JP2008285614A - Resin composition, adhesive film and light-receiving device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition with a high optical transparency, adhesive film and a light-receiving device using the same. <P>SOLUTION: The resin composition, (corresponding to the adhesive film 14), is an optically curable resin composition installed between a base substrate 12 on which the light-receiving device 11 is installed, and a transparent substrate 13, and used for keeping a gap between the base substrate 12 and the transparent substrate 13. The resin composition comprises the optically curable resin and 0.1-40 wt.% of silica having 0.03-0.4 μm of an average particle size. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition, an adhesive film, and a light receiving device that are used to maintain a gap between a base substrate provided with a light receiving portion and a transparent substrate.

Conventionally, in a light receiving device, in order to protect the light receiving portion, a transparent substrate is disposed at a position facing the base substrate on which the light receiving portion is provided.
An adhesive that surrounds the periphery of the light receiving unit is provided between the transparent substrate and the base substrate (for example, Patent Document 1).
When manufacturing such a light receiving device, a resin composition constituting an adhesive is applied on a base substrate (or a transparent substrate) provided with a light receiving portion, and a predetermined portion is exposed. Then, after selectively removing the resin composition, the base substrate and the transparent substrate are bonded.

JP 2006-070053 A

However, it has been found that the conventional method for manufacturing a light receiving device has the following problems.
When manufacturing the light receiving device, a predetermined portion of the resin composition is exposed. At this time, it is necessary to install a mask of the exposure device above the resin composition.
When installing this mask, the position of the mask and the position of the base substrate or the transparent substrate are adjusted with reference to the alignment mark formed on the base substrate or the transparent substrate. If the position is poor, the alignment mark cannot be detected, and alignment becomes difficult.

  An object of the present invention is to provide a resin composition having a high light transmittance, an adhesive film, and a light receiving device using these.

According to the present invention, a photocurable resin composition that is disposed between a base substrate provided with a light receiving portion and a transparent substrate and used to maintain a gap between the base substrate and the transparent substrate. And containing a photocurable resin and silica, wherein the silica content is 0.1 wt% or more and 40 wt% or less, and the average particle diameter of the silica is 0.03 μm or more and 0.4 μm. The following resin composition is provided.
According to this invention, it can be set as the resin composition with favorable light transmittance by the average particle diameter of a silica being 0.4 micrometer or less.
Moreover, it can be set as the resin composition with favorable light transmittance by containing 40 wt% or less of silica content.
Thereby, alignment with a base substrate etc. and a mask can be made easy.
In addition, when the average particle diameter of silica is 0.03 μm or more, there is an effect that silica is relatively easily dispersed when a resin composition is produced.
Moreover, the heat resistance and moisture resistance of a resin composition can be improved by making content of a silica into 0.1 wt% or more. Furthermore, the strength when the resin composition is disposed between the base substrate and the transparent substrate can be ensured.

Under the present circumstances, when the said resin composition is formed in a 50-micrometer-thick film form, it is preferable that the transmittance | permeability in wavelength 600nm is 7% or more and 95% or less.
Moreover, when the said resin composition is formed in the film form of thickness 50 micrometers, the transmittance | permeability in wavelength 750nm may be 20% or more and 95% or less.
In general, the alignment mark formed on the base substrate or the like is detected in the visible light region.
Therefore, by setting the transmittance at a wavelength of 600 nm to 7% or more and 95% or less, or the transmittance at a wavelength of 750 nm to 20% or more and 95% or less, it is easy to align the base substrate and the mask. Can do.

Furthermore, it is preferable that the maximum particle size of silica is 0.1 μm or more and 1.0 μm or less.
By setting the maximum particle size of silica to 1.0 μm or less, the light transmittance of the resin composition can be reliably improved. Further, when the resin composition is produced by setting the maximum particle size of silica to 0.1 μm or more, there is an effect that silica is relatively easily dispersed.

The silica is preferably subjected to a coupling treatment.
By using such silica, the adhesion between the resin component and the silica interface is increased, and the strength of the resin composition is increased.

