JPWO2019159985A1 - Method for manufacturing composition for infrared transmissive film and cover member - Google Patents

Abstract

The composition for forming an infrared transmissive film has a dye having an absorption maximum in a wavelength region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a wavelength region of 581 nm or more and 700 nm or less, and an absorption maximum in a wavelength region of 701 nm or more and 800 nm or less. It contains a dye having a dye and a solvent, and the solvent contains a solvent having a dissolution parameter of 8 (cal / cm3) 1/2 or more and 12 (cal / cm3) 1/2 or less. The composition for an infrared transmissive film may further contain a transparent resin.

Description

The present invention relates to a composition for an infrared transmissive film and a method for producing a cover member.

In recent years, mobile terminals such as smartphones, tablet-type personal computers, and notebook-type personal computers have become widespread, and it has become possible to perform information communication while looking at the screen in various environments. Further, the mobile terminal is equipped with an electronic device (sometimes called an infrared sensor) having a function of accurately grasping position information using infrared rays and a face recognition function making full use of the functions.

The infrared sensor is arranged near the display area of the mobile terminal. At this time, a black bezel is used for the cover member around the infrared sensor in order to make it difficult for the user to see the infrared sensor. The black bezel is partially provided with an opening to block visible light and provide an optical window for allowing infrared light to pass through. A film that transmits infrared rays (infrared ray transmitting film) is used for the light window portion. Patent Document 1 discloses a structure of an optical window used in an infrared sensor. Further, Patent Document 2 discloses a composition that absorbs and shields light in a part of the wavelength region by using a dye material other than black.

Jitsuto No. 3208984 Japanese Patent No. 6196109

In the case of Patent Document 1, the infrared transmissive film for the optical window is formed by a vapor deposition method. In the case of the thin film deposition method, it is formed by stacking thin films having different refractive indexes many times. However, it is difficult to obtain a sufficient film thickness with the vapor-deposited infrared transmissive film, which may be visible to the user, and it may take a long time to form a thick film.

Further, as shown in Patent Document 2, when a dye is used to absorb and shield light in a specific wavelength region, the type of dye and the content of the dye in the composition are important. However, as the type of dye and the content of the dye in the infrared transmissive film increase, the dye may precipitate during the production of the infrared transmissive film. If the dye is precipitated, it will not be possible to maintain a sufficient shielding function, and storage stability may be impaired.

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

According to one embodiment of the present invention, a dye having an absorption maximum in a wavelength region of 400 nm or more and 580 nm or less, a dye having an absorption maximum in a wavelength region of 581 nm or more and 700 nm or less, and a dye having an absorption maximum in a wavelength region of 701 nm or more and 800 nm or less. Infrared transmission, which comprises a dye having a dye 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. Membrane compositions are provided.

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

The composition for an infrared transmissive film may further contain a transparent resin.

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

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

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

In the composition for an infrared transmissive film, the solvent having a cyclic structure may be contained in an amount of 10% by mass or more when the total amount of the solvent is 100% by mass.

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

The composition for an infrared transmissive film may further contain a thickener.

In the above composition for infrared transmissive 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. Good.

In the composition for an infrared transmissive film, the dyes having an absorption maximum in the wavelength region of 701 nm or more and 800 nm or less are phthalocyanine dyes, cyanine dyes, pyrolopyrrole dyes, naphthalocyanine dyes, diimonium dyes, azo dyes, and the like. And at least one dye selected from squarylium dyes may be contained.

The composition for an infrared transmissive film further contains a dye having an absorption maximum in a region of 701 nm or more and 800 nm or less, which is different from a dye having an absorption maximum in a wavelength region of 701 nm or more and 800 nm or less, and has a second wavelength. The solubility parameter of the dye having the absorption maximum in the region of 701 nm or more and 800 nm or less may be smaller than the dissolution parameter of the dye having the absorption maximum in the region of the wavelength of 701 nm or more and 800 nm or less.

According to one embodiment of the present invention, a first masking layer having an average transmittance of 10% or less is formed on the translucent structure in a wavelength region of 400 nm or more and 700 nm or less, and the first masking is performed. An opening is formed in the layer, and the dye having an absorption maximum in the wavelength region of 400 nm or more and 580 nm, the dye having an absorption maximum in the wavelength 581 nm or more and 700 nm or less, and the absorption maximum in the wavelength region of 701 nm or more and 800 nm or less. A cover for forming a second masking layer using a composition containing a dye having a dye and 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 method of manufacturing a member is provided.

According to one embodiment of the present invention, it is possible to provide a composition for an infrared transmissive film having high storage stability, and to form an infrared transmissive film having a function of sufficiently shielding visible light from an optical window.

It is a top view explaining the electronic device which concerns on one Embodiment of this invention. It is a top view explaining the cover member which concerns on one Embodiment of this invention. It is sectional drawing between A1 and A2 of the electronic device which concerns on one Embodiment of this invention. It is sectional drawing explaining the manufacturing method of the cover member which concerns on one Embodiment of this invention. It is sectional drawing explaining the manufacturing method of the cover member which concerns on one Embodiment of this invention. It is a drawing explaining the manufacturing method of the cover member which concerns on one Embodiment of this invention. It is sectional drawing between A1 and A2 of the electronic device which concerns on one Embodiment of this invention.

