KR20200120614A - Infrared transmitting film composition and method of manufacturing a cover member - Google Patents

Abstract

The composition for forming an infrared transmission film includes a dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a region of 581 nm or more and 700 nm or less, and a dye having a wavelength of 701 nm or more and 800 nm or less. A dye having an absorption maximum in the region and a solvent are contained, and the solvent contains a solvent having a dissolution parameter of 8 (cal/cm 3) ^1/2 or more and 12 (cal/cm 3) ^1/2 or less. In the said composition for an infrared transmission film, you may contain a transparent resin further.

Description

Infrared transmitting film composition and method of manufacturing a cover member

The present invention relates to a composition for an infrared transmission film and a method of manufacturing a cover member.

In recent years, portable terminals such as smartphones, tablet personal computers, and notebook personal computers have become popular, and information communication can be performed while viewing a screen in various environments. In addition, the portable terminal is equipped with an electronic device (in some cases referred to as an infrared sensor) having an accurate grasp function of location information using infrared rays and a face authentication function utilizing the function.

The infrared sensor is disposed near the display area of the portable terminal. At this time, around the infrared sensor, a black bezel is used for the cover member in order to make the infrared sensor difficult to be recognized by the user. In the black bezel, some openings are provided, and an optical window for shielding visible light and passing infrared rays is provided. A film that transmits infrared rays (infrared ray transmitting film) is used in the light window. In Patent Document 1, a structure of a light window used for an infrared sensor is disclosed. In addition, Patent Document 2 discloses a composition for absorbing and shielding light in a partial wavelength range using a dye material other than black.

Japanese Utility Model Registration No. 3208984 Gazette Japanese Patent No. 6196109

In the case of Patent Document 1, an infrared transmissive film for a light window is formed by a vapor deposition method. In the case of the evaporation method, it is formed by overlapping thin films with different refractive indices several times. However, in the vapor-deposited infrared transmission film, it is difficult to obtain a sufficient film thickness, and there is a possibility that it is visually recognized by the user, and when forming a thick film, a long time may be required.

In addition, as shown in Patent Document 2, when using a dye to absorb and shield light in a specific wavelength range, the type of the dye and the content of the dye in the composition become important. However, due to the increase in the type of the dye and the content of the dye in the infrared transmitting film, the dye may precipitate during manufacture of the infrared transmitting film. If the pigment is precipitated, a sufficient shielding function cannot be maintained, and storage stability may be impaired.

In view of such a problem, an object of the present invention is to provide a composition for an infrared transmission film having high storage stability. Another object of the present invention is to form an infrared transmission film having a function of sufficiently shielding visible light against a light window.

According to an embodiment of the present invention, a dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a region of 581 nm or more and 700 nm or less, and a wavelength of 701 nm or more and 800 nm or less For infrared transmissive membranes containing a dye having an absorption maximum in the range of and a solvent, and the solvent contains a solvent having a dissolution parameter of 8 (cal/cm 3) ^1/2 or more and 12 (cal/cm 3) ^1/2 or less A composition is provided.

According to an embodiment of the present invention, a dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a region of 581 nm or more and 700 nm or less, and a wavelength of 701 nm or more and 800 nm or less The absolute value of the difference in dissolution parameters between the dye having the maximum absorption in the region of and a solvent and the solvent having the maximum absorption in the region of 701 nm or more and 800 nm in wavelength is 2.5 (cal/cm 3) ^{1/ A} composition for an infrared transmissive film containing ² or less solvent is provided.

In the said composition for an infrared transmission film, you may contain a transparent resin further.

In the composition for an infrared transmission film, the transparent resin may have a cyclic ether group.

In the composition for an infrared transmission film, the transparent resin may further have an acidic group.

In the composition for an infrared transmitting film, the solvent may have a cyclic structure.

In the composition for infrared-transmitting membranes described above, the solvent having a cyclic structure may be contained in an amount of 10% by mass or more when the entire solvent is 100% by mass.

In the composition for an infrared transmission membrane, the solvent may contain at least one solvent selected from cyclic ketones, cyclic ethers, lactones, lactams, and aromatic hydrocarbons.

In the said composition for infrared transmission membranes, you may contain a thickener further.

In the composition for an infrared transmitting film, the thickener may contain at least one selected from silica, talc, calcium carbonate, magnesium carbonate, bentonite, barium sulfate, zinc oxide, alumina, and cesium tungsten oxide.

In the composition for infrared transmission membranes, the dyes having the maximum absorption in the wavelength range of 701 nm to 800 nm are phthalocyanine dyes, cyanine dyes, pyrrolopyrrole dyes, naphthalocyanine dyes, dimonium dyes, and You may contain at least one pigment|dye selected from co-dye and squarylium-type pigment|dye.

The composition for an infrared transmission film further comprises a dye having an absorption maximum in a region of a second wavelength of 701 nm to 800 nm, which is different from a dye having an absorption maximum in a region of a wavelength of 701 nm to 800 nm, and a second The dissolution parameter of the dye having the maximum absorption in the region of 701 nm to 800 nm in wavelength may be smaller than the dissolution parameter of the dye having the maximum absorption in the region of 701 nm to 800 nm in wavelength.

According to an embodiment of the present invention, a first masking layer having an average transmittance of 10% or less is formed on a light-transmitting structure in a wavelength region of 400 nm to 700 nm, and an opening is formed in the first masking layer. In the opening, a dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a range of 581 nm or more and 700 nm or less, and a maximum absorption in the region of 701 nm or more and 800 nm or less. There is provided a method for manufacturing a cover member in which a second masking layer is formed by using a composition containing a solvent having a dye having a pigment and a dissolution parameter of 8 (cal/cm 3) ^1/2 or more and 12 (cal/cm 3) ^1/2 or less. .

According to an embodiment of the present invention, a composition for an infrared transmission film having high storage stability can be provided, and an infrared transmission film having a function of sufficiently shielding visible light against a light window can be formed.

1 is a top view illustrating an electronic device according to an embodiment of the present invention.
2 is a top view illustrating a cover member according to an embodiment of the present invention.
3 is a cross-sectional view between A1 and A2 of an electronic device according to an embodiment of the present invention.
4 is a cross-sectional view illustrating a method of manufacturing a cover member according to an embodiment of the present invention.
5 is a cross-sectional view illustrating a method of manufacturing a cover member according to an embodiment of the present invention.
6 is a cross-sectional view illustrating a method of manufacturing a cover member according to an embodiment of the present invention.
7 is a cross-sectional view between A1 and A2 of the electronic device according to the embodiment of the present invention.

Hereinafter, a composition for an infrared transmission film according to each embodiment of the present invention will be described in detail with reference to the drawings. In addition, each embodiment shown below is an example of embodiment of this invention, and this invention is limited to these embodiment and is not interpreted. Incidentally, in the drawings referred to in the present embodiment, the same reference numerals or similar reference numerals are attached to the same portions or portions having the same functions, and the repeated description thereof may be omitted. In addition, the dimensional ratios in the drawings may differ from the actual ratios for convenience of explanation, or a part of the configuration may be omitted from the drawings.