Furthermore, it is preferable that the minimum melt viscosity in a temperature range of 80 ° C. to 180 ° C. is 100 Pa · s or more after the film is formed and UV irradiation (700 mJ / cm ² ).
By doing in this way, when a transparent substrate and a base substrate are thermocompression-bonded, it can prevent that a resin composition collapses.

  Moreover, it is preferable that it contains the curable resin which can be hardened | cured by both light and a heat | fever, Furthermore, the said curable resin which can be hardened | cured by both light and a heat | fever is (meth) acryl modified phenol resin or (meth) It is preferable to contain an acryloyl group-containing (meth) acrylic acid polymer. Moreover, it is preferable that a silicone modified epoxy resin is included as a thermosetting resin.

Furthermore, according to this invention, the adhesive film which has the resin composition mentioned above formed in the film form can also be provided.
In addition, according to the present invention, there is provided a light receiving device including a base substrate provided with a light receiving portion and a transparent substrate disposed to face the base substrate, wherein the light receiving device is provided between the transparent substrate and the base substrate. Is a frame member that holds a gap between the base substrate and the transparent substrate and surrounds the light receiving part, and the frame member is a light receiving device that is the above-described resin composition or the above-described adhesive film. Can be provided.

  According to the present invention, there are provided a resin composition having a high light transmittance, an adhesive film, and a light receiving device using them.

First, the outline | summary of the resin composition of this invention is demonstrated.
The resin composition of the present embodiment (corresponding to reference numeral 14 in FIG. 2) is disposed between the base substrate 12 provided with the light receiving unit 11 and the transparent substrate 13, and a gap between the base substrate 12 and the transparent substrate 13. It is a photo-curable resin composition used for holding (see FIG. 2). The resin composition contains a photocurable resin and silica, the silica content is 0.1 wt% or more and 40 wt% or less, and the average particle size of the silica is 0.03 μm or more, and 0.0. It is a resin composition which is 4 micrometers or less.

Hereinafter, the resin composition will be described in detail.
The resin composition includes a photocurable resin and silica.
The content of silica is 0.1 wt% or more, preferably 10 wt% or more.
By setting the silica content to 0.1 wt% or more, particularly 10 wt% or more, the heat resistance and moisture resistance of the resin composition can be improved. Moreover, the strength when the resin composition is disposed between the base substrate 12 and the transparent substrate 13 can be ensured.
Further, the content of silica is 40 wt% or less, preferably 35 wt% or less.
By setting the silica content to 40 wt% or less, particularly 35 wt% or less, the light transmittance of the resin composition before photocuring and after photocuring can be ensured.

The average particle diameter of silica is 0.03 μm or more, preferably 0.01 μm or more.
By making the average particle diameter of silica 0.03 μm or more, particularly 0.01 μm or more, there is an effect that silica is relatively easily dispersed when a resin composition is produced.
The average particle diameter of silica is 0.4 μm or less, preferably 0.3 μm or less.
By setting the average particle diameter of silica to 0.4 μm or less, particularly 0.3 μm or less, it is possible to ensure the light transmittance of the resin composition before and after photocuring.

The method for measuring the average particle diameter of silica is as follows.
Using a laser diffraction particle size distribution analyzer SALD-7000, silica is dispersed in water by ultrasonic treatment for 1 minute, and measurement is performed. The D50 value is defined as the average particle size.

Further, the maximum particle size of silica is 0.1 μm or more, preferably 0.15 μm or more. The maximum particle size of silica is 1.0 μm or less, preferably 0.9 μm or less.
By making the maximum particle size of silica 0.1 μm or more, there is an effect that silica is relatively easily dispersed when producing a resin composition.
Moreover, the fall of the light transmittance of a resin composition can be prevented because the maximum particle diameter of a silica shall be 1.0 micrometer or less.
The maximum particle size of silica can be measured as follows.
Using a laser diffraction particle size distribution analyzer SALD-7000, silica is dispersed in water by ultrasonic treatment for 1 minute, and measurement is performed. The D100 value is taken as the maximum particle size.

Silica is preferably subjected to coupling treatment.
By using such silica, the adhesion between the resin component and the silica interface is increased, and the strength of the resin composition is increased.