Hereinafter, the composition for an infrared transmissive film according to each embodiment of the present invention will be described in detail with reference to the drawings. It should be noted that each of the embodiments shown below is an example of an embodiment of the present invention, and the present invention is not construed as being limited to these embodiments. In the drawings referred to in the present embodiment, the same parts or parts having similar functions are designated by the same reference numerals or similar reference numerals, and the repeated description thereof may be omitted. In addition, the dimensional ratio of the drawing may differ from the actual ratio for convenience of explanation, or a part of the configuration may be omitted from the drawing.

<First Embodiment>
(1-1. Composition of composition for infrared transmissive film)
The composition for an infrared transmissive film has at least one absorption maximum in a wavelength region of 701 nm or more and 800 nm or less. Further, the composition for an infrared transmissive film has at least one absorption maximum in a wavelength region of 400 nm or more and 700 nm or less. As a result, in the infrared transmitting film formed by using the composition for an infrared transmitting film, light in the visible light region (specifically, a region having a wavelength of 400 nm or more and 800 nm or less) is blocked, and infrared rays (specifically, a wavelength of 801 nm) are blocked. Near infrared rays in the region of 1200 nm or less) are transmitted. The composition for an infrared transmissive film of the present embodiment contains a dye and a solvent. It will be described in detail below.

(1-1-1 dye)
A dye is a substance that gives color by absorbing or emitting visible light. The dye may contain either an inorganic compound or an organic compound, or may contain either a dye or a pigment, but it is preferable to use a dye because the solubility is improved. The dye preferably has low absorption to infrared rays.

It is preferable to use two or more dyes having an absorption maximum in the visible light region (wavelength 400 nm or more and 800 nm or less) in combination. By using two or more kinds of dyes, light in the visible light region can be satisfactorily shielded. Examples of the dye used in the present embodiment include a dye having an absorption maximum in the wavelength region of 400 nm or more and 580 nm or less (hereinafter, also referred to as “dye (i)”), and a dye having an absorption maximum in the wavelength region of 581 nm or more and 700 nm or less (hereinafter, also referred to as “dye (i)”). Hereinafter, a dye having an absorption maximum in a region having a wavelength of 701 nm or more and 800 nm or less (hereinafter, also referred to as “dye (iii)”) and the like can be mentioned. When the composition for an infrared transmissive film contains three kinds of dyes (i) to (iii) as dyes, it is possible to more effectively shield the light in the visible light region over the entire visible light region. .. That is, when three kinds of dyes (i) to (iii) are contained as the dye, the visible light shielding performance becomes suitable. Further, the composition for an infrared transmissive film may contain a dye other than the dyes (i) to (iii) as the dye.

In the composition for an infrared transmissive film of the present embodiment, each of the dyes (i) to (iii) when the solid component excluding the solvent (resin, thickener, polymerizable compound, etc. described later) is 100% by mass. The addition amount is preferably 0.01% by mass or more and 4% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, and further preferably 0.1% by mass or more and 1% by mass or less. Further, in the composition for an infrared transmissive film of the present embodiment, the total amount of the dyes (i) to (iii) added is preferably 1% by mass or more and 5% by mass when the solid component excluding the solvent is 100% by mass. Hereinafter, it is more preferably 1.5% by mass or more and 4% by mass or less, and further preferably 1.8% by mass or more and 3.5% by mass or less. In the above description, when the total amount of the dyes (i) to (iii) added is 1% or more, the absorption characteristics of the intended wavelength are improved. Further, by setting the total addition amount of the dyes (i) to (iii) to 5% or less, the solubility is improved and the storage stability is improved.

-Dye (i)-
Examples of the dye (i) include organic dyes such as blue dyes and blue pigments.

Specific examples of the blue dye include xanthene dye, triarylmethane dye, cyanine dye, phthalocyanine dye, anthraquinone dye, tetraazaporphyrin dye, and indigo dye. Of these, cyanine dyes are particularly preferable 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 by a plurality of methine groups between two heterocycles in the molecule as a dye. Specific examples of the cyanine dye include compounds represented by the following chemical formulas (A1) and (A2) (hereinafter, also referred to as "compounds (A1) and (A2)").

In the above chemical formula (A1), Z1 is an alkyl group or a phenyl group having 1 to 12 carbon atoms. Z2 is an alkyl group, a phenyl group or a naphthyl group having 1 to 12 carbon atoms. The one or more hydrogen atoms contained in 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 above chemical formula (A2), Z3 and Z4 are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or phenyl groups. n is an integer of 1-12. X is a counter anion.

As the counter anion represented by X, for example a halide ion, ClO ₄ ^-, OH ^-, organic carboxylic acid anions, organic sulfonic acid anion, a Lewis acid anion, an organic metal complex anions, dyes derived anions, organic sulfonylimide anion , Organic sulfonylmethideate anion and the like.

Examples of the halide ion include Cl ⁻ , Br ⁻ , I ^{− and the} like. Examples of the organic carboxylic acid anion include benzoate ion, alkanoate ion, trihaloalkanoate ion, nicotinate ion and the like. Examples of the organic sulfonic acid anion include benzenesulfonic acid ion, naphthalenesulfonic acid ion, p-toluenesulfonic acid ion, alcansulfonic acid ion and the like. Examples of the Lewis acid anion include tetrafluoroborate ion, hexafluoroantimonate ion, tetrakis (pentafluorophenyl) boron anion and the like.

Specific examples of the compound (A1) include, for example, a compound represented by the following chemical 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 chemical 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. 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 can be mentioned. Among these, C.I. I. Pigment Blue 15: 6, 16, 79 are preferred.

