduced into the alkali-soluble group of a resin having an alkali-soluble group such as the alkali-soluble resin (A-1). In this case, the alkali-soluble group equivalent (molecular weight / number of alkali-soluble groups) is not particularly limited, but is preferably 30 to 2000, and particularly preferably 50 to 1000. If the alkali-soluble group equivalent is larger than the upper limit, alkali developability is lowered, and development may take a long time. On the other hand, if it is smaller than the lower limit, the alkali development resistance of the exposed area may be lowered. The alkali-soluble group equivalent is calculated using the weight average molecular weight as the molecular weight.

  Further, among the alkali-soluble resin (A-2), an acid anhydride or dicarboxylic acid is added to the hydroxyl group of a resin obtained by reacting both hydroxyl groups of a bisphenol compound with an epoxy group of a compound having a (meth) acryl group and an epoxy group. In the case of a resin into which a carboxyl group has been introduced by reacting an acid, the alkali-soluble group equivalent (molecular weight / number of alkali-soluble groups) is not particularly limited, but is preferably 30-2000, particularly preferably 50-1000. If the alkali-soluble group equivalent is larger than the upper limit value, alkali developability is lowered and development may take a long time. On the other hand, if it is smaller than the lower limit, the alkali development resistance of the exposed area may be lowered.

  As an infrared absorber used for the resin composition of this invention, Preferably, the infrared absorber which has the largest absorption wavelength in the range of 800-2500 nm is mentioned. Moreover, the minimum transmittance of the maximum absorption wavelength of the infrared absorber is 15% or less, preferably 1 to 10%, particularly preferably 2 to 5%. When the resin composition contains an infrared absorber, the via filled with the cured product of the resin composition has an infrared shielding property.

  The thermal decomposition temperature of the infrared absorber is preferably 200 ° C. or higher, particularly preferably 250 ° C. or higher. Thereby, in the process of thermosetting a resin composition, an infrared absorber does not deteriorate. Thereby, the above-mentioned property of absorbing infrared rays can be maintained even after thermosetting.

  Examples of such infrared absorbers include metal borides, titanium oxide, zirconium oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), azo compounds, aminium compounds, cyanine compounds, squarylium compounds, and anthraquinone compounds. , Funatoquinone compounds, dithiol compounds, and polymethine compounds.

Examples of the metal boride include lanthanum hexaboride (LaB ₆ ), praseodymium hexaboride (PrB ₆ ), neodymium hexaboride (NdB ₆ ), cerium hexaboride (CeB ₆ ), and gadolinium hexaboride (GdB). ₆ ), terbium hexaboride (TbB ₆ ), dysprosium hexaboride (DyB ₆ ), holmium hexaboride (HoB ₆ ), yttrium hexaboride (YB ₆ ), samarium hexaboride (SmB ₆ ), hexaboro of europium _(EuB 6), hexaboride erbium _(ErB 6), hexaboride thulium _(TmB 6), hexaboride ytterbium _(YbB 6), hexaboride lutetium _(LuB 6), hexaboride strontium (SrB ₆ ), hexaboride calcium _(CaB 6), titanium boride _(TiB 2), zirconium boride _(ZrB 2) Hafnium boride _(HfB 2), vanadium boride _(VB 2), tantalum boride _(TaB 2), chromium borides (CrB and _CrB 2), molybdenum borides _(MoB 2, _Mo 2 _{B 5} and MoB) and boric Examples thereof include tungsten halide (W ₂ B ₅ ) and mixtures thereof.

An azo compound is a compound having a —N═N— bond and a maximum absorption wavelength in the range of 800 to 2500 nm. More specifically, it is a compound having a —N═N— bond and having a hydroxyl group or a functional group derived from a hydroxyl group at the para position of the —N═N— bond. Examples of the azo compound include the following general formula (1):
R ¹ —N═N—R ² (1)
The azo compound represented by these is mentioned. In the general formula (1), R ¹ and R ² are aromatic groups and have at least one hydroxyl group or a functional group derived from a hydroxyl group at the para position of the azo group. R ¹ and R ² may be the same or different. More specifically, examples of the azo compound include azo compounds represented by the following formulas (1-1) to (1-6).

  The aminium compound is a compound in which one of the amine's unshared electron pair electrons is oxidized to become a cation to form a salt with the anion, and the maximum absorption wavelength is in the range of 800 to 2500 nm. As an aminium compound, for example, the following general formula (2):

The aminium compound represented by these is mentioned. In the general formula (2), R ³ is an alkyl group having 1 to 6 carbon atoms, A is an aromatic group, X is a group consisting of I ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ^—. It is a kind chosen from. R ³ may be the same or different.

  The anthraquinone compound has the following formula:

And a compound having a maximum absorption wavelength in the range of 800 to 2500 nm. For example, as an anthraquinone compound, the following formula (9):

The anthraquinone compound represented by these is mentioned. In said formula (9), R < ¹² > and R < ¹³ > are substituents which have a substituent which has a nitrogen atom, a hydroxyl group, and an aromatic ring, and p and q are an integer of 1-3. R ¹² and R ¹³ may be the same or different. More specifically, as an anthraquinone compound, the following formula (9-1):

で表されるアントラキノン化合物、下記式（９−２）：

An anthraquinone compound represented by the following formula (9-2):

で表されるアントラキノン化合物、下記式（９−３）：

An anthraquinone compound represented by the following formula (9-3):

で表されるアントラキノン化合物が挙げられる。

The anthraquinone compound represented by these is mentioned.

  The dithiol / metal complex compound has the following formula (10):

で表される構造を有し、且つ最大吸収波長が８００〜２５００ｎｍの範囲内にある化合物である。上記式（１０）中、Ｒ^３は炭素数１〜４のアルキル基、アリール基、アラルキル基、アルキルアミノ基、ハロゲンいずれかを表し、Ｍはニッケル、白金、パラジウムのいずれかを表す。

And a compound having a maximum absorption wavelength in the range of 800 to 2500 nm. In the above formula (10), R ³ represents an alkyl group having 1 to 4 carbon atoms, an aryl group, an aralkyl group, an alkylamino group, or halogen, and M represents any of nickel, platinum, and palladium.