<First embodiment>

(1-1. Composition of composition for infrared transmission film)

The composition for an infrared transmission film has an absorption maximum of at least one or more in a wavelength range of 701 nm or more and 800 nm or less. Moreover, the composition for an infrared transmission film has an absorption maximum of at least 1 or more in a wavelength range of 400 nm or more and 700 nm or less. Thereby, in the infrared transmission film formed using the composition for an infrared transmission film, light in the visible region (specifically, the wavelength 400 nm or more and 800 nm or less) is shielded from light, and the infrared ray (specifically, the wavelength 801 nm or more and 1200 nm) is shielded. The following areas near infrared) are transmitted. The composition for an infrared transmission film of the present embodiment contains a dye and a solvent. It will be described in detail below.

(1-1-1 pigment)

The dye is a substance that imparts color by absorption or emission of visible light. The dye may contain any of an inorganic compound and an organic compound, or may contain any of a dye and a pigment, but the solubility becomes good by using a dye, which is preferable. It is preferable that the dye has a low absorption to infrared rays.

It is preferable to use a combination of two or more kinds of dyes having an absorption maximum in a visible light region (a wavelength of 400 nm or more and 800 nm or less). By using two or more kinds of dyes, light in the visible region can be satisfactorily shielded. As a dye used in this embodiment, for example, a dye having an absorption maximum in a region having a wavelength of 400 nm or more and 580 nm or less (hereinafter, also referred to as "pigment (i)"), and a range of 581 nm or more and 700 nm or less. A dye having an absorption maximum (hereinafter, also referred to as “pigment (ii)”), a dye having an absorption maximum in a region of 701 nm or more and 800 nm or less (hereinafter, also referred to as “pigment (iii)”), and the like. . When the composition for an infrared-transmitting film contains three types of dyes (i) to (iii) as dyes, it becomes possible to more effectively shield light in the visible region over the entire visible region. That is, when the pigment|dye contains three types of pigment|dyes (i)-(iii) as a pigment|dye, it becomes suitable visible light shielding performance. In addition, the composition for infrared-transmitting membranes may contain pigments other than pigments (i) to (iii) as pigments.

In the composition for an infrared-transmitting membrane of the present embodiment, each added amount of the dyes (i) to (iii) when the solid component (resin, thickener, polymerizable compound, etc. described later) excluding the solvent is 100% by mass. , Preferably it is 0.01 mass% or more and 4 mass% or less, More preferably, it is 0.05 mass% or more and 3 mass% or less, More preferably, it is 0.1 mass% or more and 1 mass% or less. In addition, in the composition for infrared-transmitting membranes of the present embodiment, the total addition amount of the dyes (i) to (iii) when the solid component excluding the solvent is 100% by mass is preferably 1% by mass or more and 5% by mass. Below, it is more preferably 1.5% by mass or more and 4% by mass or less, and still more preferably 1.8% by mass or more and 3.5% by mass or less. In the above, by making the total addition amount of the dyes (i) to (iii) 1% or more, the absorption characteristics of the intended wavelength are improved. In addition, by making the total addition amount of the dyes (i) to (iii) 5% or less, solubility becomes good and storage stability becomes good.

-Color (i)-

As the dye (i), organic dyes, such as a blue dye and a blue pigment, are mentioned, for example.

Specific examples of the blue dye include xanthene dye, triarylmethane dye, cyanine dye, phthalocyanine dye, anthraquinone dye, tetraazaporphyrin dye, indigo dye, and the like. Among these, cyanine dyes are particularly preferred from the viewpoint of heat resistance. The cyanine dye is a dye containing only a compound having a structure in which a conjugated double bond is formed with a plurality of methine groups between two heterocycles in a molecule as a dye. Specific examples of the cyanine dye include compounds represented by the following formulas (A1) and (A2) (hereinafter, also referred to as "compounds (A1) and (A2)") and the like.

In the formula (A1), Z1 is an alkyl group or a phenyl group having 1 to 12 carbon atoms. Z2 is a C1-C12 alkyl group, a phenyl group, or a naphthyl group. At least one hydrogen atom of the phenyl group and the naphthyl group may be substituted with at least one of a halogen atom and an alkyl group having 1 to 12 carbon atoms.

In the formula (A2), Z3 and Z4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. n is an integer from 1 to 12. X is a counter-anion.

As for the anion represented by X, for example a halide ion, ClO ₄ ^-, OH ^-, organic acid anion, organic acid anion, a Lewis acid anion, and an organometallic complex anion, a dye-derived anions, organic sulfonyl imide Acid anion, organic sulfonylmethide anion, etc. are mentioned.

Examples of halide ions, such as Cl ^-, and the like ^-, Br ^-, I. As an organic carboxylic acid anion, a benzoic acid ion, an alkanoic acid ion, a trihaloalkanoic acid ion, a nicotinic acid ion, etc. are mentioned, for example. Examples of the organic sulfonic acid anion include benzene sulfonic acid ions, naphthalene sulfonic acid ions, p-toluene sulfonic acid ions, and alkane sulfonic acid ions. Examples of the Lewis acid anion include a tetrafluoroborate ion, a hexafluoroantimonate ion, and a tetrakis(pentafluorophenyl)boron anion.

Specific examples of the compound (A1) include, for example, a compound represented by the following general formula (A1-1) (hereinafter, also referred to as "compound (A1-1)"). Specific examples of the compound (A2) include, for example, a compound represented by the following formula (A2-1) (hereinafter, also referred to as "compound (A2-1)"). The maximum absorption wavelength (λmax) of the compound (A1-1) is 466 nm, and the maximum absorption wavelength (λmax) of the compound (A2-1) is 549 nm.

In addition, as a blue pigment, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like. Among these, C.I. Pigment Blue 15:6, 16, 79 are preferred.

-Color (ii)-

Examples of the dye (ii) include organic dyes such as yellow and green dyes, and yellow and green pigments. Examples of the yellow and green dyes include squarylium dyes, triarylmethane dyes, cyanine dyes, phthalocyanine dyes, and the like. Among these, triarylmethane dyes are particularly preferred from the viewpoint of heat resistance.

Examples of the triarylmethane dye include compounds represented by the following general formula (A3) (hereinafter, also referred to as "compound (A3)") and the like.

In the above formula (A3), each of Z5 is independently a hydrogen atom, an alkyl or phenyl group having 1 to 12 carbon atoms. T is an aromatic group or heterocyclic group having 3 to 10 carbon atoms which may have a substituent. X is a counter-anion.

Examples of the counter anion represented by X include halide ions, perchlorate ions, hydroxide ions, organic carboxylic acid anions, organic sulfonic acid anions, Lewis acid anions, organometallic complex anions, dye-derived anions, and organic sulfonylimide acid. An anion, an organic sulfonylmethide anion, and the like.

Specific examples of the compound (A3) include, for example, a compound represented by the following general formula (A3-1) (hereinafter, also referred to as "compound (A3-1)"). The maximum absorption wavelength (λmax) of compound (A3-1) is 604 nm.

For yellow and green pigments, as yellow pigments, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1 , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 , 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188 , 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or 231, and the like. Among these, C.I. Pigment Yellow 129, 138, 139, 150, 185, 231 are preferred. As a green pigment, for example, C.I. Pigment Green 7, 36, 58, 59, 62, 63, etc. are mentioned, and C.I. Pigment green 7, 36, 58, 59 are preferred.