-Dye (ii)-
Examples of the dye (ii) include organic dyes such as yellow and green dyes and yellow and green pigments. Specific examples of the yellow and green dyes include squarylium dyes, triarylmethane dyes, cyanine dyes, and phthalocyanine dyes. Of these, triarylmethane dyes are particularly preferable from the viewpoint of heat resistance.

Examples of the triarylmethane dye include a compound represented by the following chemical formula (A3) (hereinafter, also referred to as “compound (A3)”).

In the above chemical formula (A3), Z5 is independently a hydrogen atom and an alkyl or phenyl group having 1 to 12 carbon atoms. T is an aromatic group or a 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 ion, perchlorate ion, hydroxide ion, organic carboxylic acid anion, organic sulfonic acid anion, Lewis acid anion, organic metal complex anion, dye-derived anion, and organic sulfonyl. Examples thereof include an imidate anion and an organic sulfonylmethideate anion.

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

Regarding the yellow and green pigments, the yellow pigments include C.I. 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. I. Pigment Yellow 129, 138, 139, 150, 185, 231 are preferred. Examples of the green pigment include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like, C.I. I. Pigment Greens 7, 36, 58 and 59 are preferred.

-Dye (iii)-
Examples of the dye (iii) include organic dyes such as red dyes and red pigments. The dye (iii) is, for example, at least one pigment selected from the group consisting of phthalocyanine pigments, cyanine pigments, pyrolopyrrole pigments, naphthalocyanine pigments, diimonium pigments, azo pigments, and squarylium pigments. Contains. More specific examples of the dye (iii) include squarylium dyes and phthalocyanine dyes.

Examples of the squarylium dye include a compound represented by the following chemical formula (A4) (hereinafter, also referred to as “compound (A4)”).

In the above chemical formula (A4), 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. is there. Z6, Z7 and Z8 are independently hydrogen atoms and alkyl or phenyl groups having 1 to 12 carbon atoms. 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 chemical formula (A4-1) (hereinafter, also referred to as “compound (A4-1)”). The maximum absorption wavelength (λmax) of compound (A4-1) is 712 nm.

Examples of the phthalocyanine dye include a compound represented by the following chemical formula (A5) (hereinafter, also referred to as “compound (A5)”).

In the above chemical formula (A5), Z ¹⁰ is 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, Fe and the like. Examples of the metal oxide include VO and TiO.

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

Examples of the red pigment include C.I. 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. I. Pigment Red 166, 177, 242, 254, 264, 269 are preferred.

In the dyes (i) to (iii), the difference in absorption maximum wavelength between the dye (i) and the dye (ii) is preferably 40 nm or more and 200 nm or less. The difference in absorption maximum wavelength between the dye (ii) and the dye (iii) is preferably 80 nm or more and 200 nm or less. By setting the difference between the absorption maximum wavelengths of the dye (i), the dye (ii) and the dye (iii) within the above range, the visible region can be continuously and more effectively shielded from light, and the infrared transmitting film transmits the near infrared region. The rate can be further improved.

(1-1-2 solvent)
As the 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 is appropriately selected and used. can do.

Examples of the solvent include n-propanol, 1,2,5,6-tetrahydrobenzyl alcohol, diethylene glycol ethyl ether, 3-methoxybutanol, triacetin, propylene glycol monomethyl ether, cyclopentanone, γ-butyrolactone, cyclohexanone, and 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, 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, Examples thereof include diethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, toluene, methyl acetate, dipropylene glycol dimethyl ether, xylene, ethylbenzene, isophorone, and telepineol. As the solvent, one kind or a mixture of two or more kinds can be used.

The solvent preferably contains a solvent having a cyclic structure. By using a solvent having a cyclic structure, the solubility and dispersibility of the dye having the absorption maximum in the wavelength region of 701 nm or more and 800 nm or less are improved, and the storage stability is further improved. The solvent having a cyclic structure may be one kind or two or more kinds. The cyclic structure may be a carbon ring or a heterocycle. Further, the cyclic structure may be polycyclic or monocyclic. Further, the cyclic structure may be an aromatic ring or an adipose ring.

The solvent preferably contains, for example, at least one solvent selected from cyclic ketones, cyclic ethers, lactones (γ-butyrolactone, ε-caprolactone, etc.), lactam, and aromatic hydrocarbons (toluene, etc.). Among these, cyclic ketones, lactones and aromatic hydrocarbons are preferable, and cyclic ketones and lactones are more preferable. Such a solvent particularly improves the solubility and dispersibility of the phthalocyanine pigment, the cyanine pigment, the pyrolopyrrole pigment, the naphthalocyanine pigment, the diimonium pigment, and the squarylium pigment preferably used in the present invention. Will be possible.

Examples of the cyclic ketone include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and the like. Among these, cyclopentanone, cyclohexanone and cycloheptanone are preferable, and cyclopentanone and cyclohexanone are more preferable.

Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran and the like.

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

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

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, preferably 10 to 30% by mass. The amount is more preferred. With such an embodiment, a composition for an infrared transmissive film having good dispersibility, stability, and coatability can be obtained.

上記数式（１）において、Ｅｖは蒸発エネルギー、Ｖはモル体積、Δｅ_iは各成分の原子または原子団の蒸発エネルギー、Δｖ_iは各成分の原子または原子団のモル体積を示す。(1-1-3 Dissolution parameter)
Here, the properties of the solvent will be described using a dissolution parameter (hereinafter referred to as SP value). The SP value is R. F. Fedors, Polym. Eng. Sci. , 14, 147 (1974), is a value obtained by the following Fedors equation (1).