  Among these infrared absorbers, metal borides having excellent infrared absorbing ability and excellent heat resistance are preferable.

  An infrared absorber may be a single type or a combination of two or more types. Moreover, the resin composition of the present invention can shield infrared rays in a wide range of wavelengths by combining a plurality of infrared absorbers having different maximum absorption wavelengths. For example, by combining an infrared absorber having a maximum absorption wavelength of 871 nm, an infrared absorber having a maximum absorption wavelength of 913 nm, and an infrared absorber having a maximum absorption wavelength of 966 nm, the infrared rays in the region of 875 to 960 nm are shielded. Can do.

  In the present invention, the maximum absorption wavelength of the infrared absorbent refers to a wavelength at which the transmittance becomes the smallest when analyzed by spectral light transmittance analysis. Moreover, the thermal decomposition temperature of an infrared absorber is a value measured by thermogravimetric change analysis.

  The amount of the infrared absorber in the resin composition is preferably 0.01% by weight or more and 15% by weight or less, and more preferably 0.1% by weight or more and 10% by weight with respect to the entire resin composition. % Or less. When the content of the infrared absorber is equal to or more than the above lower limit, the effect of shielding the infrared rays from the obtained via is enhanced. Moreover, visible light transmittance with a wavelength of 400-700 nm can be 5.0% or more because content of an infrared absorber is below the said upper limit. In addition, when one type of infrared absorber is used as the infrared absorber, the content of each infrared absorber refers to the content of the one type of infrared absorber. When a plurality of infrared absorbers having different maximum absorption wavelengths are used, the content of each infrared absorber refers to the content of each of the plurality of infrared absorbers used. For example, when an infrared absorber having a maximum absorption wavelength of 871 nm, an infrared absorber having a maximum absorption wavelength of 913 nm, and an infrared absorber having a maximum absorption wavelength of 966 nm are used in combination, the content of each infrared absorber is It is preferable that it is 0.01 to 15 weight% of the whole resin composition, and it is especially preferable that it is 0.1 to 10 weight%.

  When a plurality of infrared absorbers having different maximum absorption wavelengths are used, the total content of the infrared absorbers used is preferably 0.01 to 15% by weight based on the total resin composition. It is particularly preferably 1 to 10% by weight.

  The average particle size of the infrared absorber is not particularly limited, but is preferably 10 μm or less. Furthermore, it is preferable that it is 5 micrometers or less. The “average particle size” here refers to the particle size (D50) at an integrated value of 50% in the particle size distribution determined by the laser diffraction scattering method.

  When the average particle diameter of the infrared absorbent is equal to or greater than the above upper limit, when vias are formed, the bulkiness in the thickness direction causes voids between the particles, resulting in high infrared transmittance. Therefore, unless the addition amount of the infrared absorber is increased, the infrared transmittance cannot be lowered.

  On the other hand, when the average particle diameter of the infrared absorbent is not more than the above upper limit, the dispersibility of the infrared absorbent in the resin composition is improved, and the bulk in the thickness direction can be reduced. That is, when the via is formed, the number of particles spreading in the plane direction increases, so that the filling ratio of the infrared absorbent particles can be increased as the entire via. As a result, the infrared transmittance can be lowered as a whole via.

  Thus, in the present invention, even if the content of the infrared absorber is small, the transmittance in the infrared region can be reliably lowered. Therefore, infrared shielding properties can be obtained at low cost.

  Here, among the infrared absorbents having the average particle diameter as described above, those that are inorganic can be formed by crushing under severe conditions. Examples of the method for forming the infrared absorber include a ball mill method and a bead mill method.

  The resin composition of the present invention may further contain a thermosetting resin, a photopolymerization compound, a photopolymerization initiator, a photoacid generator, an inorganic filler and the like in addition to the resin and the infrared absorber.

  The thermosetting resin includes a thermosetting resin addition type resin that forms a cured product by reacting with a thermosetting resin such as an epoxy resin, and a functional group bonded to its own molecular chain within the molecular chain. And self-condensation type resin that forms a cured product by cyclization reaction. As the thermosetting resin addition type resin, for example, (meth) acryl-modified phenol resin, (meth) acryl-modified bisphenol, and a compound having a (meth) acryl group and an epoxy group are reacted with the hydroxyl groups of both bisphenol compounds. The hydroxyl group of the resulting resin is reacted with an acid anhydride to introduce a carboxyl group into the resin, and the hydroxyl group of the resin obtained by reacting both hydroxyl groups of the bisphenol compound with a compound having a (meth) acrylic group and an epoxy group. And a resin in which a carboxyl group is introduced by reacting a dicarboxylic acid. Examples of the self-condensation type resin include, for example, a resin in which a (meth) acryl group is introduced into a polyamide-based resin, more specifically, at least one of a polybenzoxazole structure and a polyimide structure, and a main chain or side. Resin having a hydroxyl group, carboxyl group, ether group or ester group in the chain, a resin having a polybenzoxazole precursor structure, a resin having a polyimide precursor structure, a resin having a polyamic acid ester structure, etc. Introduced resin etc. are mentioned.

  By including a thermosetting resin, after the resin composition layer is developed, it is possible to obtain a resin composition that becomes a thermoset by heat curing by heating.