-Pigment (iii)-

As dye (iii), organic dyes, such as a red dye and a red pigment, are mentioned. The dye (iii) is, for example, at least one selected from the group consisting of a phthalocyanine dye, a cyanine dye, a pyrrolopyrrole dye, a naphthalocyanine dye, a dimonium dye, an azo dye and a squarylium dye. Contains the pigment of. As the dye (iii), more specifically, a squarylium dye, a phthalocyanine dye, etc. are mentioned.

Examples of the squarylium dye include compounds represented by the following general formula (A4) (hereinafter, also referred to as "compound (A4)").

In the above formula (A4), each of X is independently a methylene group or an alkylene group having 2 to 12 carbon atoms in which one or more hydrogen atoms may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group. Z6, Z7, and Z8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. Z9 is an alkyl group having 1 to 12 carbon atoms or a fluorinated alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound (A4) include, for example, a compound represented by the following formula (A4-1) (hereinafter, also referred to as "compound (A4-1)"). The maximum absorption wavelength (λmax) of compound (A4-1) is 712 nm.

As the phthalocyanine dye, a compound represented by the following general formula (A5) (hereinafter, also referred to as "compound (A5)"), etc. are mentioned, for example.

In the formula (A5), Z ¹⁰ is each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group. M is a metal atom or a metal oxide.

Examples of the metal atom include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. As a metal oxide, VO, TiO, etc. are mentioned, for example.

Specific examples of the compound (A5) include, for example, a compound represented by the following general formula (A5-1) (hereinafter, also referred to as "compound (A5-1)"). The maximum absorption wavelength (λmax) of compound (A5-1) is 738 nm.

In addition, as a red pigment, for example, C.I. Pigment Red 1, 2, 5, 17, 31, 32, 41, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 49:1, 49:2, 49:3 , 52:1, 52:2, 53:1, 54, 57:1, 58, 58:1, 58:2, 58:3, 58:4, 60:1, 63, 63:1, 63:2 , 63:3, 64:1, 68, 81, 81:1, 122, 123, 144, 149, 166, 168, 170, 171, 175, 176, 177, 178, 179, 180, 185, 187, 200 , 202, 206, 207, 209, 214, 220, 221, 224, 237, 239, 242, 243, 247, 254, 255, 262, 264, 269, 272, and the like. Among these, C.I. Pigment Red 166, 177, 242, 254, 264, 269 are preferred.

Further, in the dyes (i) to (iii), the difference between the maximum absorption wavelength of the dye (i) and the dye (ii) is preferably 40 nm or more and 200 nm or less. The difference between the maximum absorption wavelength of the dye (ii) and the dye (iii) is preferably 80 nm or more and 200 nm or less. By setting the difference in absorption maximum wavelength of the dye (i), dye (ii) and dye (iii) into the above range, the visible region can be more effectively shielded from light, and the transmittance of the near-infrared region of the infrared transmission film can be further improved. I can.

(1-1-2 solvent)

As a solvent, as long as it disperses or dissolves a resin, a thickener, and other components described later in addition to the dye, does not react with these components, and has appropriate volatility, it can be appropriately selected and used.

As a solvent, for example, n-propanol, 1,2,5,6-tetrahydrobenzyl alcohol, diethylene glycol ethyl ether, 3-methoxybutanol, triacetin, propylene glycol monomethyl ether, cyclopentanone, γ- Butyrolactone, cyclohexanone, propylene glycol-n-propyl ether, propylene glycol-n-butyl ether, dipropylene glycol methyl ether, 1,4-butanediol diacetate, 3-methoxybutyl acetate, propylene glycol diacetate, Ethyl lactate acetate, ε-caprolactone, 1,3-butylene glycol diacetate, dipropylene glycol-n-propyl ether, 1,6-hexanediol diacetate, dipropylene glycol-n-butyl ether, tripropylene glycol methyl Ether, tripropylene glycol-n-butyl ether, cyclohexanol acetate, diethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, toluene, methyl acetate, di Propylene glycol dimethyl ether, xylene, ethylbenzene, isophorone, terpineol, etc. are mentioned. Solvents can be used alone or in combination of two or more.

It is preferable that the solvent contains a solvent having a cyclic structure. By using a solvent having a cyclic structure, the solubility and dispersibility of a dye having an absorption maximum in a region of 701 nm or more and 800 nm or less in particular wavelength is improved, and storage stability is better. The number of solvents having a cyclic structure may be one or two or more. The cyclic structure may be a carbocyclic ring or a heterocyclic ring. Further, the cyclic structure may be polycyclic or monocyclic. In addition, the cyclic structure may be an aromatic ring or an aliphatic ring.

The solvent preferably contains at least one solvent selected from, for example, a cyclic ketone, a cyclic ether, a lactone (γ-butyrolactone, ε-caprolactone, etc.), a lactam, and an aromatic hydrocarbon (toluene, etc.). Among these, cyclic ketones, lactones and aromatic hydrocarbons are preferable, and cyclic ketones and lactones are more preferable. If it is such a solvent, it is preferable to particularly improve the solubility or dispersibility of the phthalocyanine dye, cyanine dye, pyrrolopyrrole dye, naphthalocyanine dye, dimonium dye and squarylium dye preferably used in the present invention. It becomes possible.

Cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, etc. are mentioned as a cyclic ketone. Among these, cyclopentanone, cyclohexanone and cycloheptanone are preferred, and cyclopentanone and cyclohexanone are more preferred.

As a cyclic ether, tetrahydrofuran, tetrahydropyran, etc. are mentioned.

Examples of the lactone include γ-butyrolactone, ε-caprolactone, and the like, and γ-butyrolactone is preferable.

Examples of the lactam include pentano-4-lactam, 5-methyl-2-pyrrolidinone, hexano-6-lactam, and 6-hexanactam.

The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent in the second masking layer 130 is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. desirable. By setting it as such a form, it is possible to obtain a composition for an infrared transmissive film having good dispersibility, stability, and coatability.

(1-1-3 dissolution parameters)

Here, the properties of the solvent will be described using a dissolution parameter (hereinafter, referred to as an SP value). The SP value is a value obtained by the following Fedors equation (1) described in R.F.Fedors, Polym.Eng.Sci., 14,147 (1974).

In the above formula (1), Ev is the evaporation energy, V is the molar volume, Δe _i is the evaporation energy of an atom or group of atoms of each component, and Δv _i is the molar volume of an atom or group of atoms of each component.

The solvent in this embodiment contains a solvent having an SP value of 8 (cal/cm 3) ^1/2 or more and 12 (cal/cm 3) ^1/2 or less. The range of the SP value is preferably 9 (cal/cm 3) ^1/2 or more and 11.5 (cal/cm 3) ^1/2 or less, and more preferably 10 (cal/cm 3) ^1/2 or more and 11 (cal/cm 3). Cm3) ^1/2 or less. For example, when a cyclic ketone is used as a solvent, the SP value of cyclobutanone is 10.8 (cal/cm 3) ^1/2 , the SP value of cyclopentanone is 10.8 (cal/cm 3) ^1/2 , and the SP of cyclohexanone The value is 9.9 (cal/cm 3) ^1/2 . By containing a solvent having an SP value within the above range, a plurality of pigments used in the present embodiment can be maintained without precipitation for a long time. As a result, a composition for forming an infrared transmission film excellent in storage properties over time is obtained.