Examples of the photocurable resin contained in the resin composition include an ultraviolet curable resin mainly composed of an acrylic compound, an ultraviolet curable resin mainly composed of a urethane acrylate oligomer or a polyester urethane acrylate oligomer, an epoxy resin, Examples thereof include an ultraviolet curable resin mainly comprising at least one selected from the group of vinylphenol resins.
Among these, an ultraviolet curable resin mainly composed of an acrylic compound is preferable. The acrylic compound has a high curing rate when irradiated with light, and thus the resin can be patterned with a relatively small amount of exposure.

  Examples of the acrylic compounds include monomers of acrylic acid esters or methacrylic acid esters, and specifically include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,6 dimethacrylate. -Bifunctional acrylates such as hexanediol, glyceryl diacrylate, glyceryl dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate And polyfunctional acrylates such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. . Among these, acrylic acid esters are preferable, and acrylic acid esters or methacrylic acid alkyl esters having 1 to 15 carbon atoms in the ester moiety are particularly preferable.

  Although content of photocurable resin (ultraviolet curable resin) is not specifically limited, 5 wt% or more and 60 wt% or less of the whole resin composition are preferable, and 8 wt% or more and 30 wt% or less are especially preferable. If the content is less than 5 wt%, the resin composition may not be patterned by ultraviolet irradiation, and if it exceeds 60 wt%, the resin may be too soft and the sheet characteristics before ultraviolet irradiation may deteriorate.

Further, the resin composition preferably contains a photopolymerization initiator.
Thereby, a resin composition can be efficiently patterned by photopolymerization.
Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin isobutyl ether, methyl benzoin benzoate, benzoin benzoic acid, benzoin methyl ether, benzylfinyl sulfide, benzyl, dibenzyl, diacetyl and the like.
Although content of the said photoinitiator is not specifically limited, 0.5 wt% or more and 5 wt% or less of the whole said resin composition are preferable, and 0.8 wt% or more and 2.5 wt% are especially preferable. If the content is less than 0.5 wt%, the effect of initiating photopolymerization may be reduced, and if it exceeds 5 wt%, the reactivity may be too high and the storage stability and resolution may be reduced.

Furthermore, it is preferable that a resin composition contains a thermosetting resin.
Examples of the thermosetting resins include phenol novolac resins, cresol novolac resins, novolac type phenol resins such as bisphenol A novolac resins, phenol resins such as resol phenol resins, bisphenol type epoxies such as bisphenol A epoxy resins and bisphenol F epoxy resins. Resin, novolak epoxy resin, cresol novolak epoxy resin, etc., novolak epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, di Epoxy resins such as cyclopentadiene-modified phenolic epoxy resins, resins with triazine rings such as urea (urea) resins and melamine resins, unsaturated Riesuteru resins, bismaleimide resins, polyurethane resins, diallyl phthalate resins, silicone resins, resins having a benzoxazine ring, cyanate ester resins, and the like. These may be used singly or in admixture. Among these, an epoxy resin is particularly preferable. Thereby, heat resistance and adhesiveness can be improved more.

  Further, it is preferable to use a silicone-modified epoxy resin as the epoxy resin. Among them, an epoxy resin that is solid at room temperature (particularly a bisphenol type epoxy resin) and an epoxy resin that is liquid at room temperature (particularly a silicone that is liquid at room temperature). A modified epoxy resin) is preferably used in combination. Thereby, it can be set as the resin composition which is excellent in both flexibility and resolution, maintaining heat resistance.

  Although content of the said thermosetting resin is not specifically limited, 10 wt% or more and 40 wt% or less of the whole resin composition are preferable, and 15 wt% or more and 35 wt% or less are especially preferable. If the content is less than 10 wt%, the effect of improving the heat resistance may be reduced, and if it exceeds 40 wt%, the effect of improving the toughness of the resin composition may be reduced.

  Further, the resin composition preferably contains a curable resin that can be cured by both light and heat. Thereby, the compatibility of the said photocurable resin and the said thermosetting resin can be improved, and the intensity | strength of the resin composition after hardening (photocuring and thermosetting) can be raised by it.