  Examples of the thermosetting resin include phenol novolac resins, cresol novolac resins, novolac type phenol resins such as bisphenol A novolac resin, phenol resins such as resol phenol resin, bisphenol type epoxy such as bisphenol A epoxy resin and bisphenol F epoxy resin. Resin, novolak epoxy resin, cresol novolak epoxy resin, etc., novolac epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene type epoxy resin, trisphenolmethane type epoxy resin, naphthalene type epoxy Resin, epoxy resin such as silicone-modified epoxy resin, urea (urea) resin, resin having triazine ring such as melamine resin, unsaturated polyester Le resins, bismaleimide resins, polyurethane resins, diallyl phthalate resins, silicone resins, resins having a benzoxazine ring, cyanate ester resins. Especially, an epoxy resin is preferable at the point which can enlarge the free volume of a resin composition and can improve the moisture permeability of hardened | cured material. Moreover, the water absorption rate of the cured product of the resin composition can be lowered. Furthermore, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, and a trisphenol methane type epoxy resin are particularly preferable in that the moisture permeability can be increased. The thermosetting resins include low molecular weight compounds having one repeating unit such as bisphenol type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin, novolac epoxy resins, cresol novolac epoxy resins, etc. High molecular weight compounds having 2 or more repeating units such as novolak type epoxy resins are also included.

  The content of the thermosetting resin is not particularly limited, but is preferably 10 to 70% by weight, more preferably 15 to 65% by weight, and particularly preferably 20 to 60% by weight in the resin composition. When the content of the thermosetting resin is within the above range, the mechanical properties of the obtained via can be enhanced.

  When an epoxy resin is used as the thermosetting resin, the resin composition of the present invention can contain a compound that acts as a curing agent for the epoxy resin. Examples of compounds that act as curing agents for epoxy resins include, but are not limited to, phenol derivatives, carboxylic acid derivatives, imidazoles, and the like. Of these, a phenol derivative is preferable because it has a function as a dissolution accelerator during exposure and development.

  Examples of the phenol derivatives include phenol novolac resins, phenol aralkyl resins having a phenylene skeleton, trisphenylmethane type phenol resins, biphenyl aralkyl type phenol resins, α-naphthol aralkyl type phenol resins, β-naphthol aralkyl type phenol resins, and the like. Among these, a phenol novolac resin is preferable in that the effect of reducing the residue after exposure and development is enhanced.

  A photopolymerizable compound is a compound that undergoes photopolymerization when irradiated with light, and is a compound having a photopolymerizable double bond. Examples of the photopolymerizable compound include a photopolymerizable monomer having a photopolymerizable double bond, a photopolymerizable oligomer, and a resin having a photopolymerizable double bond in the main chain or side chain.

  Examples of photopolymerizable monomers include bisphenol A ethylene glycol-modified di (meth) acrylate, isocyanuric acid ethylene glycol-modified di (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene glycol tri (meth) acrylate, trimethylolpropane ethylene glycol tri (Meth) acrylate, isocyanuric acid ethylene glycol modified tri (meth) acrylate, dipentaerythritol pen (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate.

  Examples of the photopolymerizable oligomer include urethane (meth) acrylate and epoxy (meth) acrylate.

  As a resin having a photopolymerizable double bond in the main chain or side chain, a glycidyl group of glycidyl (meth) acrylate is reacted with a carboxyl group of a (meth) acrylic resin having a structural unit of (meth) acrylic acid. And a resin obtained by reacting a carboxyl group of (meth) acrylic acid with a glycidyl group of a (meth) acrylic resin having a structural unit of glycidyl (meth) acrylate. As for the molecular weight of resin which has a photopolymerizable double bond in a principal chain or a side chain, 50-5000 are preferable.

  Moreover, as a photopolymerizable compound, the photopolymerizable compound which has a hydrophilic group or a hydrophilic structure is mentioned. Residues after patterning the resin composition layer can be reduced by the photopolymerizable compound having a hydrophilic group or a hydrophilic structure. The reason for this is considered to be that the affinity for water is increased by imparting a hydrophilic group or a hydrophilic structure, so that the resin composition is easily dissolved in an alkaline developer. Examples of the hydrophilic group or the hydrophilic structure include hydrophilic groups such as an alcoholic hydroxyl group, and hydrophilic structures such as an oxyethylene structure and an oxypropylene structure.

  Examples of the photopolymerizable compound having a hydrophilic group or a hydrophilic structure include an acrylic compound having a hydroxyl group, an acrylic compound having an oxyethylene structure or an oxypropylene structure, and among these, an acrylic compound having a hydroxyl group. Compounds are preferred. When the resin composition of the present invention contains an acrylic compound having a hydroxyl group or an acrylic compound having an oxyethylene structure or an oxypropylene structure, the patterning property (developability) is enhanced.

  As the acrylic compound having a hydroxyl group, a compound obtained by reacting and adding (meth) acrylic acid to an epoxy group of an epoxy compound, specifically, a compound obtained by adding methacrylic acid to ethylene glycol diglycidyl ether, A compound in which acrylic acid is added to ethylene glycol diglycidyl ether, a compound in which methacrylic acid is added to propylene glycol diglycidyl ether, a compound in which acrylic acid is added to propylene glycol diglycidyl ether, and methacrylic acid to tripropylene glycol diglycidyl ether Compound with acid added, Compound with acrylic acid added to tripropylene glycol diglycidyl ether, Compound with methacrylic acid added to bisphenol A diglycidyl ether, Bisphenol A Compound obtained by adding acrylic acid to the glycidyl ether and the like.

  The epoxy compound related to the acrylic compound having a hydroxyl group, that is, the epoxy compound to which (meth) acrylic acid is added is preferably an epoxy compound having an aromatic ring from the viewpoint of excellent shape retention. Among the acrylic compounds having a hydroxyl group, one or more compounds selected from the following formula (11) are preferable in terms of excellent shape retention in addition to the effect of reducing residues.

  Although content of the photopolymerizable compound which has a hydrophilic group or a hydrophilic structure in the resin composition of this invention is not specifically limited, 1 to 20 weight% is preferable and 2 to 8 weight% is especially preferable. When the content of the photopolymerizable compound having a hydrophilic group or a hydrophilic structure is within the above range, it is particularly excellent in the effect of improving both the effect of reducing residues and the shape retention.