In addition, the lower limit of the content of the solvent having an SP value within the above range is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass when the whole solvent is 100% by mass. % Or more. In addition, the upper limit of the content of the solvent having an SP value within the above range is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 60% by mass when the whole solvent is 100% by mass. % Or less.

In addition, in the solvent of this embodiment, the absolute value of the difference from the SP value of the dye (iii) is 2.5 (cal/cm 3) ^1/2 or less, preferably 1.5 (cal/cm 3) ^1/2 or less, more preferably It is preferable to contain a solvent of 0.5 (cal/cm 3) ^1/2 or less. This is, while the dye (iii) plays a role of shielding the wavelength region close to the wavelength region detected by the sensor, while the dye (iii) has a property that is difficult to dissolve in the solvent, and in improving the sensor sensitivity In particular, it is because it is an organic pigment that should suppress precipitation. When the solvent contains a solvent having an absolute value of 2.5 (cal/cm 3) ^1/2 or less of the difference between the SP value and the dye (iii), the affinity between the dye (iii) and the solvent increases. Thereby, it can be dissolved in a solvent without depositing the dye (iii). As a result, a composition for an infrared transmissive film having an excellent shielding function in a region of a wavelength of 701 nm or more and 800 nm or less, and excellent storage characteristics over time is obtained.

In addition, the lower limit of the content of the solvent in which the absolute value of the difference between the SP value of the dye (iii) in the dye is 2.5 (cal/cm 3) ^1/2 or less is preferably 10% by mass or more when the entire solvent is 100% by mass. And, more preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more. In addition, the upper limit of the content of the solvent is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 60% by mass or less when the entire solvent is 100% by mass.

In addition, the composition for an infrared transmission film of the present embodiment is a dye having an absorption maximum in a region having a wavelength of 701 nm or more and 800 nm or less different from the dye (iii) (hereinafter, also referred to as “pigment (iv)” or a fourth dye). You may have For the dye (iv), the same material as the dye (iii) is used. In addition, it is preferable that the SP value of the dye (iv) is smaller than the SP value of the dye (iii). For example, a squarylium dye may be used as the dye (iii), and a phthalocyanine dye may be used as the dye (iv).

(1-1-4 resin)

The composition for infrared transmission membranes may further contain a resin. Resin contains a transparent resin. As the weight average molecular weight (Mw) of a resin, it can be set as 3,000 or more and 500,000 or less, for example. The lower limit of the glass transition temperature (Tg) of the resin is preferably 110° C., so as to secure the thermal stability and solvent resistance of the infrared transmission film and exhibit resistance in a heating manufacturing process of 100° C. or higher by being applied to a display device or the like. °C is more preferred. As the upper limit of the Tg, 380°C is preferable, 370°C is more preferable, and 360°C is still more preferable.

As resin, for example, cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) Resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy Resins, polysiloxane resins, allyl ester curable resins, silsesquioxane ultraviolet curing resins, and the like. These resins can be used alone or in combination of two or more. As resin, resin shown below is preferable.

(Cyclic olefin resin)

As the cyclic olefin resin, a resin obtained from at least one of a monomer represented by the following formula (X0) and a monomer represented by the following formula (Y0), and a resin obtained by hydrogenating the resin are preferable.

In the formula (X0), R ^x1 to R ^x4 are each independently an atom or group selected from the following (i) to (viii). k ^x , m ^x and p ^x are each independently 0 or a positive integer.

(i) hydrogen atom

(ii) halogen atom

(iii) trialkylsilyl group

(iv) an unsubstituted hydrocarbon group having 1 to 30 carbon atoms or having a substituent containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

(v) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

(vi) polar groups (except (iv))

(vii) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^x1 to R ^x4 not involved in the bonding are each independently, the above (i) to (vi) Represents an atom or group selected from

(viii) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding to each other, and R ^x1 to R ^x4 not involved in the bond are each independently, the above represents an atom or group selected from (i) to (vi), or R ^x2 and R ^x3 represent a monocyclic hydrocarbon ring or heterocycle formed by bonding to each other, and R ^x1 to R ^x4 not involved in the bond, Each independently represents an atom or group selected from (i) to (vi).

In the formula (Y0), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i) to (vi), or represent the following (ix), and k ^y and p ^y are each Independently, it represents 0 or a positive integer.

(ix) R ^y1 and R ^y2 represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon, or heterocycle formed by bonding to each other.

(Aromatic polyether resin)

As the aromatic polyether resin, a resin having at least one of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) is preferable.

In the formula (1), R ¹ to R ⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms. a to d are each independently an integer of 0 to 4.

In Formula (2), R ¹ to R ⁴ and a to d each independently have the same meaning as R ¹ to R ⁴ and a to d of Formula (1). Y is a single bond, -SO ₂ -or -CO-. R ⁷ and R ⁸ are each independently a halogen atom, a nitro group, or a monovalent organic group having 1 to 12 carbon atoms. g and h are each independently an integer of 0 to 4. m is 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

It is preferable that the aromatic polyether resin further has at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In the above formula (3), R ⁵ and R ⁶ are each independently a monovalent organic group having 1 to 12 carbon atoms. Z is a single bond, -O-, -S-, -SO ₂ -, -CO-, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms. e and f are each independently an integer of 0 to 4. n is 0 or 1.

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h each independently have the same meaning as R ⁷ , R ⁸ , Y, m, g and h in the formula (2). R ⁵ , R ⁶ , Z, n, e and f each independently have the same meaning as R ⁵ , R ⁶ , Z, n, e and f of the formula (3).

(Polyimide resin)

The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in the repeating unit. The polyimide resin can be synthesized by a method described, for example, in JP 2006-199945, JP 2008-163107, and the like.

(Fluorene polycarbonate resin)

The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety. Fluorene polycarbonate resin can be synthesized by a method described in Japanese Patent Laid-Open No. 2008-163194, for example.

(Fluorene polyester resin)

The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. The fluorene polyester resin can be synthesized by a method described in Japanese Patent Laid-Open 2010-285505, Japanese Patent Laid-Open 2011-197450, for example.

(Fluorinated aromatic polymer resin)

As the fluorinated aromatic polymer resin, a polymer having an aromatic ring having at least one fluorine atom, and a repeating unit including at least one bond selected from an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond If it is, it is not specifically limited. The fluorinated aromatic polymer resin can be synthesized by a method described in Japanese Patent Laid-Open No. 2008-181121, for example.

((Modified) acrylic resin)

Examples of the (modified) acrylic resin include an acrylic resin that is a polymer of one or two or more (meth)acrylic acid esters, and a modified acrylic resin that is a copolymer of a (meth)acrylic acid ester and another monomer. As the modified acrylic resin, the acrylic resin obtained by polymerization may be modified. The (modified) acrylic resin may have a polymerizable group such as a cyclic ether group, a vinyl group, or a (meth)acryloyl group in the side chain. Examples of such (modified) acrylic resins include (modified) acrylic resins containing glycidyl (meth)acrylate as a monomer.