In the above formula (1), Ev is the evaporation energy, V is the molar volume, Δe _i is the evaporation energy of the atom or atomic group of each component, and Δv _i is the molar volume of the atom or atomic group 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. It is 11 (cal / cm ³ ) ^1/2 or less. For example, when a cyclic ketone is used as the solvent, the SP value of cyclobutanone is 10.8 (cal / cm ³ ) ^1/2 , and the SP value of cyclopentanone is 10.8 (cal / cm ³ ) ^1/2. The SP value of cyclohexanone is 9.9 (cal / cm ³ ) ^1/2 . By containing a solvent having an SP value within the above range, the plurality of dyes used in the present embodiment can be retained without being precipitated for a long period of time. As a result, a composition for forming an infrared transmissive film having excellent storage characteristics over time can be obtained.

Further, the lower limit of the content of the solvent having the SP value within the above range is preferably 10% by mass or more, more preferably 30% by mass or more, when the whole solvent is 100% by mass. More preferably, it is 50% by mass or more. Further, the upper limit of the content of the solvent having the SP value within the above range is preferably 90% by mass or less, more preferably 80% by mass or less, when the whole solvent is 100% by mass. More preferably, it is 60% by mass or less.

Further, in the solvent of the present 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 /.} It is desirable to contain a solvent of ² or less, more preferably 0.5 (cal / cm ³ ) ^1/2 or less. This is because the dye (iii) plays a role of shielding a wavelength region close to the wavelength region sensed by the sensor, while the dye (iii) may have a property of being difficult to dissolve in a solvent, which improves the sensor sensitivity. This is because it is an organic dye whose precipitation should be particularly suppressed. If the solvent contains a solvent in which the absolute value of the difference in SP value from the dye (iii) is 2.5 (cal / cm ³ ) ^1/2 or less, the affinity between the dye (iii) and the solvent The sex increases. As a result, the dye (iii) can be dissolved in the solvent without precipitating. As a result, a composition for an infrared transmissive film having an excellent shielding function in a wavelength region of 701 nm or more and 800 nm or less and having excellent storage characteristics over time can be obtained.

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

Further, the composition for an infrared transmissive film of the present embodiment is also referred to as 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 “dye (iv)” or a fourth dye. ) May have. As the dye (iv), the same material as the dye (iii) is used. It is desirable 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 an infrared transmissive film may further contain a resin. The resin contains a transparent resin. The weight average molecular weight (Mw) of the resin can be, for example, 3,000 or more and 500,000 or less. As the lower limit of the glass transition temperature (Tg) of the resin so as to ensure the thermal stability and solvent resistance of the infrared transmissive film and to show resistance in the heating manufacturing process of 100 ° C. or higher when applied to display devices and the like. Is preferably 110 ° C., more preferably 120 ° C. The upper limit of Tg is preferably 380 ° C., more preferably 370 ° C., and even more preferably 360 ° C.

Examples of the resin include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, and polysulphon resins. Resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, polysiloxane resin, allyl Examples thereof include ester-based curable resins and silsesquioxane-based ultraviolet curable resins. These resins may be used alone or in admixture of two or more. As the resin, the following resins are preferable.

(Cyclic olefin resin)
The cyclic olefin resin is obtained by hydrogenating a resin obtained from at least one of a monomer represented by the following chemical formula (X0) and a monomer represented by the following chemical formula (Y0), and further adding the resin. The resulting resin is preferred.

In the above chemical formula (X0), R ^{x1 to} R ^x4 are atoms or groups independently 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) Carbide having a substituent containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom or having an unsubstituted carbon number of 1 to 30 Hydrocarbon group (v) substituted or unsubstituted hydrocarbon group (vi) polar group having 1 to 30 carbon atoms (excluding (iv))
(Vi) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by mutual bonding, and R ^{x1 to} R ^{x4 that} are not involved in the bond are independently described in (i) above. Represents an atom or group selected from ~ (vi).
(Viii) R ^x1 to R ^x4 representing a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by mutually bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 , and R ^{x1 to} R ^x4 not involved in the bond. Each independently represents an atom or group selected from (i) to (vi) above, or a monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other. Representing, R ^{x1 to} R ^x4 not involved in the bond each independently represent an atom or group selected from the above (i) to (vi).

In the above chemical formula (Y0), R ^y1 and R ^y2 are each independently represent an atom or a group selected from the above (i) ~ (vi), represents the following (ix), k ^y and p ^y are , Each independently represents 0 or a positive integer.
(Ix) Represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon, or heterocycle formed by bonding R ^y1 and R ^y2 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 chemical formula (1) and a structural unit represented by the following chemical formula (2) is preferable.

In the above chemical formula (1), R ^{1 to} R ⁴ are independently monovalent organic groups having 1 to 12 carbon atoms. a to d are independently integers of 0 to 4.

In the above chemical formula (2), R ^{1 to} R ⁴ and a to d are independently synonymous with R ^{1 to} R ⁴ and a to d in the above chemical formula (1), respectively. Y is a single bond, -SO _2- or -CO-. R ⁷ and R ⁸ are independently halogen atoms, nitro groups, or monovalent organic groups having 1 to 12 carbon atoms. g and h are independently integers from 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 the structural unit represented by the following chemical formula (3) and the structural unit represented by the following chemical formula (4).

In the above chemical formula (3), R ⁵ and R ⁶ are independently monovalent organic groups 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 independently integers from 0 to 4. n is 0 or 1.