  Moreover, a polyfunctional photopolymerizable compound is mentioned as a photopolymerizable compound. By including the polyfunctional photopolymerizable compound (G-2), the patternability can be further improved together with the alkali-soluble resin described above. The polyfunctional photopolymerizable compound is a photopolymerizable compound having two or more photopolymerizable double bonds and different from the photopolymerizable compound having a hydrophilic group or a hydrophilic structure. Here, being different from a photopolymerizable compound having a hydrophilic group or a hydrophilic structure means that the structure, molecular weight and the like are different.

  Examples of the polyfunctional photopolymerizable compound (G-2) include glycerin dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythrole hexaacrylate. Etc.

  The polyfunctional photopolymerizable compound (G-2) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. When the resin composition of the present invention contains a trifunctional or higher polyfunctional photopolymerizable compound, the shape retention is excellent even when the filler is substantially not contained.

  Examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. The reason why the resin composition of the present invention includes a polyfunctional photopolymerizable compound having three or more functional groups and is excellent in shape retention even when it contains substantially no filler is three-dimensionally photocrosslinked. This is probably because the photocrosslinking density increases and the thermal modulus does not decrease.

  Although content of the polyfunctional photopolymerizable compound in the resin composition of this invention is not specifically limited, 5 to 50 weight% is preferable and 10 to 40 weight% is especially preferable. If the content of the polyfunctional photopolymerizable compound (G-2) exceeds the above upper limit, the adhesion strength may be lowered. On the other hand, if it is less than the above lower limit, the shape retention may be lowered.

  A pattern is formed by using a photopolymerizable compound (G-1) having a hydrophilic group or a hydrophilic structure in combination with a polyfunctional photopolymerizable compound (particularly, a trifunctional or higher polyfunctional photopolymerizable compound). Thus, a resin composition excellent in both the effect of reducing the residue during the treatment and the effect of retaining the shape of the pattern can be obtained. When used in combination, the ratio of the content of the photopolymerizable compound (G-1) having a hydrophilic group or hydrophilic structure to the content of the polyfunctional photopolymerizable compound (G-2) (hydrophilic group or hydrophilic structure The content of the photopolymerizable compound having a content / the content of the polyfunctional photopolymerizable compound) is not particularly limited, but is preferably 0.05 to 1.5, and particularly preferably 0.1 to 1.0. When the ratio of the photopolymerizable compound (G-1) having a hydrophilic group or a hydrophilic structure to the polyfunctional photopolymerizable compound is within the above range, in addition to the above-mentioned residue reducing effect and shape retaining effect, Excellent in workability, fine workability and reliability.

  The photopolymerization initiator is not particularly limited. For example, diazoquinone, benzophenone, acetophenone, benzoin, benzoin isobutyl ether, methyl benzoin benzoate, benzoin benzoic acid, benzoin methyl ether, benzylfinyl sulfide, benzyl, benzyldimethyl ketal , Dibenzyl, diacetyl and the like. Of these, benzophenone and benzyldimethyl ketal, which are excellent in patternability, are preferable.

  Although content of a photoinitiator is not specifically limited in the resin composition of this invention, 0.5 to 10 weight% of the whole resin composition is preferable, and 1 to 5 weight% is especially preferable. If the content of the photopolymerization initiator is less than the lower limit, the effect of initiating photopolymerization may be reduced. Moreover, when the said upper limit is exceeded, reactivity will become high too much and the preservability of the resin composition before use and the resolution after patterning may become low. Therefore, by setting the content of the photopolymerization initiator within the above range, a resin composition having an excellent balance between the effect of initiating photopolymerization and the effect of increasing the storage stability before use and the resolution after patterning. You can get things.

  The photoacid generator is a substance that decomposes by absorbing exposure light to generate an acid. Since the acid generated by light improves the solubility of the exposed portion of the resin composition in an alkaline developer, the patternability of the resin composition can be improved.

  Examples of the photoacid generator include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Specific examples include ester compounds represented by the formulas (16) to (19). The photoacid generator (C) may be one type or a combination of two or more types.

  In formulas (16) to (19), Q is selected from any one of a hydrogen atom and a structure represented by formula (20) and formula (21). Here, at least one of Q of each compound has a structure represented by formula (20) or formula (21).

  The content of the photoacid generator (C) in the resin composition of the present invention is preferably 1 to 50 parts by weight, particularly preferably 10 to 40 parts by weight, based on 100 parts by weight of the resin used. The sensitivity is particularly excellent when the content of the photoacid generator (C) is within the above range.

  Examples of inorganic fillers include silicates such as talc, calcined clay, unfired clay, mica, glass, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), silica powder such as crystalline silica, etc. Oxides, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, Examples thereof include borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride. These inorganic fillers may be used alone or in combination of two or more. Of these, silica powder such as fused silica and crystalline silica is preferred, and spherical fused silica is particularly preferred.

  When the resin composition of the present invention contains an inorganic filler, the cured resin composition has high heat resistance, moisture resistance, strength, and the like. The shape of the inorganic filler is not particularly limited, but is preferably a true sphere.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 to 50 nm, particularly preferably 10 to 30 nm. If the average particle size of the inorganic filler is less than the above lower limit value, the inorganic filler tends to aggregate, and thus the distribution of the inorganic filler in the resin composition may vary. On the other hand, when the above upper limit is exceeded, resolution by exposure and development may become too low.

  The resin composition of this invention can contain the compound (compound E) which has a phenolic hydroxyl group and a carboxyl group. Thereby, the affinity between the resin composition and the alkaline developer can be increased. Moreover, compatibility with the other component which comprises a resin composition can be improved. Therefore, the residue after exposure and development can be reduced. Increasing the carboxyl group concentration in one molecule improves the affinity for an alkaline developer. However, if the concentration is too high, the crystallinity between the molecules of this compound will be too high, and the compatibility with other components constituting the photosensitive resin composition will be low. Therefore, in addition to the carboxyl group, the photosensitive resin composition includes the compound E having an affinity for an alkaline developer that is not as high as that of the carboxyl group. It is possible to achieve compatibility with other resin components.