(Epoxy resin)

As an epoxy resin, for example, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a trisphenol type epoxy resin, a tetraphenol type epoxy resin, a phenol-xylylene type epoxy resin, and naphthol-xylyl A ren type epoxy resin, a phenol-naphthol type epoxy resin, a phenol-dicyclopentadiene type epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

The polyurethane resin is not particularly limited as long as it has a urethane bond as a repeating unit, and can be produced by reaction of a diisocyanate compound and a diol compound. As diisocyanate compounds, aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Aliphatic or aliphatic cyclic structure-containing diisocyanates, such as methane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate, can be used alone or in combination of two or more. As a diol compound, ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, saccharose, methylene glycol, Glycols, such as glycerin and sorbitol, are mentioned.

(Commercial product)

As a commercially available product of the resin, as a commercially available product of a cyclic olefin resin, for example, "ARTON" by JSR, "Zeonoa" by Nippon Xeon, "APEL" by Mitsui Chemical, and "TOPAS" by Polyplastics. As a commercial item of a polyether sulfone resin, "Sumika Excel PES" by Sumitomo Chemical Co., etc. is mentioned, for example. As a commercial item of a polyimide-type resin, "Neo anulim L" etc. of Mitsubishi Gas Chemical Co., etc. are mentioned, for example. As a commercial item of a polycarbonate-type resin, the "Pure Ace" etc. of Teijin are mentioned, for example. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. "Upzeta" EP-5000" etc. are mentioned, for example. As a commercial item of a fluorene polyester-type resin, "OKP4HT" etc. of Osaka Gas Chemicals are mentioned, for example. As a commercial item of the (modified) acrylic resin, "Acreia" by Nippon Shokubai, "Maproof G-0250SP" by Nichiyu, etc. are mentioned, for example. As a commercial item of silsesquioxane-based UV cured resin, "Silplus" of Shinnittetsu Chemical Co., etc. is mentioned, for example.

As the resin, among these, cyclic olefin resins and (modified) acrylic resins are preferable. Further, as the resin, a resin having a polymerizable group such as a cyclic ether group, a vinyl group, or a (meth)acryloyl group is also preferable, and a resin having a cyclic ether group as a polymerizable group is particularly preferable.

As said cyclic ether group, an oxirane group or oxetanyl group is mentioned preferably. If it is such a group, since it has high polymerizability, heat resistance of the infrared-transmitting film obtained can be improved. In addition, when using a resin having a cyclic ether group, the resin also has a carboxyl group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group, or an acidic group that is a combination thereof, thereby promoting the ring-opening polymerization of the cyclic ether group, and the resin It is preferable because the polymerization property of can be further improved. Among the above acidic groups, those having an acidic group that is a carboxyl group, a sulfo group, a phenolic hydroxyl group, or a combination thereof are more preferable, and a carboxy group is particularly preferable.

(1-1-5 thickener)

The composition for infrared transmission membranes may further contain a thickener. The thickener is used in order to adjust the viscosity of the composition for an infrared transmission film. Specifically, the thickener is contained so that the viscosity of the composition for an infrared transmission film is 0.1 Pa·s or more and 1000 Pa·s or less. If it is within the above range, it becomes easy to adjust the film thickness and shape of the infrared transmission film. As a thickener, an inorganic filler or an organic filler is used. As the inorganic filler, at least one selected from the group consisting of silica, talc, calcium carbonate, magnesium carbonate, bentonite, barium sulfate, zinc oxide, alumina, and cesium tungsten oxide may be contained. The organic filler may contain synthetic organic fine particles such as polystyrene, polyacrylonitrile, polymethyl methacrylate, polypropylene, polyethylene, polyvinyl chloride, or natural organic fine particles such as cellulose. Moreover, since the dispersibility and handling property are favorable, it is preferable to use an inorganic filler as a thickener. By using a thickener, it is possible to stabilize the pattern shape upon screen printing.

(1-1-6 polymerizable compound)

Moreover, the composition for infrared transmission membranes may contain a polymeric compound. As the polymerizable compound, a photopolymerizable compound or a thermally polymerizable compound can be used, and may be used in combination. Specific examples of the polymerizable compound include vinyl compounds, urethane, urethane acrylate, acrylate, epoxy and epoxy acrylate resins, and isocyanate resins.

(1-1-7 additive)

In addition, the composition for forming an infrared transmission film may contain various additives as necessary. Examples of the additives include surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, residue improving agents, and catalysts.

As surfactant, a fluorine surfactant, a silicone surfactant, etc. are mentioned. As the content of the surfactant in the total solid content in the composition for infrared transmission membranes, it can be, for example, 0.01% by mass or more and 5% by mass or less.

As an adhesion promoter, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2) -Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrime And oxysilane.

As antioxidants, 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t -Butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1 -Dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ] And the like. The content of the antioxidant in the total solid content in the composition for infrared transmission films can be, for example, 0.01% by mass or more and 5% by mass or less.

Examples of the ultraviolet absorber include 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones.

Examples of the anti-aggregation agent include sodium polyacrylate.

As a catalyst, a metal such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, or a salt thereof, Alkoxides or organic compounds can be used. Particularly preferred are compounds such as sodium, titanium, zirconium, and tin, such as sodium hydride, titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, and dibutyl Tin dilaurate, dibutyl tin dimethoxide, dibutyl tin oxide, etc. are mentioned.

(1-2. Configuration of mobile terminal)

The above-described composition for an infrared transmission film is used as an infrared transmission film (the second masking layer 130 to be described later) for a cover member of an electronic device (specifically, a portable terminal such as a smartphone). 1 is a top view of an electronic device 10. The electronic device 10 includes an infrared sensor 100, a cover member 110, a camera 200, a speaker unit 300, a housing 400, a display panel 500, and a microphone unit 600. A touch panel is employed for the display panel 500, and the display panel 500 has an input function in addition to a display function. At this time, the infrared sensor 100 is disposed in the vicinity of the display panel 500 of the electronic device 10.

In addition, in this embodiment, although a smartphone was illustrated as an electronic device, it is not limited to this. The electronic device 10 may be a tablet-type personal computer, a notebook-type personal computer, or may be a display device or a touch panel attached to various devices. That is, the electronic device 10 may be an electronic device in which an optical sensor is incorporated under the cover member 110.

The cover member 110 is disposed on the surface of the electronic device 10. 2 shows a top view of the cover member 110. As shown in FIG. 2, the cover member 110 includes a light-transmitting structure 115, a first masking layer 120, an opening 125, and a second masking layer 130. Details of each configuration will be described later.

3 is a cross-sectional view between A1 and A2 of the display device 10 shown in FIG. 1.

As shown in FIG. 3, between A1 and A2, the display device 10 includes an infrared sensor 100, a cover member 110, a package substrate 170, and a housing 180. Further, although not shown, a light-emitting element (for example, an infrared lamp) may be disposed in the vicinity of the infrared sensor.