  Examples of the curable resin curable by both light and heat include, for example, a thermosetting resin having a photoreactive group such as an acryloyl group, a methacryloyl group, and a vinyl group, an epoxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, Examples thereof include a photocurable resin having a thermally reactive group such as a carboxyl group, an acid anhydride group, an amino group, and a cyanate group. Specific examples include (meth) acryl-modified phenolic resins, acrylic copolymer resins having a carboxyl group and an acrylic group in the side chain, and (meth) acryloyl group-containing (meth) acrylic acid polymers. Among these, a (meth) acryl-modified phenol resin is preferable. Thereby, not only an organic solvent but an alkaline aqueous solution with a small environmental load can be applied to the developer, and heat resistance can be maintained.

  In the case of the thermosetting resin having the photoreactive group, the modification rate (substitution rate) of the photoreactive group is not particularly limited, but the entire reactive group of the curable resin that can be cured by both light and heat (light 20% or more and 80% or less of the total of the reactive groups and the thermally reactive groups) is preferable, and 30% or more and 70% or less are particularly preferable. When the modification amount is in the range of 20% or more and 80% or less, the resolution is particularly excellent.

  In the case of the photocurable resin having the thermally reactive group, the modification rate (substitution rate) of the thermally reactive group is not particularly limited, but the entire reactive group of the curable resin that can be cured by both light and heat (light 20% or more and 80% or less of the total of the reactive groups and the thermally reactive groups) is preferable, and 30% or more and 70% or less are particularly preferable. When the modification amount is 20% or more and 80% or less, the resolution is particularly excellent.

  The content of the curable resin that can be cured by both light and heat is not particularly limited, but is preferably 15 wt% or more and 50 wt% or less, and particularly preferably 20 wt% or more and 40% or less of the entire resin composition. If the content is less than 15 wt%, the effect of improving the compatibility may be reduced, and if it exceeds 50 wt%, the developability or resolution may be reduced.

  The resin composition can contain additives such as a plastic resin, a leveling agent, an antifoaming agent, a coupling agent, and an organic peroxide as long as the object of the present invention is not impaired.

When such a resin composition is formed into a film having a thickness of 50 μm, the transmittance at a wavelength of 750 nm is 20% or more and 95% or less. Especially, it is preferable that the transmittance | permeability is 30% or more. Moreover, it is preferable that it is 90% or less.
By setting the transmittance to 20% or more, the light transmittance of the resin composition is ensured, and the alignment between the base substrate 12 coated with the resin composition and the mask of the exposure apparatus can be easily performed.

The transmittance is measured as follows.
On a transparent PET (polyethylene terephthalate) film (film thickness 25 μm), the resin composition is formed into a film with a film thickness of 50 μm.
Thereafter, the resin composition with the transparent PET film still attached is set in an ultraviolet-visible spectrophotometer UV-160A (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 750 nm is measured.
In addition, the transmittance | permeability of this resin composition is the transmittance | permeability before photocuring the resin composition.
However, the transmittance at a wavelength of 750 nm after curing the resin composition is also preferably 20% or more and 95% or less. By doing in this way, position alignment with the base substrate 12 and the transparent substrate 13 mentioned later can be performed easily.

Further, the resin composition is formed into a film shape, and after UV irradiation (700 mJ / cm ² ), the minimum melt viscosity in the temperature range of 80 ° C. to 180 ° C. is 100 Pa · s or more.
Among these, the minimum melt viscosity is more preferably 500 pa · s or more, and the minimum melt viscosity is preferably 50000 pa · s or less. By setting the minimum melt viscosity to 50000 pa · s or less, the fluidity of the resin composition can be ensured after patterning by exposure and development. Therefore, the transparent substrate 13 and the base substrate 12 provided with the light receiving portion 11 are provided. It can be securely bonded when thermocompression bonding.

The minimum melt viscosity is measured as follows.
A resin composition is formed into a film having a thickness of 50 μm on a PET film. Thereafter, three samples cut into 30 mm squares are prepared. Each sample is irradiated with broadband light. The amount of light is 700 mJ / cm ² with a wavelength of 365 nm. The film-like resin composition is peeled off from the PET film, and three sheets are stacked and set on a dynamic viscoelasticity measuring device Rheo Stress RS150 (manufactured by HAAKE). The gap between the plates is measured from room temperature to 250 ° C. at 100 μm, frequency 1 Hz, and heating rate 10 ° C./min.