  Although the weight average molecular weight of the compound (E) which has a phenolic hydroxyl group and a carboxyl group is not specifically limited, Preferably it is 100-5000, More preferably, it is 150-3000, Most preferably, it is 200-2000. By making the weight average molecular weight of a compound (E) into the said range, the effect which makes compatible the compatibility with the other resin component which comprises the affinity with an alkali developing solution and the other photosensitive resin composition increases. Here, the weight average molecular weight is measured by the same method as described above.

  Although the compound (E) which has a phenolic hydroxyl group and a carboxyl group will not be specifically limited if it has a phenolic hydroxyl group and a carboxyl group, For example, the compound shown by the following general formula (22)-(24) is mentioned. It is done. The resin composition of the present invention includes a compound represented by the following general formulas (22) to (24) as the compound (E) having a phenolic hydroxyl group and a carboxyl group, thereby reducing residues after exposure and development. The effect is further increased.

In the general formula (22), R ²¹ represents an organic group other than aromatic, and a and b are integers of 1 to 3. Although a and b are not specifically limited, a = 1 and b = 2 are preferable. By setting a = 1 and b = 2, both the effect of reducing the residue after exposure and development of the resin composition and the effect of improving the compatibility with other resin components constituting the resin composition can be achieved. it can.

R ²¹ is not particularly limited as long as it is an organic group other than aromatic, and examples thereof include a single bond and a linear or branched hydrocarbon group having 1 to 20 carbon atoms. When b is 1, specific examples include methylene, ethylene, n-propylene, i-propylene, i-pentylene, sec-pentylene, t-pentylene, methylbutyl, 1,1, dimethylpropylene, n-hexylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 4-methylpentylene, 1-ethylbutylene, 2-ethylbutylene, 3-ethylbutylene, 1,1-dimethylbutylene, 2,2- Dimethylbutylene, 3,3-dimethylbutylene, 1-ethyl-1-methylpropylene, n-heptylene, 1-methylhexylene, 2-methylhexylene, 3-methylhexylene, 4-methylhexylene, 5-methyl Hexylene, 1-ethylpentylene, 2-ethylpentylene, 3-ethylpentylene, 4-ethylpentylene 1,1-dimethylpentylene, 2,2-dimethylpentylene, 3,3-dimethylpentylene, 4,4-dimethylpentylene, 1-propylbutylene, n-octylene, 1-methylheptylene, 2-methylheptylene 3-methylheptylene, 4-methylheptylene, 5-methylheptylene, 6-methylheptylene, 1-ethylhexylene, 2-ethylhexylene, 3-ethylhexylene, 4-ethylhexylene, 5-ethylhexylene, 6-ethyl Hexylene, 1,1-dimethylhexylene, 2,2-dimethylhexylene, 3,3, -dimethylhexylene, 4,4-dimethylhexylene, 5,5-dimethylhexylene, 1-propylpentylene, 2-propylpentylene and the like can be mentioned, and a linear or branched group having 1 to 6 carbon atoms is preferable. By setting the number of carbon atoms to 1 to 6, the effect of reducing the residue after exposure and development of the resin composition and the effect of improving the compatibility with other resin components constituting the resin composition can be improved. .

  Moreover, when b is 2, the group shown by the following general formula (25) is specifically illustrated.

In the general formula (25), R ²³ and R ²⁴ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear alkylene group having 1 to 20 carbon atoms (the terminal is a carboxyl group). ), A carboxyl group. * Is bonded to a benzene ring having a phenolic hydroxyl group in the general formula (22). However, both R ^{23 and} R ²⁴ are not a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and one of R ²³ or R ²⁴ is a hydrogen atom, 1 to carbon atoms. When it is a 20 linear or branched alkyl group, the other is a linear alkylene group having 1 to 20 carbon atoms (terminal is a carboxyl group).

At least one of R ²³ and R ^{24 in} the general formula (25) is a linear or branched alkylene group having 1 to 10 carbon atoms (terminal is a carboxyl group). Thereby, the residue after exposure and development of the resin composition can be reduced. Moreover, the effect which improves compatibility with the other resin component which comprises a resin composition can be made high. Furthermore, it is especially preferable that it is a C1-C6 linear or branched alkylene group (a terminal is a carboxyl group).

  When b is 3, specifically, a group represented by the following general formula (26) is exemplified.

In the general formula (26), R ²⁵ represents a linear or branched alkylene group having 1 to 20 carbon atoms (terminal is a carboxyl group) or a carboxyl group, and * represents a phenol in the general formula (22). A benzene ring having a functional hydroxyl group is bonded.

In General Formula (26), R ²⁵ is, for example, a linear or branched alkylene group having 1 to 10 carbon atoms (terminal is a carboxyl group). Thereby, the residue after exposure and development of the resin composition can be reduced. Moreover, the effect which improves compatibility with the other resin component which comprises a resin composition can be made high. Furthermore, it is especially preferable that it is a C1-C6 linear or branched alkylene group (a terminal is a carboxyl group).

  In general formula (23), c and d are integers of 1 to 5. The compound represented by the general formula (23) is not particularly limited, and 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4- Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, etc. 2,3-dihydroxybenzoic acid in that the effect of reducing the residue after exposure and development of the resin composition and the effect of improving the compatibility with other resin components constituting the resin composition are increased. 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-tri Dorokishi benzoic acid, 2,4,6-trihydroxy benzoic acid.

  In general formula (24), e and f are integers of 1-3. e and f are not particularly limited, but e = 1 and f = 2, for example. Thereby, the residue after exposure and development of the resin composition can be reduced. Moreover, the effect which improves compatibility with the other resin component which comprises a resin composition can be made high.