The infrared sensor 100 has a function of performing image recognition (for example, face authentication) by detecting infrared rays reflected by irradiation to an object. In addition, the infrared sensor 100 is not limited to image recognition, and may have gas detection, flame detection, moisture detection, temperature detection, human body detection functions, and the like.

The infrared sensor 100 is connected to the package substrate 170. In the infrared sensor 100, a relay substrate may be provided between the package substrate 170.

The housing 180 is formed of a member that blocks light, and houses the infrared sensor 100. In FIG. 2, the cover member 110 and the package substrate 170 are provided outside the housing 180, but may be provided inside the housing 180.

(1-3. Configuration of cover member 110)

The cover member 110 is provided on the infrared sensor 100. The cover member 110 has a function of absorbing light in a predetermined wavelength region and a function of transmitting light in a predetermined wavelength region at the same time. Hereinafter, the configuration of the cover member 110 will be described in detail.

The light-transmitting structure 115 is disposed on the outer surface of the electronic device 10. For the light-transmitting structure 115, a light-transmitting member is used. For example, tempered glass obtained by ion exchange is used for the light-transmitting structure 115. Tempered glass can be used as a cover glass of a smartphone for the purpose of protecting the display screen.

The first masking layer 120 has an average transmittance of 10% or less in a wavelength region of 400 nm or more and 700 nm or less. That is, the first masking layer 120 has a function of blocking light in the visible light region. As the first masking layer 120, a black material is used. For example, for the first masking layer 120, an organic resin material containing carbon black is used. The film thickness of the first masking layer 120 may be appropriately set in a range of 5 µm or more and 50 µm or less.

Further, for the first masking layer 120, pigments such as titanium black pigment, bisbenzofuranone pigment, azomethine pigment, and perylene pigment may be used, or an azo dye may be used. Further, the first masking layer 120 may contain one or more selected from these materials.

The opening 125 is provided in the first masking layer 120. Among the openings 125, the diameter R125 on the side of the light-transmitting structure 115 has a size that is visible. The diameter R125 of the opening 125 on the side of the light-transmitting structure 115 is preferably 0.5 mm or more and 5 mm or less, and more preferably 1 mm or more and 2 mm or less. For example, the diameter R125 on the side of the translucent structure 115 is 1 mm.

The second masking layer 130 is disposed to overlap the infrared sensor 100. In this example, the thickness of the second masking layer 130 is equal to that of the first masking layer 120. Further, the second masking layer 130 may have a portion thinner than the film thickness of the first masking layer 120, or may be partially overlapped and disposed on the upper surface of the first masking layer 120. For the second masking layer 130, the above-described composition for an infrared transmission film is used.

(1-4. Manufacturing method of cover member)

Next, the manufacturing method of the cover member 110 shown in FIGS. 2 and 3 is demonstrated using FIGS. 4-6.

First, a light-transmitting structure 115 is prepared as shown in FIG. 4. Tempered glass obtained by ion exchange is used for the translucent structure 115. In addition, the light-transmitting structure 115 is not limited to the tempered glass obtained by ion exchange, and other glass materials may be used. For example, as the light-transmitting structure 115, soda-lime glass, borosilicate glass, crown glass, alkali-free glass, and quartz glass may be used.

In addition, a resin material may be used for the translucent structure 115. For example, as a light-transmitting structure, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, cyclic olefin resins, norbornene resins, and polyacrylates , Acrylic resin such as polymethyl methacrylate, urethane resin, vinyl chloride resin, fluorine resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, polyimide resin, polyetherimide resin, polyamide resin , Polyamide-imide resin, or the like may be used.

Further, a crystal material may be used for the light-transmitting structure 115. Examples include birefringent crystals such as quartz, lithium niobate, and sapphire.

Subsequently, as shown in FIG. 5, a first masking layer 120 is formed on the light-transmitting structure 115. An organic resin material containing a black material such as carbon black is used for the first masking layer 120. Moreover, the 1st masking layer 120 is formed so that the said film thickness may be 5 micrometers or more and 50 micrometers or less. Therefore, it is preferable to use a screen printing method capable of forming a thick film to form the first masking layer 120. Thereby, in the wavelength region of 400 nm or more and 700 nm or less, the average value of the transmittance becomes 10% or less.

After the first masking layer 120 is formed, it may be appropriately cured by ultraviolet (UV) irradiation treatment or heat treatment.

Then, an opening 125 is formed. At this time, the opening 125 is formed so that the diameter of the opening 125 is 0.5 mm or more and 5 mm or less. The openings 125 are formed at the same time when the first masking layer 120 is formed by a screen printing method. In addition, the opening 125 may be formed using a photolithography method, an etching method, or the like.

In addition, it is preferable that the end of the first masking layer 120 in which the opening 125 is provided has a tapered shape. By having a tapered shape, it is possible to prevent a gap from occurring when forming the second masking layer.

Next, as shown in FIG. 6, a second masking layer 130 is formed in the opening 125. For the second masking layer 130, the above-described composition for an infrared transmission film is used. It is preferable that the thickness of the second masking layer 130 is about the same as the thickness of the first masking layer 120. In this case, the second masking layer 130 may become a thick film. Therefore, it is preferable that the second masking layer 130 is formed by a screen printing method. By forming by a screen printing method, high productivity is obtained.

Further, the composition for an infrared transmission film described above has high storage stability. Thereby, when forming the second masking layer 130 (infrared ray transmitting film), precipitation of the pigment in the second masking layer 130 is suppressed. Accordingly, the second masking layer 130 may sufficiently absorb visible light and have good infrared transmittance.

In addition, in the present embodiment, the second masking layer 130 may be formed in the opening 125. That is, as in the case of using the evaporation method, it is prevented that the thickness of the entire cover member 110 increases by overlapping the second masking layer 130 on the first masking layer 120. That is, it becomes possible to reduce the height of the cover member.

In addition, it is preferable to appropriately cure the second masking layer 130 by ultraviolet (UV) irradiation treatment or heat treatment. Accordingly, the shape of the second masking layer 130 can be further stabilized. By the above, the cover member 110 is manufactured.

<2nd embodiment>

(2-1. Configuration of photoelectric conversion element 101)

In this embodiment, a photoelectric conversion element used in a face authentication device (face authentication sensor) via infrared rays will be described. 7 is a cross-sectional view of the electronic device 10-1 between A1-A2. The electronic device 10-1 includes a cover member 110, a photoelectric conversion element 101, a package substrate 170, and a housing 180.

As shown in FIG. 7, the photoelectric conversion element 101 includes an optical element such as a lens 140 and a chipped semiconductor element 160 including a transistor.

The lens 140 has a function of focusing light. In the lens 140, a large number of microscopic lenses are arranged in a grid. Therefore, the lens 140 is called a microlens array.

The semiconductor element 160 has a function as a central processing unit (CPU) or a storage device, a function of receiving an optical signal, and a function of converting a received optical signal into an electric signal. In the above, it can be said that the semiconductor device 160 includes a photoelectric conversion device. In the semiconductor element 160, the light receiving unit 150 is arranged in an array shape. In addition, the semiconductor element 160 and the package substrate 170 are connected using a bump electrode or the like containing tin, silver, or the like. Further, a relay substrate may be provided between the semiconductor device 160 and the package substrate 170.