  By dissolving the resin constituting the resin composition of the present invention in an organic solvent, an organic solvent such as N-methyl-2-pyrrolidone, anisole, methyl ethyl ketone, toluene, ethyl acetate, etc., the resin composition is varnished. can do. By removing the solvent from the varnish-like resin composition and drying it, an adhesive film having the resin composition formed into a film can be obtained.

Next, the usage method of the adhesive film which used the said resin composition as the film form is demonstrated.
As shown in FIGS. 1A and 1B, an adhesive film 14 is attached to a base substrate 12 provided with a plurality of light receiving portions 11 so as to cover the base substrate 12. Here, the thickness of the adhesive film 14 is 5 μm or more and 100 μm or less.
Next, the base substrate 12 with the adhesive film 14 attached is aligned with an exposure apparatus (not shown).
At this time, an alignment mark (not shown) is formed on the surface of the base substrate 12 to which the adhesive film 14 is attached. With this alignment mark as a reference, alignment between the mask of the exposure apparatus and the base substrate 12 is performed. The alignment is performed in the visible light region.

  When the alignment between the base substrate 12 and the exposure apparatus is completed, the exposure apparatus selectively irradiates the adhesive film 14 with light (ultraviolet rays). Thereby, the part irradiated with light among the adhesive films 14 is photocured. When the exposed adhesive film 14 is developed with a developer (for example, an alkaline aqueous solution, an organic solvent, etc.), the light irradiated portion remains without being dissolved in the developer. The adhesive film 14 is left in a grid pattern so as to surround the light receiving portions 11 in a region other than each light receiving portion 11 on the base substrate 12 (see FIG. 1C).

Thereafter, the transparent substrate 13 is placed on the adhesive film 14, and the base substrate 12 and the transparent substrate 13 are bonded by the adhesive film 14. For example, the base substrate 12 and the transparent substrate 13 are heated and pressed and bonded via the adhesive film 14. The temperature at the time of thermocompression bonding is 80 ° C to 180 ° C.
At this time, the transparent substrate 13 is set with reference to the alignment mark formed on the base substrate 12.

After that, the bonded base substrate 12 and transparent substrate 13 are divided according to the light receiving unit (see FIG. 1D). Specifically, a cut 12B is made by a dicing saw from the transparent substrate 13 side, and the base substrate 12 and the transparent substrate 13 are divided according to the light receiving unit 11 unit.
Through such a process, the light receiving device 1 shown in FIG. 2 can be obtained. That is, the light receiving device 1 is a light receiving device including a base substrate 12 provided with a light receiving unit 11 and a transparent substrate 13 disposed to face the base substrate 12, and includes a transparent substrate 13 and a base substrate 12. A frame member is disposed between the base substrate 12 and the transparent substrate 13 so as to surround the light receiving unit 11. This frame material is an adhesive film 14.

Next, the effect of this embodiment is demonstrated.
The resin composition of this embodiment contains 0.1 wt% or more and 40 wt% or less of silica having an average particle size of 0.03 μm or more and 0.4 μm or less.
By setting the average particle size of silica to 0.4 μm or less, it is possible to obtain a resin composition having good light transmissivity in at least the visible light region.
Moreover, it can be set as the resin composition with the sufficient light transmittance in visible region at least by making content of a silica into 40 wt% or less.
Thereby, alignment with the base substrate 12 and the mask of exposure apparatus can be performed easily. In addition, the base substrate 12 and the transparent substrate 13 after the resin composition is cured can be easily aligned.
Furthermore, when the average particle diameter of silica is 0.03 μm or more, there is an effect that silica is relatively easily dispersed when producing a resin composition. Moreover, the heat resistance and moisture resistance of a resin composition can be improved by making content of a silica into 0.1 wt% or more. Moreover, the strength when the resin composition is disposed between the base substrate 12 and the transparent substrate 13 can be ensured.

  Further, when the resin composition is a film having a thickness of 50 μm, the base substrate 12 and the mask can be easily aligned with each other by setting the transmittance at a wavelength of 750 nm to 20% or more and 95% or less.