In the above chemical formula (4), R ⁷ , R ⁸ , Y, m, g and h are independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the above chemical formula (2). .. ^{R 5, R 6, Z,} n, e , and f are each independently the same meanings as ^{R 5, R 6, Z,} n, e and f of 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 the methods described in, for example, JP-A-2006-199945 and JP-A-2008-163107.

(Fluorene polycarbonate resin)
The fluorene polycarbonate-based resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety. The fluorene polycarbonate-based resin can be synthesized, for example, by the method described in JP-A-2008-163194.

(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 the methods described in, for example, JP-A-2010-285505 and JP-A-2011-197450.

(Fluorinated aromatic polymer resin)
The fluorinated aromatic polymer resin is a repeating unit containing an aromatic ring having at least one fluorine atom and 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. The polymer is not particularly limited as long as it has. The fluorinated aromatic polymer resin can be synthesized by, for example, the method described in JP-A-2008-181121.

((Modified) acrylic resin)
The (modified) acrylic resin is an acrylic resin which is a polymer of one or more kinds of (meth) acrylic acid esters, and a copolymer of (meth) acrylic acid ester and another monomer. Examples thereof include modified acrylic resins. The modified acrylic resin may be a modified acrylic resin obtained by polymerization. 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 a (modified) acrylic resin include a (modified) acrylic resin containing glycidyl (meth) acrylate as a monomer.

(Epoxy resin)
Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, and phenol. -Naftor type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like can be 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 the reaction of a diisocyanate compound and a diol compound. Examples of the diisocyanate compound include aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate. The aliphatic or aliphatic cyclic structure-containing diisocyanate of the above can be used alone or in combination of two or more. Examples of the diol compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, saccharose and methylene. Examples thereof include glycols such as glycol, glycerin and sorbitol.

(Commercial item)
Commercially available resins include, for example, JSR's "ARTON", Nippon Zeon's "Zeonor", Mitsui Chemicals'"APEL", and Polyplastics'"TOPAS". Can be mentioned. Examples of commercially available products of the polyether sulfone-based resin include "Sumika Excel PES" manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include "Neoprim L" manufactured by Mitsubishi Gas Chemical Company. Examples of commercially available polycarbonate-based resins include "Pure Ace" manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate-based resins include "Iupizeta EP-5000" manufactured by Mitsubishi Gas Chemical Company. Examples of commercially available fluorene polyester-based resins include "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available (modified) acrylic resins include "Acriviewer" manufactured by Nippon Shokubai Co., Ltd. and "Marproof G-0250SP" manufactured by NOF Corporation. Examples of commercially available products of silsesquioxane-based UV curable resin include "Silplus" manufactured by Nippon Steel Chemical Co., Ltd.

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

As the cyclic ether group, an oxylan group or an oxetanyl group is preferably mentioned. Since such a group has high polymerizable property, the heat resistance of the obtained infrared transmissive film can be improved. When a resin having a cyclic ether group is used, the resin further has a carboxy group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group, or an acidic group which is a combination thereof, whereby the cyclic ether group is ring-opened. It is preferable because polymerization is promoted and the polymerizable property of the resin can be further improved. Among the above acidic groups, it is more preferable to have an acidic group which is a carboxy group, a sulfo group, a phenolic hydroxyl group, or a combination thereof, and a carboxy group is particularly preferable.

(1-1-5 thickener)
The composition for an infrared transmissive film may further contain a thickener. Thickeners are used to adjust the viscosity of the infrared transmissive film composition. Specifically, the thickener is contained so that the viscosity of the composition for an infrared transmissive film is 0.1 Pa · s or more and 1000 Pa · s or less. Within the above range, it becomes easy to adjust the film thickness and shape of the infrared transmissive film. As the thickener, an inorganic filler or an organic filler is used. The inorganic filler may include 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. The organic filler may include synthetic organic fine particles such as polystyrene, polyacrylonitrile, polymethyl methacrylate, polypropylene, polyethylene and polyvinyl chloride, or natural organic fine particles such as cellulose. It is desirable to use an inorganic filler as the thickener because it has good dispersibility and handleability. By using a thickener, the pattern shape when screen-printed can be stabilized.

(1-1-6 polymerizable compound)
Moreover, the composition for an infrared transmissive film may contain a polymerizable compound. As the polymerizable compound, a photopolymerizable compound or a thermopolymerizable compound can be used, and may be used in combination. Specific examples of the polymerizable compound include vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxy acrylate-based resins, and isocyanate-based resins.

(1-1-7 Additive)
In addition, the composition for forming an infrared transmissive film may contain various additives, if necessary. Examples of the additive include a surfactant, an adhesion accelerator, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, a residue improving agent, a catalyst and the like.

Examples of the surfactant include a fluorine surfactant, a silicone surfactant and the like. The content of the surfactant in the total solid content of the composition for an infrared transmissive film can be, for example, 0.01% by mass or more and 5% by mass or less.

Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl). -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane.

Antioxidants include 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 can be mentioned. The content of the antioxidant in the total solid content of the composition for an infrared transmissive film 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, alkoxybenzophenones and the like.

Examples of the anti-aggregation agent include sodium polyacrylate and the like.

As the catalyst, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, or salts thereof. , Alkoxides or organic compounds can be used. Particularly preferred are compounds such as sodium, titanium, zirconium, tin, for example sodium hydride, titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin. Examples thereof include dimethoxydo and dibutyltin oxide.