The second masking layer 130 is disposed to overlap the photoelectric conversion element 101.

By using the cover member 110 and the photoelectric conversion element 101 shown in FIG. 7, infrared rays irradiated from a light-emitting element (for example, an infrared lamp, not shown) are reflected from a human face, and a light-transmitting structure 115 And passes through the second masking layer 130. At this time, ambient light including visible light is shielded. The transmitted infrared rays are received by the light receiving unit 150 via the lens 140. The received light is photoelectrically converted by the semiconductor element 160, and an image is recognized. Based on this image, face authentication is performed. In this embodiment, the second masking layer 130 is formed in the opening 125. That is, as in the case of using the vapor deposition method, it is prevented that the overall thickness of the cover member 110 increases by overlapping the second masking layer 130 on the first masking layer 120. That is, it becomes possible to reduce the height of the cover member and further downsize the electronic device.

Further, the present embodiment is not limited to the portable terminal, and may be applied to various electronic devices having an infrared sensor.

Example

Hereinafter, one embodiment of the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples at all. In addition, "part" in a description means "mass part" unless otherwise stated. In addition, the measuring method of each physical property value is as follows.

(3-1. Each condition of infrared transmission film)

In this example, as the dye (A), a dye containing the following compounds was used. For the dye (i), a dye containing compound A1-1 and compound A2-1 was used. For the dye (ii), a dye containing compound A3-1 was used. For the dye (iii), a dye containing compound A4-1 was used. In addition, in some conditions, a dye containing compound A5-1 was used for the dye (iv).

(B-1) cyclopentanone having an SP value of 10.8 or (B-2) dipropylene glycol dimethyl ether having an SP value of 7.9 was used as the solvent (B) of the present example.

In the resin (C) of this example, (C-1) benzyl methacrylate/styrene/N-phenylmaleimide/2-hydroxyethyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid=14/ 10/12/15/29/20 (mass ratio) copolymer, (C-2) styrene/methyl methacrylate/butyl acrylate/2-hydroxyethyl methacrylate/methacrylic acid, t-butylperoxy Copolymer of -2-ethylhexanoate/t-butylperoxybenzoate=150/150/236/58/6/22/3 (mass ratio), (C-3) glycidyl methacrylate/methacryl A copolymer of benzyl acid/styrene=15/15/70 (mass ratio), (C-4) a copolymer of methacrylic acid/glycidyl methacrylate/styrene=10/50/40 (mass ratio), (C- 5) A copolymer of methacrylic acid/glycidyl methacrylate/tricyclo methacrylate[5.2.1.0 ^2,6 ]decane-8-yl and styrene=10/50/40 was used.

In addition, (D-1) silica (manufactured by Nippon Aerosil Co., Ltd., brand name: RX50) or (D-2) calcium carbonate (manufactured by IMERYS, brand name: Carbital 95) of the present Example Used.

In addition, in the (E) polymerizable compound of this example, (E-1) dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku, brand name: KAYARAD DPHA, or (E-2) hexamethylene diisocyanate-based block body ( Asahi Kasei Co., Ltd. make, brand name: TPA-B80E) was used.

(3-2. Evaluation of transmission at 400 to 700 nm in condition 1)

For transmission evaluation of 400 to 700 nm, the composition for an infrared transmission film was applied on a smooth glass plate, dried at 23° C. for 8 hours, and then the coating film was further dried at 50° C. for 3 hours under reduced pressure, and an infrared transmission film having a thickness of 10 μm was formed. Got it. Further, after drying and before heat curing, an exposure machine ("MPA-600FA" manufactured by Canon: an ultra-high pressure mercury lamp was used) was used to expose the entire surface of the coating film without passing through a mask to obtain a curable film.

Subsequently, it measured about the average transmittance of the visible region (400-700 nm) of the obtained film. The average transmittance in the visible region is a value obtained by measuring the transmittance at each point in the range of 400 nm to 700 nm at intervals of 2 nm, and obtaining the average value of the transmittance. When the average transmittance of 400 to 700 nm is 20% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the average transmittance was evaluated according to the following criteria.

A: less than 1%

B: 1% or more and less than 10%

C: 10% or more to less than 20%

D: 20% or more

(3-3. 701 to 800 nm transmission evaluation in condition 1)

Using the above-described evaluation sample, the average transmittance of the near-infrared region (701 to 800 nm) was calculated. The average transmittance in the visible region is a value obtained by measuring the transmittance of each point at intervals of 2 nm in the range of 701 nm to 800 nm, and obtaining the average value of the transmittances. When the average transmittance at an average transmittance of 701 to 800 nm is 60% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the average transmittance was evaluated according to the following criteria.

A: less than 20%

B: 20% or more and less than 30%

C: 30% or more to less than 60%

D: more than 60%

(3-4. Evaluation of transmission at 400 to 700 nm in condition 2)

For evaluation of transmission of 400 to 700 nm, the composition for infrared transmission film is applied on a smooth glass plate, dried at 100° C. for 5 minutes, and then the coating film is further heated and cured at 150° C. for 1 hour under reduced pressure to transmit infrared rays having a thickness of 10 μm. I got the membrane.

Subsequently, it measured about the average transmittance of the visible region (400-700 nm) of the obtained film. The average transmittance in the visible region is a value obtained by measuring the transmittance at each point in the range of 400 nm to 700 nm at intervals of 2 nm, and obtaining an average value of the transmittance. When the average transmittance of 400 to 700 nm is 20% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the average transmittance was evaluated according to the following criteria.

A: less than 1%

B: 1% or more and less than 10%

C: 10% or more to less than 20%

D: 20% or more

(3-5. 701 to 800 nm transmission evaluation in condition 2)

Using the above-described evaluation sample, the average transmittance of the near-infrared region (701 to 800 nm) was calculated. The average transmittance in the visible region is a value obtained by measuring the transmittance of each point at intervals of 2 nm in the range of 701 nm to 800 nm, and obtaining the average value of the transmittances. When the average transmittance at an average transmittance of 701 to 800 nm is 60% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the average transmittance was evaluated according to the following criteria.

A: less than 20%

B: 20% or more and less than 30%

C: 30% or more to less than 60%

D: more than 60%

(3-6. Heat resistance evaluation in condition 1)

Using the above-described evaluation sample, after measuring the average transmittance (average transmittance before heating) of 400 to 700 nm, heated on a hot plate at 180° C. for 30 minutes, and again the average transmittance of 400 to 700 nm (average transmittance after heating) ) Was measured. And the absolute value (heat resistance) of the difference between the average transmittance before heating and the average transmittance after heating was evaluated according to the following criteria.

A: less than 3%

B: 3% or more and less than 5%

C: 5% or more and less than 10%

D: 10% or more and less than 20%

(3-7. Heat resistance evaluation in condition 2)

The composition for an infrared transmission film was applied on a smooth glass plate, dried at 100°C for 5 minutes, and then the coating film was further heated and cured at 150°C for 1 hour under reduced pressure to obtain an infrared transmission film having a thickness of 10 μm. And the absolute value (heat resistance) of the difference between the average transmittance before heating and the average transmittance after heating was evaluated according to the following criteria.