Furthermore, by setting the maximum particle size of silica to 1.0 μm or less, the light transmittance of at least the visible light region of the resin composition can be reliably improved. Further, when the resin composition is produced by setting the maximum particle size of silica to 0.1 μm or more, there is an effect that silica is relatively easily dispersed.
In addition, the resin composition is formed into a film shape, and after UV irradiation (700 mJ / cm ² ), the minimum melt viscosity in the temperature range of 80 ° C. to 180 ° C. is 100 Pa · s or more, When thermocompression bonding with the base substrate 12, the resin composition (adhesive film 14) can be prevented from being crushed or melted and flowing.

It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
In the above embodiment, when the resin composition is formed into a film with a thickness of 50 μm, the transmittance at a wavelength of 750 nm is 20% or more and 95% or less, but the resin composition is further formed into a film with a thickness of 50 μm. In this case, the transmittance at a wavelength of 600 nm may be 7% or more and 95% or less.
By doing in this way, the light transmittance of a resin composition can be improved and position alignment with the base substrate 12 and the transparent substrate 13 can be performed more easily in visible region.

When the resin composition is formed into a film having a thickness of 50 μm, the transmittance at a wavelength of 600 nm is 7% or more and 95% or less, or the transmittance at a wavelength of 750 nm is 20% or more and 95% or less. There may be.
Even when the transmittance at a wavelength of 600 nm is 7% or more and 95% or less, the base substrate 12 and the transparent substrate 13 can be easily aligned.

In addition, the measuring method of the transmittance | permeability is as follows.
On a transparent PET (polyethylene terephthalate) film (film thickness 25 μm), the resin composition is formed into a film with a film thickness of 50 μm.
Thereafter, the resin composition with the transparent PET film still attached is set in an ultraviolet-visible spectrophotometer UV-160A (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 600 nm is measured.
The transmittance here is the transmittance before the resin composition is cured.

Furthermore, in the said embodiment, although the adhesive film 14 which formed the resin composition in the film form was affixed on the base substrate 12, and the base substrate 12 and the transparent substrate 13 were adhere | attached, not only this but a transparent substrate An adhesive film may be affixed to. In this case, the alignment mark formed on the transparent substrate and the mask are aligned.
Moreover, in the said embodiment, although the adhesive film 14 was affixed on the base substrate 12, and the transparent substrate 13 was bonded together with the adhesive film 14, it diced, but it is not restricted to this, The adhesive film 14 is attached to the base substrate 12. After pasting, the base substrate 12 may be diced for each light receiving unit, and then the transparent substrate 13 may be pasted.
Moreover, in the said embodiment, although the adhesive film 14 which formed the resin composition in the film form was affixed on the base substrate 12, not only this but a varnish-like resin composition may be apply | coated to the base substrate 12. . After applying the varnish-like resin composition to the base substrate 12, it is dried, exposed and developed. Thereafter, the light receiving device 1 may be configured by attaching the transparent substrate 13 in the same manner as in the above embodiment. At this time, the thickness of the varnish-like resin composition after drying may be the same as that of the adhesive film of the embodiment.
Furthermore, the adhesive film 14 may be one in which a protective film or the like is attached on a resin composition formed in a film shape.

Next, examples and comparative examples of the present invention will be described.
Examples 1 to 4 and Comparative Examples 1 and 2
(Synthesis of methacryl-modified bisphenol A novolac resin (curable resin curable by both light and heat))
500 g of a solid content 60% MEK (methyl ethyl ketone) solution of bisphenol A novolak resin (Phenolite LF-4871, manufactured by Dainippon Ink & Chemicals) was put into a 2 L flask, and 1.5 g of tributylamine was added as a catalyst thereto. Further, 0.15 g of hydroquinone was added as a polymerization inhibitor and heated to 100 ° C. Into this, 180.9 g of glycidyl methacrylate was added dropwise over 30 minutes, and the mixture was reacted with stirring at 100 ° C. for 5 hours to obtain a methacryl-modified bisphenol A novolak resin (methacryloyl modification rate 50%) having a nonvolatile content of 74%.