In General Formula (24), R ²² represents an organic group other than aromatic, and is not particularly limited, and is a single bond, a hydrogen atom, or a linear or branched hydrocarbon group having 1 to 20 carbon atoms. Is mentioned. R ²² is, for example, a linear or branched hydrocarbon group having 1 to 10 carbon atoms. Thereby, the residue after exposure and development of the resin composition can be reduced. Moreover, the effect which improves compatibility with the other resin component which comprises a resin composition can be made high. Furthermore, it is especially preferable that it is a C1-C6 linear or branched hydrocarbon group.

  The compound represented by the general formula (24) is not particularly limited, and examples thereof include phenol phthaline and phenol phthaline derivatives. Thereby, phenolphthaline can reduce the residue after exposure and development of the resin composition. Moreover, the effect which improves compatibility with the other resin component which comprises a resin composition can be made high.

  Although content of the compound (E) which has a phenolic hydroxyl group and a carboxyl group is not specifically limited, Preferably it is 0.1-30 weight% in a resin composition, More preferably, it is 0.3-20 weight %, Particularly preferably 0.5 to 15% by weight. When content of a compound (E) exists in the said range, the effect of reducing the residue after exposure and image development of the photosensitive resin composition increases. Furthermore, compatibility with other resin components constituting the resin composition can be ensured.

  The resin composition of this invention can contain additives, such as a ultraviolet absorber, a leveling agent, a coupling agent, antioxidant, as needed.

  The resin composition can be obtained by mixing the above components by a method usually used in the art. The cured product obtained by curing the resin composition thus obtained has a light transmittance T with respect to light having a wavelength of 800 nm to 2500 nm at a thickness of 20 μm of 15% or less, preferably 1 to 15%. Most preferably, it is 2 to 10%. Thereby, it is possible to prevent infrared rays that cause the light receiving element to malfunction from being incident from the side surface and the lower surface of the silicon substrate. Therefore, the light receiving device of the present invention can operate stably.

  Further, the cured product of the resin composition of the present invention has a minimum transmittance T ′ for light having a wavelength of 800 nm to 2500 nm after heating at 260 ° C. for 10 minutes at a thickness of 20 μm, preferably 15% or less, preferably 1 -15%, particularly preferably 2-10%. The cured product of the resin composition of the present invention is suppressed from increasing its infrared transmittance even after heat treatment. For this reason, the heat treatment received by the resin composition during via formation suppresses the increase in infrared transmittance.

The following examples further illustrate the present invention, but the scope of the present invention is not limited to these examples.
Example 1
1. Synthesis of resin having alkali-soluble group and double bond (curable resin curable with both light and heat: methacryl-modified bisphenol A type phenol novolac resin: MPN) Bisphenol A type novolak resin (Phenolite LF-4871, large 500 g of a 60% solid content MEK solution (manufactured by Nippon Ink Chemical Co., Ltd.) was put into a 2 L flask. Next, 1.5 g of tributylamine as a catalyst and 0.15 g of hydroquinone as a polymerization inhibitor were added thereto, and the mixture was heated to 100 ° C. The glycidyl methacrylate 180.9g was dripped in it in 30 minutes, and it was made to react by stirring at 100 degreeC for 5 hours. As a result, a methacryl-modified bisphenol A type novolak resin (MPN) (methacrylic modification rate 50%) having a nonvolatile content of 74% was obtained.

2. Preparation of resin varnish 57.0% by weight of the above methacryl-modified bisphenol A type phenol novolak resin (MPN) as an alkali-soluble resin, and Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator %, Trisphenol type epoxy resin E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.) 33.0% by weight, phenol novolac type resin PR53647 (manufactured by Sumitomo Bakelite Co., Ltd.) 4.0% by weight as a phenol resin, infrared As an absorbent, lanthanum boride LaB6-F (manufactured by Nippon Shin Metal Co., Ltd.) 3.0% by weight was dissolved in methyl ethyl ketone (MEK, manufactured by Daishin Chemical Co., Ltd.) to obtain a resin varnish. In addition, lanthanum boride LaB6-F, an infrared absorbent, was formed by crushing under severe conditions.

3. Preparation of adhesive film The resin varnish described above was applied to a supporting base polyester film (manufactured by Teijin DuPont Films, Inc., RL-07, thickness 38 μm) with a comma coater, dried at 70 ° C. for 10 minutes, and a film thickness of 20 μm. An adhesive film was obtained.

(Example 2)
43.0% by weight of the above methacryl-modified bisphenol A type phenol novolak resin (MPN) as the alkali-soluble resin, and 12.0% by weight of trimethylolpropane trimethacrylate light ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) as the acrylic resin, Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 3.0% by weight as a photopolymerization initiator, trisphenol type epoxy resin E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.) 33.0% by weight, and phenol resin Phenol novolac resin PR53647 (manufactured by Sumitomo Bakelite Co., Ltd.) 4.0% by weight, and lanthanum boride LaB6-F (manufactured by Nippon Shin Metals Co., Ltd.) 5.0% by weight as an infrared absorber, methyl ethyl ketone (MEK, Dissolved in Daishin Chemical Co., Ltd.) to obtain a resin varnish. The adhesive film was prepared in the same manner as in Example 1. As in Example 1, lanthanum boride LaB6-F, an infrared absorber, was formed by crushing under severe conditions.

(Example 3)
42.0% by weight of the methacryl-modified bisphenol A type phenol novolak resin (MPN) as the alkali-soluble resin, and 12.0% by weight of trimethylolpropane trimethacrylate light ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) as the acrylic resin, As a compound having a phenolic hydroxyl group and a carboxyl group, 1.0% by weight of 4,4′-bis (p-hydroxyphenyl) pentanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and Irgacure 651 as a photopolymerization initiator (B) (Ciba Specialty Chemicals Co., Ltd.) 3.0% by weight, Trisphenol type epoxy resin E1032H60 (Japan Epoxy Resin Co., Ltd.) 33.0% by weight, and phenol novolac type resin PR53647 (phenol resin) Sumitomo Bake Ito Co., Ltd.) 4.0% by weight, and as an infrared absorber, lanthanum boride LaB6-F (manufactured by Nippon Shin Metal Co., Ltd.) 5.0% by weight, methyl ethyl ketone (MEK, manufactured by Daishin Chemical Co., Ltd.) The resin varnish was obtained. The adhesive film was prepared in the same manner as in Example 1. As in Example 1, lanthanum boride LaB6-F, an infrared absorber, was formed by crushing under severe conditions.