(1-2. Configuration of mobile terminal)
The above-mentioned composition for an infrared transmissive film is used as an infrared transmissive film (second masking layer 130 described later) as a cover member of an electronic device (specifically, a mobile terminal such as a smartphone). FIG. 1 is a top view of the 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 adopted for the display panel 500, and the display panel 500 has an input function in addition to the display function. At this time, the infrared sensor 100 is arranged in the vicinity of the display panel 500 of the electronic device 10.

In the present embodiment, a smartphone is exemplified as an electronic device, but the present invention is not limited to this. The electronic device 10 may be a tablet-type personal computer, a notebook-type personal computer, or 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 built under the cover member 110.

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

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

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. Although not shown, a light emitting element (for example, an infrared lamp) may be arranged in the vicinity of the infrared sensor.

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

The infrared sensor 100 is connected to the package substrate 170. The infrared sensor 100 may be provided with a relay board between the infrared sensor 100 and the package board 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 on the outside of the housing 180, but may be provided on the inside of 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. The configuration of the cover member 110 will be described in detail below.

The translucent structure 115 is arranged on the outer surface of the electronic device 10. For the translucent structure 115, a member having translucency is used. For example, tempered glass obtained by ion exchange is used for the translucent structure 115. Tempered glass can be used as a cover glass for smartphones 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. A black material is used for the first masking layer 120. For example, an organic resin material containing carbon black is used for the first masking layer 120. The film thickness of the first masking layer 120 may be appropriately set in the range of 5 μm or more and 50 μm or less.

Further, for the first masking layer 120, pigments such as titanium black pigments, bisbenzofuranone pigments, azomethine pigments, and perylene pigments may be used, or azo dyes 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. The diameter R125 on the translucent structure 115 side of the opening 125 has a visible size. The diameter R125 of the opening 125 on the side of the translucent structure 115 is preferably 0.5 mm or more and 5 mm or less, more preferably 1 mm or more and 2 mm or less. For example, the diameter R125 on the translucent structure 115 side is 1 mm.

The second masking layer 130 is arranged so as to superimpose on the infrared sensor 100. In this example, the film thickness of the second masking layer 130 has the same film thickness as that of the first masking layer 120. 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 with the upper surface of the first masking layer 120. For the second masking layer 130, the above-mentioned composition for an infrared transmissive film is used.

(1-4. Manufacturing method of cover member)
Next, a method of manufacturing the cover member 110 shown in FIGS. 2 and 3 will be described with reference to FIGS. 4 to 6.

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

Further, a resin material may be used for the translucent structure 115. For example, as a translucent structure, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene and ethylene vinyl acetate copolymers, cyclic olefin resins, norbornene resins, polyacrylates and polymethylmethacrylates can be used. Acrylic resin, urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, polyimide resin, polyetherimide resin, polyamide resin, polyamideimide resin and the like may be used.

Further, a crystal material may be used for the translucent structure 115. For example, birefringent crystals such as quartz, lithium niobate, and sapphire can be mentioned.

Next, as shown in FIG. 5, the first masking layer 120 is formed on the translucent structure 115. For the first masking layer 120, an organic resin material containing a black material such as carbon black is used. Further, the first masking layer 120 is formed so that the film thickness is 5 μm or more and 50 μm or less. Therefore, it is desirable to use a screen printing method capable of forming a thick film for forming the first masking layer 120. As a result, the average value of the transmittance becomes 10% or less in the wavelength region of 400 nm or more and 700 nm or less.

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

Next, the 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 opening 125 is formed at the same time when the first masking layer 120 is formed by the screen printing method. Further, the opening 125 may be formed by using a photolithography method, an etching method, or the like.

It is desirable that the end portion of the first masking layer 120 provided with the opening 125 has a tapered shape. By having the tapered shape, it is possible to prevent a gap from being generated when the second masking layer is formed.

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-mentioned composition for an infrared transmissive film is used. It is desirable that the film thickness of the second masking layer 130 is about the same as the film thickness of the first masking layer 120. In this case, the second masking layer 130 may be a thick film. Therefore, it is desirable that the second masking layer 130 is formed by a screen printing method. High productivity can be obtained by forming by the screen printing method.

The above-mentioned composition for an infrared transmissive film has high storage stability. As a result, when the second masking layer 130 (infrared transmitting film) is formed, the dye in the second masking layer 130 is prevented from being precipitated. Therefore, the second masking layer 130 can sufficiently absorb visible light and have good infrared transmittance.

Further, in the case of the present embodiment, the second masking layer 130 can be formed in the opening 125. That is, it is possible to prevent the thickness of the entire cover member 110 from increasing due to the second masking layer 130 overlapping the first masking layer 120, as in the case of using the thin-film deposition method. That is, the height of the cover member can be reduced.

Further, it is desirable that the second masking layer 130 is appropriately cured by ultraviolet (UV) irradiation treatment or heat treatment. Thereby, the shape of the second masking layer 130 can be further stabilized. As described above, the cover member 110 is manufactured.

<Second Embodiment>
(2-1. Configuration of photoelectric conversion element 101)
In this embodiment, a photoelectric conversion element used in a face recognition device (face recognition sensor) via infrared rays will be described. FIG. 7 is a cross-sectional view between A1 and A2 of the electronic device 10-1. 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 minute lenses are arranged in a grid pattern. Therefore, the lens 140 is called a microlens array.

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

The second masking layer 130 is arranged so as to be superimposed on the photoelectric conversion element 101.