(Adjustment of resin composition and production of adhesive film)
A resin composition was prepared according to the formulation shown in Table 1.
Specifically, methacryl-modified bisphenol A novolak resin (non-volatile content 74%), Epicron N-865 (bisphenol A novolac type epoxy resin, manufactured by Dainippon Ink & Chemicals, Inc.), BY16-115 (silicone-modified epoxy resin, Toray Dow Corning Silicone Co.), silica, NK ester 3G (triethylene glycol dimethacrylate, Shin-Nakamura Chemical Co., Ltd.) dissolved in MEK (methyl ethyl ketone, Daishin Chemical Co., Ltd.) and solid The partial concentration was adjusted to 71%. Next, silica is dispersed using a bead mill (bead diameter 400 μm, processing speed, 6 g / s, 5 passes), a photosensitizer is added, and the mixture is stirred for 1 hour with a stirring blade (450 rpm). A resin composition was prepared.
Thereafter, the resin composition was applied onto transparent PET (film thickness 25 μm) and dried at 80 ° C. for 15 minutes to form a film (adhesive film). The thickness of the adhesive film (film-like resin composition) is 50 μm.

The average particle diameter and maximum particle diameter of silica used in each example and each comparative example are as shown in Table 2.

The method for measuring the average particle diameter, maximum particle diameter, transmittance, and minimum melt viscosity of silica is as described in the above embodiment.
After the adhesive film of each Example was attached to the base substrate, exposure was performed. At this time, the alignment mark on the base substrate could be easily detected with visible light, and the alignment between the base substrate and the mask could be easily performed (as shown in Table 1, the alignment was good. )
On the other hand, when the adhesive film of each comparative example was affixed to the base substrate and then exposed, it was difficult to detect the alignment mark on the base substrate with visible light. For this reason, it is difficult to align the base substrate and the mask (alignment was poor as shown in Table 1).

It is a schematic diagram which shows the manufacturing process of the light-receiving device concerning embodiment of this invention. It is a figure which shows a light-receiving device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light receiver 11 Light receiver 12 Base substrate 13 Transparent substrate 14 Adhesive film

Claims (11)

A photocurable resin composition that is disposed between a base substrate provided with a light receiving portion and a transparent substrate, and is used to maintain a gap between the base substrate and the transparent substrate,
A photocurable resin;
Containing silica,
The silica content is 0.1 wt% or more and 40 wt% or less,
The resin composition whose average particle diameter of the said silica is 0.03 micrometer or more and 0.4 micrometer or less. The resin composition according to claim 1,
A resin composition having a transmittance of 7% or more and 95% or less at a wavelength of 600 nm when the resin composition is formed into a film having a thickness of 50 μm. In the resin composition according to claim 1 or 2,
A resin composition having a transmittance of 20% or more and 95% or less at a wavelength of 750 nm when the resin composition is formed into a film having a thickness of 50 μm. In the resin composition in any one of Claims 1 thru | or 3,
A resin composition having a maximum particle size of the silica of 0.1 μm or more and 1.0 μm or less. In the resin composition in any one of Claims 1 thru | or 4,
The silica is a resin composition that has been subjected to a coupling treatment. In the resin composition in any one of Claims 1 thru | or 5,
A resin composition which is formed into a film and has a minimum melt viscosity of 100 Pa · s or more in a temperature range of 80 ° C. to 180 ° C. after UV irradiation (700 mJ / cm ² ). In the resin composition in any one of Claims 1 thru | or 6,
A resin composition comprising a curable resin curable with both light and heat. The resin composition according to claim 7,
The curable resin curable by both light and heat is a resin composition containing a (meth) acryl-modified phenol resin or a (meth) acryloyl group-containing (meth) acrylic acid polymer. In the resin composition in any one of Claims 1 thru | or 8,
A resin composition comprising a silicone-modified epoxy resin as a thermosetting resin.   The adhesive film which has the resin composition in any one of Claims 1 thru | or 9 formed in the film form. A base substrate provided with a light receiving portion;
A light receiving device comprising a transparent substrate disposed opposite to the base substrate,
Between the transparent substrate and the base substrate, while holding a gap between the base substrate and the transparent substrate, a frame material surrounding the light receiving portion is disposed,
The light receiving device, wherein the frame member is the resin composition according to any one of claims 1 to 9, or the adhesive film according to claim 10.

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