A: less than 3%

B: 3% or more and less than 5%

C: 5% or more and less than 10%

D: 10% or more and less than 20%

(3-8. Evaluation of precipitation over time)

The composition for infrared-transmitting membranes containing a solvent was left in a sealed bottle under the condition of 25°C and 1 atmosphere, and evaluated according to the criteria below the condition of deposition of organic dyes.

A: For 3 months or more, precipitation of the pigment was not observed.

B: During 1 month or more and less than 3 months, precipitation of the pigment was not observed.

C: For 2 weeks or more and less than 1 month, precipitation of the pigment was not observed.

D: In less than 2 weeks, precipitation of the pigment was confirmed.

(3-9. Printing evaluation)

After curing, the mesh wire diameter of the screen plate and the thickness of the screen plate were adjusted so that the film thickness became 10 μm, and the composition for infrared transmission films was screen-printed on a smooth glass plate. The print pattern shape was evaluated based on the following criteria.

A: The edge portion was rectangular and no non-uniformity was observed

B: Disturbance or unevenness in the edge portion was partially confirmed

C: Disturbance or non-uniformity of the edge portion was confirmed at each point

D: Disturbance or non-uniformity of the edge portion was completely confirmed

(3-10. Evaluation result)

As can be seen from the results of Table 1, in each of the conditions of Examples 1 to 15 containing all of (A) a dye (i), a dye (ii) and a dye (iii), (A) a dye (i), a dye Compared to Comparative Examples 1 to 3 having neither (ii) nor dye (iii), good results were obtained in any case of transmission evaluation at 400 to 700 nm and transmission evaluation at 701 to 800 nm. In addition, in each of the conditions of Examples 1 to 15 in which the absolute value of the difference between the SP value of the (A) dye (iii) and the SP value of the solvent (B) becomes 0.1 (cal/cm 3) ^1/2 , precipitation evaluation over time A good result of C or more was obtained.

Further, the infrared transmission film formed of the composition for an infrared transmission film of each example had good results in all of the 400 to 700 nm transmission evaluation, the 701 to 800 nm transmission evaluation, and the elapsed precipitation evaluation. That is, by using one embodiment of the present invention, a composition for an infrared transmission film having high storage stability can be obtained, and an infrared transmission film having a high shielding function against visible light can be formed.

In addition, in the (B) solvent, favorable results were obtained in the precipitation evaluation over time under the condition of containing a large amount of the (B-1) solvent. In particular, in Examples 1 to 15 in which (B-1) the proportion of the solvent is 20% by mass or more relative to the total amount of the (B) solvent, (B-1) precipitation over time compared to Comparative Examples 4 and 5 without a solvent. Good results were obtained in the evaluation. In addition, in addition to obtaining good heat resistance properties, good coating performance was also obtained under the condition of (B-1) having a solvent ratio of 90 mass% or less.

In addition, (C) in most conditions containing resin, good results were obtained in heat resistance evaluation. In particular, by using the resin (C-4) or (C-5), favorable results were obtained also in each evaluation other than the heat resistance evaluation.

In addition, in any condition containing the (D) thickener, good results were obtained in evaluating the printing performance. That is, by using one embodiment of the present invention, it is possible to stabilize the pattern shape of the infrared transmission film when screen printed.

10: electronic device
100: infrared sensor
101: photoelectric conversion element
110: cover member
115: light-transmitting structure
120: masking layer
125: opening
130: masking layer
140: lens
150: light receiving unit
160: semiconductor device
170: package substrate
180: housing
200: camera
300: speaker unit
350: normal
400: housing
500: display panel
600: microphone unit

Claims (14)

A dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, and
A dye having an absorption maximum in a region of 581 nm or more and 700 nm or less in wavelength, and
A dye having an absorption maximum in a region of wavelength 701 nm or more and 800 nm or less,
Contains a solvent,
The solvent contains a solvent having a dissolution parameter of 8 (cal/cm 3) ^1/2 or more and 12 (cal/cm 3) ^1/2 or less. A dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, and
A dye having an absorption maximum in a region of 581 nm or more and 700 nm or less in wavelength, and
A dye having an absorption maximum in a region of wavelength 701 nm or more and 800 nm or less,
Contains a solvent,
The composition for an infrared transmissive membrane, wherein the solvent contains a solvent having an absolute value of a difference in a dissolution parameter of a dye having an absorption maximum in a region of 701 nm or more and 800 nm or less and 2.5 (cal/cm 3) ^1/2 or less. The composition for an infrared transmission film according to claim 1 or 2, further comprising a transparent resin. The composition for an infrared transmission membrane according to claim 3, wherein the transparent resin has a cyclic ether group. The composition for an infrared transmission film according to claim 4, wherein the transparent resin further has an acidic group. The composition for an infrared transmission membrane according to claim 1 or 2, wherein the solvent contains a solvent having a cyclic structure. The composition for an infrared transmission membrane according to claim 6, wherein the solvent having the cyclic structure is contained in an amount of 10% by mass or more when the total amount of the solvent is 100% by mass. The composition for an infrared transmission membrane according to claim 6, wherein the solvent contains at least one solvent selected from cyclic ketones, cyclic ethers, lactones, lactams and aromatic hydrocarbons. The composition for an infrared transmission membrane according to claim 8, wherein the solvent having the cyclic structure is contained in an amount of 10% by mass or more when the total amount of the solvent is 100% by mass. The composition for an infrared transmission film according to claim 1 or 2, further containing a thickener. The composition for an infrared transmission film according to claim 10, wherein the thickener contains at least one selected from silica, talc, calcium carbonate, magnesium carbonate, bentonite, barium sulfate, zinc oxide, alumina and cesium tungsten oxide. The dye according to claim 1 or 2, wherein the dye having the maximum absorption in the region of the wavelength of 701 nm to 800 nm is a phthalocyanine dye, a cyanine dye, a pyrrolopyrrole dye, a naphthalocyanine dye, or a dimonium dye A composition for an infrared transmission film containing at least one dye selected from a dye, an azo dye and a squarylium dye. The dye according to claim 1 or 2, further comprising a dye having an absorption maximum in a region having a second wavelength of 700 nm or more and 800 nm or less, which is different from a dye having an absorption maximum in the region of the wavelength 701 nm or more and 800 nm or less. and,
The dissolution parameter of the dye having an absorption maximum in the region of the second wavelength 700 nm or more and 800 nm or less is smaller than the dissolution parameter of the dye having an absorption maximum in the region of the wavelength 700 nm or more and 800 nm or less. On the light-transmitting structure,
In a wavelength region of 400 nm or more and 700 nm or less, a first masking layer having an average transmittance of 10% or less is formed,
Forming an opening in the first masking layer,
In the opening, a dye having an absorption maximum in a region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a region of 581 nm or more and 700 nm in a wavelength, and a maximum absorption in a region of 701 nm or more and 800 nm or less. A method for producing a cover member, wherein a second masking layer is formed using a composition containing a solvent having a dye and a dissolution parameter of 8 (cal/cm 3) ^1/2 or more and 12 (cal/cm 3) ^1/2 or less.

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