By using the cover member 110 and the photoelectric conversion element 101 shown in FIG. 7, infrared rays emitted from a light emitting element (for example, an infrared lamp, not shown) are reflected by a human face, and the translucent structure 115 and the first 2 It passes through the masking layer 130. At this time, ambient light including visible light is blocked. 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 the image is recognized. Face recognition is performed based on this image. In the case of this embodiment, the second masking layer 130 is formed in the opening 125. That is, it is possible to prevent the thickness of the entire cover member 110 from increasing due to the second masking layer 130 overlapping the first masking layer 120, as in the case of using the thin-film deposition method. That is, it is possible to reduce the height of the cover member and further reduce the size of the electronic device.

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

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. In addition, "part" in the description means "mass part" unless otherwise specified. The method for measuring each physical property value is as follows.

(3-1. Conditions for infrared transmissive film)
In this example, as the dye (A), a dye composed of the following compounds was used. As the dye (i), a dye composed of compound A1-1 and compound A2-1 was used. As the dye (ii), a dye composed of compound A3-1 was used. As the dye (iii), a dye composed of compound A4-1 was used. Further, under some conditions, a dye composed of compound A5-1 was used as the dye (iv).

As the solvent (B) of this example, (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. ..

The (C) resin of this example includes (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-2-ethylhexanoate / t-butylper Copolymer of oxybenzoate = 150/150/236/58/6/22/3 (mass ratio), (C-3) glycidyl methacrylate / benzyl methacrylate / styrene = 15/15/70 (mass ratio) Copolymer, (C-4) methacrylic acid / glycidyl methacrylate / styrene = 10/50/40 (mass ratio) copolymer, (C-5) methacrylic acid / glycidyl methacrylate / tricyclo methacrylate [5. 2.1.0 ^2,6 ] A copolymer of decane-8-yl and styrene = 10/50/40 was used.

The (D) thickener of this example includes (D-1) silica (manufactured by Nippon Aerosil Co., Ltd., trade name: RX50) or (D-2) calcium carbonate (manufactured by IMERYS, trade name:). Carbital 95) was used.

Further, the (E) polymerizable compound of this example includes (E-1) dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA, or (E-2) hexamethylene diisocyanate-based block product. (Manufactured by Asahi Kasei Corporation, trade name: TPA-B80E) was used.

(3-2. 400-700 nm transmission evaluation under condition 1)
For evaluation of transmission of 400 to 700 nm, an infrared transmissive film composition was applied onto 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 to obtain a thickness. An infrared transmissive film of 10 μm was obtained. After drying and before heat curing, an exposure machine (“MPA-600FA” manufactured by Canon Inc .: using an ultrahigh pressure mercury lamp) was used to expose the entire surface of the coating film without using a mask to obtain a curable film.

Next, the average transmittance in the visible region (400 to 700 nm) of the obtained film was measured. The average transmittance in the visible region is a value obtained by measuring the transmittance at each point every 2 nm in the range of 400 nm to 700 nm and obtaining the average value of the transmittance. When the average transmittance at 400 to 700 nm is 20% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the above 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 and less than 20% D: 20% or more

(3-3. Evaluation of 701-800 nm transmission under condition 1)
Using the evaluation sample described above, the average transmittance in 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 at each point in the range of 701 nm to 800 nm at intervals of 2 nm and obtaining the average value of those transmittances. When the average transmittance of 701 to 800 nm is 60% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the above 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 and less than 60% D: 60% or more

(3-4. 400-700 nm transmission evaluation under condition 2)
For evaluation of transmission of 400 to 700 nm, the composition for an infrared transmissive film is applied onto a smooth glass plate, dried at 100 ° C. for 5 minutes, and then the coating film is further heat-cured at 150 ° C. under reduced pressure for 1 hour. An infrared transmissive film having a thickness of 10 μm was obtained.

Next, the average transmittance in the visible region (400 to 700 nm) of the obtained film was measured. The average transmittance in the visible region is a value obtained by measuring the transmittance at each point every 2 nm in the range of 400 nm to 700 nm and obtaining the average value of the transmittance. When the average transmittance at 400 to 700 nm is 20% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the above 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 and less than 20% D: 20% or more

(3-5. Evaluation of 701-800 nm transmission under Condition 2)
Using the evaluation sample described above, the average transmittance in 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 at each point in the range of 701 nm to 800 nm at intervals of 2 nm and obtaining the average value of those transmittances. When the average transmittance of 701 to 800 nm is 60% or more, the sensor sensitivity when used as infrared transmittance decreases. Therefore, the above 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 and less than 60% D: 60% or more

(3-6. Evaluation of heat resistance under condition 1)
After measuring the average transmittance at 400 to 700 nm (average transmittance before heating) using the above-mentioned evaluation sample, the mixture is heated at 180 ° C. for 30 minutes on a hot plate and again has an average transmittance at 400 to 700 nm (average after heating). Transmittance) was measured. Then, 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. Evaluation of heat resistance under condition 2)
The composition for an infrared transmissive film is applied onto a smooth glass plate, dried at 100 ° C. for 5 minutes, and then the coating film is further heat-cured at 150 ° C. under reduced pressure for 1 hour to obtain an infrared transmissive film having a thickness of 10 μm. Obtained. Then, 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 an infrared transmissive film containing a solvent was left in a closed bottle at 25 ° C. and 1 atm, and evaluated according to the following criteria.
A: No dye precipitation was confirmed for 3 months or more.
B: No dye precipitation was confirmed for 1 month or more and less than 3 months.
C: No dye precipitation was confirmed for 2 weeks or more and less than 1 month.
D: Dye precipitation was confirmed in less than 2 weeks.