Example 4
The blending amount of trimethylolpropane trimethacrylate light ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) as an acrylic resin is changed from 12.0 parts by weight to 10.0 parts by weight. Lanthanum boride LaB6-F (manufactured by Nippon Shin Metals Co., Ltd.) The resin varnish and the adhesive film were prepared in the same manner as in Example 2 except that the blending amount was changed from 5.0% by weight to 7.0% by weight. As in Example 2, the infrared absorbing lanthanum boride LaB6-F was formed by crushing under severe conditions.

(Example 5)
42.0% by weight of the above-mentioned methacryl-modified bisphenol A type phenol novolak resin (MPN) as the alkali-soluble resin (A) and 12.0% by weight of trimethylolpropane trimethacrylate light ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) as the acrylic resin %, Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, 3.0% by weight, trisphenol type epoxy resin E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.), 33.0% by weight And phenol novolac resin PR53647 (manufactured by Sumitomo Bakelite Co., Ltd.) as a phenol resin, and 4.0 wt% tin-doped indium oxide ITO powder (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) as an infrared absorber. And It was dissolved in ethyl ketone (MEK, manufactured Daishinkagaku Co.), to obtain a resin varnish. The adhesive film was prepared in the same manner as in Example 1. In addition, the tin-doped indium oxide ITO powder of the infrared absorber was formed by crushing under severe conditions.

(Example 6)
Except for changing the weight of tin-doped indium oxide ITO powder 6.0 wt% to 6.0 wt% of antimony-doped tin oxide conductive powder T-1 (Mitsubishi Materials Electronics Chemical Co., Ltd.) as an infrared absorber. In the same manner as in Example 5, a resin varnish and an adhesive film were prepared. In addition, the antimony dope tin oxide electroconductive powder T-1 of an infrared absorber was formed by crushing on severe conditions.

(Example 7)
Phenol novolac resin S-3 (manufactured by Sumitomo Bakelite Co., Ltd.) 54.0% by weight as the alkali-soluble resin (A), and silicon-modified epoxy resin BY16-115 (manufactured by Toray Dow Corning Silicone Co., Ltd.) as the epoxy resin 29. 0 parts by weight, instead of the photopolymerization initiator (B), 9.0% by weight of sulfonic acid ester of trisphenol and naphthoquinonediazide represented by the following formula as a photoacid generator (C), and an infrared absorber, Preparation of adhesive film except that lanthanum boride LaB6-F (made by Nippon Shin Metal Co., Ltd.) 5.0% by weight was dissolved in methyl ethyl ketone (MEK, made by Daishin Chemical Co., Ltd.) to obtain a resin varnish. Was carried out in the same manner as in Example 1. As in Example 1, lanthanum boride LaB6-F, an infrared absorber, was formed by crushing under severe conditions.

(Comparative Example 1)
45.0% by weight of the methacryl-modified bisphenol A type phenol novolak resin (MPN) as the alkali-soluble resin, and 12.0% by weight of trimethylolpropane trimethacrylate light ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) as the acrylic resin, Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 3.0% by weight as a photopolymerization initiator, trisphenol type epoxy resin E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.) 35.0% by weight, and phenol resin Preparation of an adhesive film except that a phenol novolac type resin PR53647 (Sumitomo Bakelite Co., Ltd.) 5.0% by weight was dissolved in methyl ethyl ketone (MEK, Daishin Chemical Co., Ltd.) to obtain a resin varnish. Line as in Example 1 It was.

(Comparative Example 2)
45.0% by weight of the methacryl-modified bisphenol A type phenol novolak resin (MPN) as the alkali-soluble resin, and 12.0% by weight of trimethylolpropane trimethacrylate light ester TMP (manufactured by Kyoeisha Chemical Co., Ltd.) as the acrylic resin, Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 3.0% by weight as a photopolymerization initiator, trisphenol type epoxy resin E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.) 33.0% by weight, and phenol resin Phenol novolac resin PR53647 (manufactured by Sumitomo Bakelite Co., Ltd.) 4.0% by weight, and as an infrared absorber, phthalocyanine compound e-excolor 910 (manufactured by Nippon Shokubai Co., Ltd.) 3.0% by weight, methyl ethyl It was dissolved in tons (MEK, manufactured Daishinkagaku Co.), to obtain a resin varnish. The adhesive film was prepared in the same manner as in Example 1.

(Comparative Example 3)
Comparative Example 2 except that 3.0 wt% of phthalocyanine compound e-ex color 906 (manufactured by Nippon Shokubai Co., Ltd.) is used as an infrared absorber instead of phthalocyanine compound e-ex color 910 (manufactured by Nippon Shokubai Co., Ltd.). In the same manner as above, a resin varnish and an adhesive film were prepared.

(Comparative Example 4)
Comparative example except that diimonium-based compound KAYASORB IRG-068 (manufactured by Nippon Kayaku Co., Ltd.) is used instead of phthalocyanine-based compound e-excolor 910 (manufactured by Nippon Shokubai Co., Ltd.) as an infrared absorber. In the same manner as in No. 2, a resin varnish and an adhesive film were prepared.