(3-9. Printing evaluation)
The mesh wire diameter of the screen plate and the thickness of the screen plate were adjusted so that the film thickness after curing was 10 μm, and the composition for an infrared transmissive film was screen-printed on a smooth glass plate. The print pattern shape was evaluated according to the following criteria.
A: The edge part is rectangular and no unevenness is confirmed. B: Disturbance or unevenness of the edge part is confirmed in part C: Disturbance or unevenness of the edge part is confirmed in various places D: Disturbance or unevenness of the edge part is confirmed. Fully confirmed

(3-10. Evaluation result)

As can be seen from the results in Table 1, under each of the conditions of Examples 1 to 15 containing all of (A) dye (i), dye (ii), and dye (iii), (A) dye (i), dye. Good results were obtained in both the 400 to 700 nm transmission evaluation and the 701 to 800 nm transmission evaluation as compared with Comparative Examples 1 to 3 having neither (ii) nor the dye (iii). Further, under each condition of Examples 1 to 15, the absolute value of the difference between the SP value of the dye (iii) and the SP value of the solvent (B) is 0.1 (cal / cm ³ ) ^1/2 . Good results of C or higher were obtained in the time-dependent precipitation evaluation.

In addition, the infrared transmissive film formed from the composition for the infrared transmissive film of each example gave good results in all of the 400 to 700 nm permeation evaluation, the 701 to 800 nm permeation evaluation, and the time-dependent precipitation evaluation. That is, by using one embodiment of the present invention, a composition for an infrared transmissive film having high storage stability can be obtained, and an infrared transmissive film having a high shielding function against visible light can be formed.

In addition, good results were obtained in the time-dependent precipitation evaluation under the condition that the solvent (B-1) was contained in a large amount among the solvents (B). In particular, in Examples 1 to 15 in which the ratio of the solvent (B-1) to the total amount of the solvent (B) is 20% by mass or more, Comparative Examples 4 and 5 having no solvent (B-1) In comparison, good results were obtained in the evaluation of precipitation over time. Further, under the condition that the ratio of the solvent (B-1) was 90% by mass or less, good heat resistance characteristics were obtained, and good coating performance was also obtained.

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

In addition, good results were obtained in the printing performance evaluation under any of the conditions containing the (D) thickener. That is, by using one embodiment of the present invention, the pattern shape of the infrared transmissive film when screen-printed can be stabilized.

10 ... Electronic device, 100 ... Infrared sensor, 101 ... Photoelectric conversion element, 110 ... Cover member, 115 ... Translucent structure, 120 ... Masking layer, 125 ... -Opening, 130 ... masking layer, 140 ... lens, 150 ... light receiving part, 160 ... semiconductor element, 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 the region of wavelength 400 nm or more and 580 nm or less,
A dye having an absorption maximum in the wavelength region of 581 nm or more and 700 nm or less,
A dye having an absorption maximum in the wavelength region of 701 nm or more and 800 nm or less,
Containing with solvent,
The solvent is a composition for an infrared transmissive membrane containing 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 the region of wavelength 400 nm or more and 580 nm or less,
A dye having an absorption maximum in the wavelength region of 581 nm or more and 700 nm or less,
A dye having an absorption maximum in the wavelength region of 701 nm or more and 800 nm or less,
Containing with solvent,
The solvent is an infrared transmissive film containing a solvent having an absolute value of 2.5 (cal / cm ³ ) ^1/2 or less of the difference in solubility parameter from a dye having an absorption maximum in a wavelength region of 701 nm or more and 800 nm or less. Composition for. The composition for an infrared transmissive film according to claim 1 or 2, further containing a transparent resin. The composition for an infrared transmissive film according to claim 3, wherein the transparent resin has a cyclic ether group. The composition for an infrared transmissive film according to claim 4, wherein the transparent resin further has an acidic group. The composition for an infrared transmissive film according to claim 1 or 2, wherein the solvent contains a solvent having a cyclic structure. The composition for an infrared transmissive film according to claim 6, wherein the solvent having a 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 transmissive film 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 transmissive film according to claim 8, wherein the solvent having a 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 transmissive film according to claim 1 or 2, further containing a thickener. The infrared transmissive 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. Composition for. The dye having an absorption maximum in the wavelength region of 701 nm or more and 800 nm or less is selected from phthalocyanine dyes, cyanine dyes, pyrolopyrrole dyes, naphthalocyanine dyes, diimonium dyes, azo dyes, and squarylium dyes. The composition for an infrared transmissive film according to claim 1 or 2, which contains at least one dye. Further, it contains a dye having an absorption maximum in a second wavelength region of 700 nm or more and 800 nm or less, which is different from the dye having an absorption maximum in the wavelength range of 701 nm or more and 800 nm or less.
The solubility parameter of the dye having an absorption maximum in the second wavelength region of 700 nm or more and 800 nm or less is smaller than the solubility parameter of the dye having an absorption maximum in the wavelength region of 700 nm or more and 800 nm or less, according to claim 1 or 2. Composition for infrared transmissive membrane. On a translucent structure,
In the 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.
An opening is formed in the first masking layer,
A dye having an absorption maximum in a wavelength region of 400 nm or more and 580 nm, a dye having an absorption maximum in a wavelength region of 581 nm or more and 700 nm or less, a dye having an absorption maximum in a wavelength region of 701 nm or more and 800 nm or less, and a dissolution parameter in the opening. A method for producing a cover member, wherein a second masking layer is formed using a composition containing a solvent having a size of 8 (cal / cm ³ ) ^1/2 or more and 12 (cal / cm ³ ) ^1/2 or less.

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