1. Transmittance evaluation The transmittance of the adhesive films obtained in each Example and Comparative Example was measured with a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation), and the wavelength at which the transmittance at a wavelength of 400 to 700 nm was minimized and at that time The minimum transmittance (1), the wavelength at which the transmittance at a wavelength of 360 to 400 nm is minimum (maximum absorption wavelength) and the transmittance at that time are the minimum transmittance (2), and further, the wavelength at 800 nm to 2500 nm The wavelength with the minimum transmittance (maximum absorption wavelength) and the transmittance at that time were defined as the minimum transmittance (3). Further, after the film was heated at 260 ° C. for 10 minutes, the transmittance was measured by the above method. The transmittance at which the transmittance at a wavelength of 800 nm to 2500 nm, which was measured after heating the film at 260 ° C. for 10 minutes, was the minimum transmittance (4).
The results are shown in Table 1 below.

2. Elastic modulus at 25 ° C. and 260 ° C. The adhesive films obtained in each Example and Comparative Example were exposed under the conditions of wavelength: 365 nm and exposure amount: 700 mJ / cm ² , and further, conditions of 180 ° C. and 5 hours. The storage elastic modulus was measured with a dynamic viscoelasticity measuring device (DMA) under conditions of frequency: 10 Hz, temperature increase rate: 3 ° C./min), and the storage elastic modulus at 25 ° C. and 260 ° C. was measured. It was.

3. Flux resistance Adhesive films obtained in each Example and Comparative Example were attached to a semiconductor wafer, exposed at a wavelength of 365 nm and an exposure amount of 700 mJ / cm ² , and further at 180 ° C. for 5 hours. After heat curing, M34-226C-21-10.8H (manufactured by Senju Metal Industry Co., Ltd.) was applied on the adhesive film as a solder paste and heated on a hot plate at 250 ° C. for 10 minutes to aggregate the solder. . Next, the flux on the adhesive film was washed at 70 ° C. for 10 minutes using Pine Alpha ST-1000SX (made by Arakawa Chemical Co., Ltd.), which is a flux washing solution, and further, 45 ° C. using pure water. Washing was performed at 1 minute + 25 ° C. for 1 minute. Then, the surface state of the adhesive film was confirmed with a microscope.
○: No difference in surface condition is observed before and after chemical solution treatment. ×: Wrinkles and swelling are observed on the surface after chemical solution treatment.

4). Evaluation of water absorption rate The adhesive films obtained in each Example and Comparative Example were bonded together using a laminator set at 60 ° C. to produce an adhesive film with a thickness of 100 μm, wavelength: 365 nm, exposure amount: 700 mJ / cm ^2. Then, the adhesive film was thermally cured under the conditions of 180 ° C. and 5 hours. The obtained heat-cured adhesive film was pulverized to about 5 mm square, and further weighed about 10 mg to prepare a measurement sample. Next, the measurement sample is heat-treated at 85 ° C. for 10 minutes, and the weight of the measurement sample is precisely weighed (the weight at this time is a), and then the measurement sample is 85 ° C., 85% humidity, 10% Wet heat treatment for minutes, and weigh the weight after the wet heat treatment (the weight at this time is b). The water absorption was calculated by the following formula.
Water absorption rate (%) = ((ba) / a) × 100

5. Average linear expansion coefficient α1
The adhesive films obtained in each Example and Comparative Example were exposed under the conditions of wavelength: 365 nm and exposure amount: 700 mJ / cm ² . Furthermore, thermosetting was performed under the conditions of 180 ° C. and 5 hours to prepare a measurement sample. Using the obtained measurement sample, the linear expansion coefficient was measured with a thermomechanical property measuring apparatus (TMA) (mode: tension, load: 30 mN, temperature increase rate: 5 ° C./min), and the ambient temperature was 0 ° C. to 30 ° C. The average linear expansion coefficient was taken as the measured value.
The results are shown in Table 1 below.

  As described above, in Comparative Example 1, since the infrared absorbent was not included, the minimum transmittance of light having a wavelength of 800 to 2500 nm showed a large value of 85.4%. When the adhesive film of this comparative example is used for the via of the light receiving element, the light receiving element malfunctions due to infrared rays that penetrate through the via from the side surface of the circuit board.

(Light receiving device)
A light receiving device was fabricated in the following procedure. First, as shown in FIG. 1, the adhesive film of Example 4 was pressure-bonded to the circuit board. Next, exposure and development were performed, the adhesive film was patterned, and then heat-cured to form a via. Next, a circuit board was pressure-bonded on the obtained via, and a light receiving device was arranged on the circuit board, thereby manufacturing a light receiving device. Since this light-receiving device has a good light-shielding property for infrared rays, it can operate stably without causing a malfunction in the light-receiving element.

DESCRIPTION OF SYMBOLS 1 Light receiving device 11 1st wiring circuit 12 2nd wiring circuit 13 Resin layer 14 Silicon substrate 15 Spacer 15a Photosensitive resin composition layer 16 for spacers Transparent substrate 17 Insulating film 18 Solder 19 Light receiving element 20 Via 21 Gap 22 Wiring circuit 33 Mask 34 Exposure light

Claims (5)

A first wiring circuit formed on the upper surface of the silicon substrate;
A second wiring circuit formed on the lower surface of the silicon substrate;
A via provided in the silicon substrate to connect the first wiring circuit and the second wiring circuit;
A light receiving element provided on the upper surface of the first wiring circuit,
The via is filled with a resin composition,
The minimum transmittance T for light having a wavelength of 800 nm to 2500 nm of the thermosetting resin composition having a thickness of 20 μm is 15% or less.
Light receiving device.   2. The light receiving device according to claim 1, wherein the resin composition having a thickness of 20 μm has a minimum transmittance T ′ of 15% or less with respect to light having a wavelength of 800 nm to 2500 nm after heating at 260 ° C. for 10 minutes.   The light receiving device according to claim 1, wherein the resin composition contains an infrared absorber.   The infrared absorber is a metal boride, titanium oxide, zirconium oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), azo compound, aminium compound, cyanine compound, squarylium compound, anthraquinone compound, funatoquinone compound, dithiol The light receiving device according to claim 1, wherein the light receiving device is at least one selected from a compound and a polymethine compound.   The light-receiving device according to claim 4, wherein the metal boride is lanthanum hexaboride.

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